RCCT-2013 - Abstracts Book

XIX International Conference on Chemical Thermodynamics in
Russia (RCCT-2013) (June 24-28, 2013, Moscow) : Abstracts. –

М.: MITHT Publisher, 2013. – 468 р.
ISBN 978-5-904742-16-4
© MITHT Publisher, 2013

Оrganizing Committee
Chair:
Anatoly I. Rusanov, Academician of RAS, St.-Petersburg
Vice-chairs:
Konstantin S. Gavrichev, D.Sci. (Chem.), Moscow
Alla K. Frolkova, D.Sci. (Tech.), Moscow
Scientific secretaries:
Sergei M. Pestov, D.Sci. (Chem.), Moscow. E-mail: rcct-9@mitht.org
Alexander V. Knyazev, D.Sci. (Chem.), Nizhni Novgorod. E-mail:
knyazevav@gmail.com
Members of the Organizing Committee

Andrey S. Alikhanyan, D.Sci. (Chem.), Moscow
Vladimir I. Belevantsev, D.Sci. (Chem.), Novosibirsk
Vladimir I. Valyashko, D.Sci. (Chem.), Moscow
Alexey I. Victorov, D.Sci. (Chem.), St.-Petersburg
Gennady F. Voronin, D.Sci. (Chem.), Moscow
Valery V. Fomichev, D.Sci. (Chem.), Moscow
Viktor V. Gusarov, Corr.-member of RAS, St.-Petersburg
Vladimir A. Durov, D.Sci. (Chem.), Moscow
Anatoly G. Zakharov, D.Sci. (Chem.), Ivanovo
Oskar I. Koifman, Corr.-member of RAS, Ivanovo
Arkady M. Kolker, D.Sci. (Chem.), Ivanovo
Nikolay T. Kuznetsov, Academician, Moscow
Oleg L. Kuskov, Corr.-member of RAS, Moscow
Valery V. Lunin, Academician, Moscow
Andrey K. Lyashchenko, D.Sci. (Chem.), Moscow
Vladimir A. Mikhaylov, D.Sci. (Chem.), Moscow
Oleg V. Mikhaylov, D.Sci. (Chem.), Kazan
Vladimir M. Novotortsev, Academician, Moscow
Andrey A. Pimerzin, D.Sci. (Chem.), Samara
Leonid A. Serafimov, D.Sci. (Chem.), Moscow
Lev N. Sidorov, D.Sci. (Chem.), Moscow
Natalia A. Smirnova, Corr.-member of RAS, St.-Petersburg
Natalia N. Smirnova, D.Sci. (Chem.), Nizhni Novgorod
Alexander K. Shchekin, D.Sci. (Phys.-math.), St.-Petersburg
Valentina L. Stolyarova, Corr.-member of RAS, St.-Petersburg
Alexander M. Toikka, D.Sci. (Chem.), St.-Petersburg
Yuri D. Tretyakov, Academician, Moscow
Pavel P. Fedorov, D.Sci. (Chem.), Moscow
Yury V. Tsvetkov, Academician, Moscow
Aslan Yu. Tsivadze, Academician, Moscow
Bulat R. Churagulov, Dr.Sci. (Chem.), Moscow
Viktoria D. Yulovskaya, Ph.D. (Chem.), Moscow
Andrey B. Yaroslavtsev, Corr.-member of RAS, Moscow
International Committee:
Prof. Sergey P. Verevkin (Rostock, Germany)
Prof. Gennadiy J. Kabo (Minsk, Belarus)
Prof. Joseph W. Bozzelli (Newark, USA)
Prof. Edward Maginn (Notre Dame, USA)
Dr. Michael Frenkel (Colorado, USA)
Dr. Robert Chirico (Colorado, USA)
Prof. James S. Chickos (Missouri, USA)
Dr. Stefano Vecchio (Roma, Italy)
Prof. Manuel Eduardo Minas da Piedade (Lisbon, Portugal)
Dr. Kvetoslav Ruzicka (Praha, Czech Republic)
Prof. Christoph Schick (Rostock, Germany)
Prof. Gabriele Sadowski (Dortmund, Germany)
Prof. Joan Brennecke (Notre Dame, USA)
Prof. Vahur Oja (Tallinn, Estonia)
Prof. Douglas MacFarlane (Melbourn, Australia)
Prof. Adolf Mikula (Vienna, Austria)
Prof. Luís Paulo N. Rebelo (Lisbona, Potugal)
Prof. Tapani Pakkonen (Joensuu, Finland)
Prof. Li-Xian SUN (Guilin, China)
Prof. Hans-Jörg Mögel (Freiberg, Germany)
Local Organizing Committee:

Valery V. Fomichev, Group leader Anastasiya V. Frolkova
Viktoria D. Yulovskaya Zoya A. Kudryashova
Sergei M. Pestov Sergei A. Kutylev
Olga A. Ahapkina Marina V. Lebedeva
Tatyana N. Dorohova Evgeny Yu. Matveev
Address of organizing committee:

86, Prospect Vernadskogo, Moscow, 119571, Russia
Lomonosov Moscow State University of Fine Chemical Technologies (MITHT),
To: RCCT2013 Organizing committee
Fax: +7 (495) 434-87-11 E-mail: RCCT@mitht.org
Website: http://rcct2013.ru
Contents
Plenary lectures 7
Section 1 23
Section 2 77
Section 3 197
Section 4 337
Section 5 397
Author Index 455
Plenary Lectures
8♦ XIX International Conference on Chemical Thermodynamics in Russia
PECULIAR THERMODYNAMICS OF SUPERCOOLED WATER

Anisimov M.A.
Institute for Physical Science & Technology
and Department of Chemical & Biomolecular Engineering,
University of Maryland, College Park, USA
e-mail: anisimov@umd.edu
Twenty years ago it was suggested that the anomalous properties of supercooled water
may be caused by a critical point that terminates a line of metastable liquid-liquid separation
of lower-density and higher-density water. In this presentation I explain how supercooled
water can unmix. I describe a phenomenological model in which liquid water at low
temperatures is viewed as athermal “solution” of two hydrogen-bond network structures with
different entropies and densities. Alternatively to lattice-gas models, in which fluid phase
separation is driven by energy, the phase transition in the athermal two-state water is driven by
entropy upon increasing the pressure, while the critical temperature is defined by the reaction
equilibrium constant. The order parameter is associated with the entropy, while the ordering
field is a combination of temperature and pressure. The model predicts the location of density
maxima at the locus of a near-constant fraction of the lower-density structure. Another
example of entropy-driven liquid polyamorphism is the transition between the structurally
ordered “Blue Phase III” and disordered liquid in some chiral materials. Thermodynamics of
this transition is remarkably similar to that of the hypothesized liquid-liquid transition in
supercooled water. However, unlike the metastable transition in supercooled water, the
transition between the Blue Phase III and ordinary liquid state is located in the stable region
and is experimentally accessible.
Plenary lectures ♦9
THERMOCHEMISTRY AND BOND DISSOCIATION ENERGIES OF NORMAL

VERSUS BRANCHED ALKANES, EFFECTS OF BRANCHING
Hudzik J.M., Snitsiriwat S., Bozzelli J.W.
Department of Chemistry, Chemical Engineering and Environmental Science
New Jersey Institute of Technology, Newark, NJ 07102
Initial reactions of alkyl hydrocarbons in the combustion environment often involve
radical formation, where the radical can react with O2 which is present at high concentration.
Enthalpies (ΔH°f 298), entropies, heat capacities and carbon - hydrogen bond dissociation
energies (C—H BDEs) are reported for a number of C7 and C8 branched alkane
hydrocarbons. ΔH°f 298 and C—H BDEs are calculated using isodesmic reactions selected for
similar bonding environments on both sides of the reaction. Calculation methods include
B3LYP (using the 6-31G(d,p) and 6-311G(2d,2p) basis sets), CBS-QB3, and G3MP2B3
levels of theory. Structures, moments of inertia, vibrational frequencies, and internal rotor
potentials are calculated at the B3LYP/6-31G(d,p) level for contributions to entropy and heat
capacities. C—H bond energies on carbons adjacent to different branching structures are
found to vary. Well depths and kinetic analysis of isomerization reactions on peroxy radicals
resulting from reactions of oxygen molecule association to the carbon radical on the branched
alkanes are evaluated and compared for several of the systems.
10 ♦ XIX International Conference on Chemical Thermodynamics in Russia
APPLIED THERMODYNAMICS IN CHEMICAL AND BIOCHEMICAL ROUTES

FOR ENERGY PRODUCTION FROM BIOMASS
Сardona C.A., Forero H.A., Restrepo J.B., Jaramillo J.J., Valencia M.J.
Universidad Nacional de Colombia Sede Manizales. Departamento de Ingenieria Quimica,
Manizales-Colombia
e-mail: ccardonaal@unal.edu.co
Most of the processes for obtaining energy from biomass are based on the use of
thermodynamics for understanding and design of the reaction and separation stages. However,
during the conceptual analysis and synthesis of respective flowsheets, the maximum energy
benefit, chemical and phase equilibria restrictions are not usually considered and some times
the net energy really produced could ne negative. Along with this problem the environmental
consequences of the bad thermodynamic analysis could result on increases of pollution and
Gren House Gases emissions.
The above mentioned discussion based on theoretical and experimental results is
presented for 3 raw materials: rice husk, sugarcane bagasse and algae, where the processes for
producing energy includes the main possible reactions (combustion, gasification, pyrolisis,
digestion to biogas, fermentation to fuel alcohols or transesterification to biodiesels). It is
found that in these cases the use of a good thermodynamic analysis can imply new
technological approaches and improvements for energy production of biomass.
Plenary lectures ♦ 11
THERMODYNAMICS AND CHEMICAL INFORMATICS: MARRIAGE MADE

IN HEAVEN FOR THE 21-ST CENTURY
Frenkel M.
Thermodynamics Research Center, Applied Chemicals and Materials Division, National
Institute of Standards and Technology, Boulder, Colorado 80305-3337 USA
e-mail: frenkel@boulder.nist.gov
Enormous growth of the information pertaining to experimental measurements of
thermophysical and thermochemical properties of chemical systems now doubling every 10
years created principal challenges in its validation, critical evaluation, processing,
communication, and “bundling” for the use in ever-growing variety of scientific and
engineering applications.
In order to address these challenges in a comprehensive manner, the concept of the
Global Information Systems in Science and Engineering has been developed and implemented
for the field of Thermodynamics (ThermoGlobe) at the Thermodynamics Research Center of
the U. S. National Institute of Standards and Technology. Global Information Systems in
Science and Engineering can be defined as information systems designed to collect, process,
integrate, evaluate, and communicate the entire “body of knowledge” pertaining to a field and
to support any application requiring this knowledge in an “on-demand” mode with definitive
information quality assessments. The components of this system include software tools for
mass-scale data capture (Guided Data Capture Software), a comprehensive data storage
facility (SOURCE Data Archival System), the NIST/TRC Data Entry Facility, a data
communication standard (ThermoML – IUPAC standard for thermodynamic data
communications), data “reader” software (ThermoML opener into Microsoft Excel), expert
system software (NIST ThermoData Engine), and a Web communication portal (NIST Web-
Oracle data dissemination channel). The role and principle structure of all the components
will be discussed with the emphasis on the profound impact of the ThermoGlobe
implementation on various areas of research and engineering including, but not limited to,
efficiency of information delivery, journal publication quality, chemical process design,
molecular modeling and property prediction, and chemical engineering education.
The capabilities of the NIST ThermoData Engine as well as its Web implementation,
NIST Web ThermoTables (http://www.nist.gov/srd/nistwebsub3.cfm) will be demonstrated.
Technology of the NIST ThermoData Engine is incorporated into online software to aid
the process of experiment planning for property measurements (ThermoPlan,
http://www.nist.gov/srd/nist167.cfm ). This software is extensively used by experimentalists
through open domain free Web access worldwide. NIST Literature Report Builder
(ThermoLit, http://trc.nist.gov/thermolit/main/home.html) provides free and open access to
literature information contained in the NIST SOURCE Data Archival System general purpose
comprehensive relational storage facility for experimental thermophysical and thernochemical
property data. The tool is intended to aid scientists and engineers worldwide involved in
thermophysical property research in determining relevant literature sources for a given
experimental measurement. ThermoPlan and ThermoLit are now integral parts of the article
review process used by five major journals in the field.
TOWARDS THE HYDROGEN ECONOMY  PROGRESS

ON THE ENERGETICS OF WATER SPLITTING
MacFarlane D.R.
Australian Centre for Electromaterials Science,
Monash University, Clayton, Victoria 3800
Efficient production of hydrogen from water would represent a significant step towards
truly sustainable supplies of energy. Ultimately, solar-driven water electrolysis could supply
most of the world’s fuel needs1, while on a more immediate timeframe there is growing
interest in generating hydrogen from non-fossil energy sources. However, water electrolysis is
currently too low in efficiency to be practical, due mainly to energy losses at the water
oxidation electrode. We describe a novel high efficiency catalyst material based on manganese
oxide that is stabilized by a surface phosphorylation reaction in an ionic liquid electro-
deposition process2,3. The catalyst supports high rates of water oxidation and exhibits a light
stimulation effect such that water oxidation rates are higher under illumination. More than 80
hours of continuous water oxidation have been demonstrated.
The product of the water oxidation process over these catalysts is dependent on the
electrolyte and this provides insights into the thermodynamic and kinetic factors involved4. In
normal inorganic salt electrolyte solutions the product is substantially oxidation to oxygen via
a four electron process. On the other hand in a hydrated ionic liquid electrolyte the product
under certain conditions is hydrogen peroxide via a two electron oxidation process. This
appears to offer a uniquely low over potential route to water oxidation.
This talk will discuss these recent developments and their impact on global trends in
artificial photosynthesis.
References
1. Faunce T.; Styring S.; Wasielewski M.R.; Brudvig G.W.; Rutherford A.W.; Messinger
J.; Lee A.F.; Hill C.L.; deGroot H.; Fontecave M.; MacFarlane D.R.; Hankamer B.;
Nocera D.G.; Tiede D.M.; Dau H.; Hillier W.; Wang L.; Amal R.: Artificial
photosynthesis as a frontier technology for energy sustainability. // Energy &
Environmental Science. 2013.
2. Zhou F.L.; Izgorodin A.; Hocking R.K.; Spiccia L.; MacFarlane D.R.: Electrodeposited
MnOx Films from Ionic Liquid for Electrocatalytic Water Oxidation. // Advanced
Energy Materials. 2012, 2, 1013-1021.
3. Zhou F.; Izgorodin A.; Hocking R.K.; Armel V.; Spiccia L.; MacFarlane D.R.
Improvement of Catalytic Water Oxidation on MnOx Films by Heat Treatment. //
Chem. Sus. Chem. 2013, 10.1002/cssc.201200849
4. Izgorodin A.; Izgorodina E.; MacFarlane D.R. Low overpotential water oxidation to
hydrogen peroxide on a MnOx catalyst. // Energy & Environmental Science. 2012, 5,
9496-9501.
THERMODYNAMIC AND TRANSPORT PROPERTIES OF LIQUID PRODUCTS

FROM OIL SHALE PYROLYSIS
Oja V.
Tallinn University of Technology, Tallinn
e-mail: vahur.oja@ttu.ee
World oil shale reserves are estimated to be equivalent to more than 2.9 trillion barrels
of recoverable oil and therefore the oil shale has potential to become a considerably
significant source for high-value oil products and chemicals. Although oil shale resources are
abundant and these are widespread throughout the world, there are only few countries that
presently use oil shale in commercial scale. The main reason for this is that oil shale is a low
grade solid fossil fuel (organic matter ranging typically from 10% to 40%). Oil shales
similarly to coals are solid fossil fuels, however, with organic matter richer in hydrogen and
with significantly higher mineral content.
Commercial ex-situ shale oil production facilities are in operation for example in
Estonia, Barzilia and China. Shale oil is produced via low-temperature pyrolysis up to about
500 oC, known as retorting. The total shale oil, or so called „synthetic crude oil“, from ex-situ
industrial retorts can be classified based on API gravity as „heavy crude oil“, generally with
less than 50% useable as a fuel oil. Depending on the parent oil shale composition the shale
oil can be also specific heteratom rich, for example shale oil from Kukersite oil shale
(Estonia) can contain more than 5% oxygen, from El-lajjun oil shale (Jordan) 8% sulfur, from
Green River oil shale (USA) 2% nitrogen. The actual shale oil characteristics depend on the
retorting technology applied as the chemical compositions and properties may vary
considerably with process conditions.
Publicly available data on thermodynamic and transport properties of oil shale liquid
thermochemical conversion products, from commercial or pilot units, are sparse. Also the
supportive characterization information needed in predictive methods are not systematic from
a property estimation point of view. As a matter a fact, the current information to be found is
likely that from fuel oil material safety data sheets and specifications. Despite this,
thermodynamic and transport properties of shale oils and phase-equilibrium characterization
of shale oil based systems are needed both for oil shale upgrading technologies, including
those involving co-processing of shale oil with fuels from other sources, and handling. There
has been also significant current interest in the general environmental area, particularly with
respect to enviromental regulations.
In this work, we shall discuss relevant characteristics of oxygen rich kukersite oil shale
pyrolysis liquids (compared to petroleum crudes and coal liquids), thermodynamic and
transport properties of interest, and illustrate them with the available information
(experimental data and predictions).
PHYSICO-CHEMICAL BASIS FOR DEVELOPMENT

OF REACTIVE DISTILLATION PROCESSES
Pisarenko Yu.A.
Lomonosov Moscow State University of Fine Chemical Technologies, Moscow
e-mail: pisarenko_yu@mail.ru
Industrial examples of reactive distillation processes show that its competent organization
can reduce energy costs on average about 20-25% and also lead to a simplification of process
flowsheet, which is also accompanied by a reduction of capital costs. This fact determines the
relevance of the modern scientific methods of development technologies, including combined
processes.
One of the most promising areas of the theory of the reactive distillation process is their
analysis of static. The analysis of statics, based on the limited information on the combined
process, allows us to set the stationary states with the maximum yield of the desired product, it
make it possible to evaluate the conditions of their implementation, and to offer method of their
organization.
The analysis of statics is qualitative theory, which is based on a thermodynamic model of
the process - the theoretical stage with chemical interactions. Also in the analysis of statics we are
considering the working modes of the columns, which are characterized by an infinite separation
capability (∞/∞). Key concepts of static analysis: the phase space of the process, pseudoinitial
mixture, manifold of chemical interactions (MChI) and the manifold of chemical equilibrium
(MChE).
In the case of a localized reaction zone of the phase space is a concentration simplex. In
conditions when the process carries out near chemical equilibrium the phase space is MChE.
Availability of singular points of the process, which are mainly pure substances, as well as
conventional azeotropes and chemiazeotropes leads to the division of the phase space into
regions, each of which is filled with a single beam trajectories. To localize these areas is
necessary to formulate the necessary and sufficient conditions for the occurrence chemiazeotropy.
Analysis of the structure of the phase space is the subject of thermodynamic-topological
analysis and allows us to establish the composition and flowrate of flows, on which can be
divided pseudoinitial multicomponent mixture which formed from the feed mixture which enters
the column. The composition of pseudoinitial mixture corresponds to the stoichiometry of
chemical transformation and belongs linear manifold of chemical interactions (MChI), located
within a concentration simplex.
The restrictions of the analysis of statics make it possible to uniquely associate trajectory of
reactive distillation process with the composition of the pseudoinitial mixture. Thus, the
stationary state of the reaction process can be represented in the form of points, located on the
MChI.
In the case of a process with a localized reaction zone the possibility of practical
implementation of each of such selected steady states is decided on the basis of the relative
position of its corresponding test trajectory and manifold of chemical equilibrium - if the part of
test trajectory located in the region of direct reaction then steady state is feasible. For practical
implementation of a steady state in conditions of the process near the chemical equilibrium is
sufficient the presence on the chemical equilibrium surface of test trajectory which will
subtending the material balance line corresponding to steady state that we consider.
The analysis of statics was used in the development of a number of reactive distillation
processes, some of which have been introduced into the industry.
SALTY CHEMISTRY – INTERDISCIPLINARY CASE STUDIES

INVOLVING IONIC LIQUIDS
Rebelo L.P.N.
Instituto de Tecnologia Química e Biológica, UNL, Oeiras, Portugal, www.itqb.unl.pt
A short, recent overview of some aspects of the field will be provided. It will be
followed by some topical issues – among other reports, I will include: (i) making ionic liquids
even more ionic, (ii) turning them to be active pharmaceutical ingredients, and (iii) finding the
most suitable ILs to promote complex crystallization phenomena. Ionic liquids are distinct
from other chemical substances because they may be designed and engineered in such a
fashion that all chemical tools already known to exist in all other chemicals may
simultaneously be present.
Making them more organic-like has been a major task. However, providing ionic liquids with
an even greater ionic (salt-like) character, without losing their liquid status, had not previously
been exploited [1].
Most drugs are solid. Solids often present distinct polymorphic forms and many drugs
are composed of several of these polimorphs; however, oftentimes, only one is medically
effective. Thus, liquid pharmaceuticals are generally superior. Following some pioneering
works (e.g., Robin Rogers, Doug McMarlane, among others) we have used ampicillin as the
anion and several biocompatible cations to develop novel ionic liquids with antibiotic
properties [2].
Analysing protein crystals is a way to determine their structure and infer their function.
However, forming crystals out of proteins is still a complex mix of empiricism and art. Now
ionic liquids have entered into protein chemistry as helpers for their crystallization [3].
Figure 1 – Ionic liquids in the crystallization of proteins. Lysozyme crystal grown from a neat
ionic liquid (IL) solution with the IL cation and anion incorporated in the structure.
References
1. Pereiro A.B., Araújo J.M.M., Esperança J.M.S.S., Marrucho I.M., Rebelo L.P.N. // Chem.
Comm. 2012, 48, 3656–3658; ibid - J. Chem. Thermodyn., 2012, 55, 29–36.
2. Ferraz R., Branco L.C., Marrucho I.M., Araújo J.M.M., Rebelo L.P.N., da Ponte M.N.,
Prudêncio C., Noronha J.P., Petrovski Z. // Med. Chem. Comm. 2012, 3, 494–497.
3. Kowacz M., Mukhopadhyay A., Carvalho A.L.M., Esperança J.M.S.S., Romão M.J.,
Rebelo L.P.N. // Cryst. Eng. Comm., 2012, 14, 4912–4921.
THERMODYNAMICS AND SUPRAMOLECULAR CHEMISTRY

Rusanov А.I.
Saint Petersburg State University, Saint Petersburg
e-mail: rusanov@AR1047.spb.edu
The conceptualization of supramolecular chemistry is ascensive up to the works of D.I.
Mendeleev on the chemical theory of solutions. He wrote: “Every solution should be understood
as a case of a chemical compound complicated by the formation of a variety of chemical
compounds simultaneously”. Their multitude in the modern world is complemented by the
concept of weak chemical bonds characteristic of supramolecules. Hundred years earlier, the
founder of the Russian science M.V. Lomonosov declared quite another point of view. He
considered any attraction between bodies to be impossible and explained the cohesion of
molecules as a result of action of an external medium. This concept, looking as quite hopeless,
acquired a partial rehabilitation only in 20th century when the micellization in surfactant solutions
was discovered. Indeed, direct micelles (typical supramolecular objects) appear even from likely
charged ions, the hydrophobic effect being a driving force of the process. It is of remind that the
hydrophobic (generally, solvophobic) effect is of the entropic nature. At the isothermal condition,
processes move spontaneously down in free energy F, which is related to energy U and entropy S
as F= U − TS where T is temperature. The mutual repulsion of ions leads to an increase of
energy and produces an increasing contribution to free energy, which does not promote the
micellization. However, the entropy of water dramatically increases at the formation of micelles,
and the entropic contribution becomes dominating. As a result, free energy decreases, and
micellization proceeds spontaneously. Thus, one can say that absolutizing the chemical bond (the
basement of supramolecular chemistry) and Lomonosov’s concept are two equally erroneous
extremes. The verity lies in between, and this is to be taken into account in every theory.
Supramolecules occupy an intermediate position between macroscopic phases and
molecules. Ordinary thermodynamics considers only internal energy and neglect external energy
for macroscopic phases and, the reverse, takes into account only external energy for molecules
(the internal energy is usually regarded as constant except for the case of macromolecules). As for
the case of supramolecules, the allowance for both the kinds of energy is equally important. This
is attained by introducing the supramolecular chemical potential
µ{n} = G{0n} + kT ln(c{n}Λ{3n} f{n} ) ,
where G{0n} is the Gibbs energy of a supramolecule of sort {n} with the resting center of mass in a
given medium in the absence of other particles, k is the Boltzmann constant, Λ{n} and f{n} are the
de Broglie wavelength and the activity coefficient of supramolecules, respectively. The
interaction between supramolecules and a medium has been taken into account in quantity G{0n} .
As for the activity coefficient f{n}, it mirrors the interaction between supramolecules. Since
thermodynamics is not related to the nature of chemical or other forces, the approach based on the
supramolecular chemical potential is applicable to any mechanism of formation of
supramolecules. It is shown in this lecture that the thermodynamics in such “supramolecular”
version is equally productive as compared with the traditional phase approach. The dimensions of
supramolecules require the account of both their surface phenomena and their size dependence.
This is illustrated by the size-dependence of solubility of supramolecules.
The work was done under financial support of the program “Leading scientific schools of
Russian Federation” (Grant NS-4464.2012.3).
THERMODYNAMICS OF BIOLOGICAL SYSTEMS

Sadowski G., Held C.
Technische Universität Dortmund
e-mail: gabriele.sadowski@bci.tu-dortmund.de
Biological systems are complex, aqueous systems, which’s properties and even function
depend on a various parameters, such as temperature, concentration and pH. They usually
contain a whole variety of substances, such as amino acids, peptides and proteins, osmolytes,
salts or even polyelectrolytes. Knowing the thermodynamic properties of these systems is
crucial for exploring reaction pathways and designing product-separation steps in down-
stream processing. The properties which are of particular interest are the activity coefficients
of the various components, osmotic coefficients and solubilities.
The talk gives an overview about measurement and modelling of these properties and
demonstrates how they can help to understand e.g. the effect of salts, compatible solutes, or
other additives on the osmotic pressure in cells or the effect of pH on solubility. Moreover it
will be shown that activity coefficients need to be accounted for also when considering
bioreaction equilibria and that they are helpful towards predicting the influence of reaction
conditions on equilibrium concentrations.
THERMODYNAMICAL-TOPOLOGICAL ANALYSIS AS THE BASIS OF RESEARCH

OF CHEMICAL TECHNOLOGY DYNAMIC SYSTEMS
Serafimov L.A.
The concept of «dynamic system» covers as chemical, so and mass-transfer processes in
chemical technology. In flow-through systems, which apply to open systems from the
thermodynamical point of view, the development of the system is aimed to the equilibrium state,
in the first case, to each phase, in the second - to equilibrium between phases. Thermodynamical-
topological analysis (ТТА) allows to study as stationary, so and non-stationary processes. The
analysis is based on the local and non-local topological regularities of certain classes of
dynamical systems in the broadest sense. Actually it is the qualitative research of specific
features of dynamic systems as a discrete, so and differential type. In the basis of ТТА local
regularities lies the concept of singular points and varieties, which are the objects of chemical
and phase equilibrium and correspond to stationary processes. Non-stationary processes are
represented set of trajectories. Together with special points they define the structure of a vector
space of a dynamic system.
The Poincare index of a singular point is used for the study of non-local regularities. Non-
local regularities are determined by a theorem of Poincare - Hopf about the algebraic sum of
singular points, which is equal to the the Euler characteristic.
For today there are two separate forms of the rule of the algebraic sum of singular points.
The first form (proposed V.T. Zharov) has the form:
(1)
The second form, proposed by us, has the form:
(2)
Here N-nodes, C-saddles, top index +, - is a sign of the Poincare index of a singular point,
m is the dimension of the space, corresponding to dynamical system.
The Equation 1 is based on a geometric accordance of the surface of the octahedron
analogues, consisting of triangles. The Equation 2 is based on the formation of diedr from two
concentration simplexes and its mapping on the sphere of the corresponding dimension. The
Equation 2 is more common, it describes the equilibrium chemical varieties, corresponding to
geometric complexes and the boundary conditions, associated with the bifurcation of dynamic
systems. The Equation 1 describes the dynamic systems only in the concentration simplexes.
Both equations for the case of ternary mixtures transferred into the equation YU.V. Guricov. To
present days, the atlases of dynamic systems of the open-equilibrium evaporation of ternary
mixtures with one, two or three azeotropic point on one element of the simplex are formed. The
crystallization dynamic systems for solid-liquid mixtures and for steady solid-solid mixtures are
studied. The dynamic systems of processes taking place in the space of two dimensions, i.e. in
the so-called two-dimensional phases, are studied by A.I. Rusanov and V.T. Zharov. Of
particular interest are the processes in multiphase systems, in which to the addition to vapor
phase, the liquid is represented by a number of phases. Here the atlases for binary and ternary
systems are formed.
The works devoted to the study of dynamic systems, taking place in the mixtures
containing three, four and five components, are made in Lomonosov Moscow State University of
Fine Chemical Technology at present. It should be noted that the number of stationary states, as
a characteristic of the phase portrait, determines the stability of the studying process, its
capabilities and behavior of each component in the processes of separation and chemical
processes.
HYDROGEN STORAGE/PHASE CHANGE MATERIALS

AND THEIR THERMODYNAMIC STUDY
Sun L.X. 1,2*, Xu F.1, Zhou H.Y. 1, Chu H.L.1, Zhang H.Z.1, Zhou Y.J.1, Xiang C.L.1, Qiu S.J 1
1
Key Lab. of Guangxi Information Materials, School of Material Science & Engineering,
Guilin University of Electronic Technology, Guilin, China
2
Materials and Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian, China
*
e-mail: sunlx@guet.edu.cn; xufen@guet.edu.cn
Studies of economic, highly efficient and safe hydrogen storage materials (HSMs) play
an important role in the development of fuel cells in vehicles. The application of phase change
materials (PCMs) for solar thermal-energy storage has received considerable attention in
recent years due to their high storage density.
In recent years, studies on HSMs and PCMs were performed in our lab. The promising
materials for HSMs studied in our laboratory include MHx: M= Mg, La, Ni, etc., alanate,
borohydride and MOF were performed. Furthermore, a series of microencapsulated PCMs
with good performance have been synthesized through in-situ polymerization and their
applications in thermal regulation of gypsum boards are presented. Their thermodynamic
performance were discussed.
References
1. Song L.F., Sun L.X., Xu F., et al., Thermodynamics study of hydrogen storage materials. //
J. Chem. Thermodyn. 2012. 46. 86-93.
2. Zhang J., Sun L.X., Xu F., et al., H2 storage and CO2 capture on a nanoscale metal organic
framework with high thermal stability. // Chem. Commun. 2012. 48. 759–761.
3. Si X.L., Sun L.X., Xu F., et al., High and selective CO2 uptake, H-2 storage and methanol
sensing on the amine-decorated 12-connected MOF CAU-1 // Energy and Environmental
Science. 2011. 4. 4522-4527.
4. Jiang T., Sun L.X., Li W.X. First-principles study of hydrogen absorption on Mg(0001) and
formation of magnesium hydride. // Physical Review B. 2010. 81. 035416.
5. Fan M.Q., Sun L.X., Zhang Y., Xu F., et al., The catalytic effect of additive Nb2O5 on the
reversible hydrogen storage performances of LiBH4-MgH2 composit. //, Int. J. Hydrog.
Energy. 2008. 33. 74-80
6. Song L.F., Jiang C.H., Zhang J., Sun L.X., Xu F., et al., Heat capacities and thermodynamic
properties of a novel mixed-ligands MOFs. // Journal of Thermal Analysis and
Calorimetry. 2010. 100. 679-684.
7. Zhang H.Z., Sun L.X., Xu F., et al., Preparation and thermal performance of gypsum boards
incorporated with microencapsulated phase change materials for thermal regulation. //
Solar Energy Materials And Solar Cells. 2012. 102. 93-102.
Acknowledgements: This work was financially supported by the “973 Project”

(2010CB631303), NSFC (51071146, 21173111, 20903095, 51071081, 51101145 and
51102230), Liaoning BaiQianWan Talents Program (2010921050), IUPAC (Project No.
2008-006-3-100).
SOME FEATURES OF SUB- AND SUPERCRITICAL PHASE BEHAVIOR

IN HYDROTHERMAL SYSTEMS
Valyashko V.M.
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow
e-mail: Valyashko@mail.ru
This presentation is a review of sub- and supercritical phase behavior for binary and ternary
hydrothermal mixtures in a wide range of p-T-x parameters which provides a fundamental basis
for modern SC fluid technologies.
Topological schemes of phase diagram for mixtures of different volatility components are
independent on its nature and similar for organic, inorganic, water-organic and water-salt
systems. Fluid phase diagrams show only fluid (gas, liquid and/or SC fluid) phase behavior, while
complete phase diagrams describe both fluid and solid phase equilibria in a wide range of
temperature and pressure. A special feature of homogeneous SC fluids is a continuous change of
their properties from gas-like to liquid-like with pressure increasing. The region of SC fluid
equilibria exists in all systems at temperature above the critical temperature of the most
nonvolatile salt component. However, starting from the binary mixtures there are two types of
systems, where one type is characterized by only one SC region above the critical temperature of
nonvolatile/salt component, and the another type has two SC regions – one is the same as in the
first type (high-temperature SC region) and the second one (low-temperature SC region) takes
place at much lower temperature, above the critical point (l=g) of the volatile component (water)
but below the triple point (l-g-s) of the salt component. The systematic classification of binary
systems with components of different volatility and some special limitations (such as a
prohibition of formation of binary compounds and some types of immiscibility regions) contains
17 schemes of complete phase diagrams [1], which demonstrates a continuous topological
transformation of one type into another through the special boundary version of phase diagrams,
containing the nonvariant equilibria possible only in the ternary mixtures.
Combination of two binary subsystems with one common volatile component and two
nonvolatile ones gives three classes of ternary systems. While a transition from one binary
subsystem to another, the phase diagrams of the binary subsystems must undergo continuous
topological transformations in the three-component region of composition. Using theoretical
method of the continuous topological transformation and available experimental data, several
regularities and general features of sub- and supercritical phase behavior were established in
ternary mixtures for such transformations as (1) disappearance/appearance of immiscibility
regions of different types, (2) heterogenization of homogeneous SC fluid, (3) transition of
metastable immiscibility equilibria into the stable ones, (4) continuous transition of one
monovariant phase equilibrium into another one without generation of nonvariant equilibrium and
(5) appearance of new versions of nonvariant critical equilibria (tricritical and double critical
points). The mentioned transformations of phase equilibria will be shown as the schemes of
ternary phase diagrams and illustrated by the experimental examples. Particular attention will be
given to the last experimental results concerning a heterogenization of homogeneous SC fluid into
liquid-gas and liquid-liquid equilibria in ternary water-salt mixtures [2-4].
References
1. Valyashko V.M., in “Hydrothermal Properties of Materials”, John Wiley & Sons, Ltd.
2008. P. 1-120.
2. Valyashko V.M. // Fluid Phase Equilib., 2010. 290. 80-87.
3. Urusova M.A., Valyashko V.M. // Russ. J. Inorg. Chem. 2011. 56. 430-441.
4. Urusova M.A., et al, Supercrit. Fluids: Theory & Pract. (Russ.). 2011. 6. 92-113.
VAPORIZATION STUDY OF DIFFERENT CLASSES OF ORGANIC COMPOUNDS

BY THERMOGRAVIMETRY
Vecchio S.
Sapienza University of Rome, Rome, Italy
e-mail: stefano.vecchio@uniroma1.it
The knowledge of parameters like vapor pressure (actually its temperature dependence
in a relatively small temperature region) and vaporization enthalpy of a compound are of
paramount importance in deriving information regarding the strength of molecular interactions
occurring among molecules. In addition, there are various methods reported in literature for
estimating the vapor pressures of materials from their molecular structure [1]. Many of these
procedures have been implemented in computer molecular modeling software extending the
number of pure compounds whose vapor pressure, enthalpies of sublimation and vaporization
data are available in literature [2, 3]. In spite of this, such information for many compounds is
not yet available and the investigator either has to resort to prediction or direct measurement.
Price and Hawkins applied thermogravimetry (TG) for the first time to determine vapor
pressure and vaporization enthalpies measurements from isothermal and non-isothermal TG
data after a suitable correction of the usual procedure [1]. Later, Dollimore developed, and
successfully used a TG procedure based on a reference compound to characterize compounds
of pharmacological interest [2], followed by Pieterse and Focke, who suggested some
corrections to take into account the influence of diffusion on the mass loss rates needed to
determine the lnP vs. 1/T data points [3]. Barontini and Cozzani reported a careful isothermal
TG study, in which corrections due to the contribution of diffusion enabled reliable vapor
pressure data to be determined over solid molecular compounds. Recently, vaporization
enthalpies of acetanilides, simetryn, ametryn, terbutryn, alachor, and other pesticides were
calculated using a TG unit under both non-isothermal and the isothermal conditions [5]. More
recently, Verevkin and co-workers developed a new thermogravimetric method to determine
vaporization enthalpies of extremely low volatile ionic liquids using a commercially available
TG apparatus [6].
Several examples will be presented that will demonstrate the important advantages
offered by TG method in comparison to the well-established "more traditional" methods to
calculate vaporization enthalpies: small amounts of sample (some 30–50 mg), short
experimental times (from some hours until one day), and the commercial availability of the
experimental setup. This method is highly suitable for a rapid screening of the order of
magnitude of vaporization enthalpies, which could be further ascertained by additional
measurements using the traditional techniques, e.g., Knudsen, static or quartz-crystal
microbalance (QCM) methods. However, the thermogravimetric method still needs further
development and more experiences.
References
1. Price D.M., Hawkins M. // Thermochim. Acta. 1998. 315. 19–24.
2. Dollimore D. // Thermochim. Acta. 1999. 340. 19–29.
3. Pieterse N., Focke W.W. // Thermochim. Acta. 2003. 406. 191–198.
4. Barontini F., Cozzani V. // Thermochim. Acta. 2007. 460. 15–21.
5. Vecchio S. // J. Therm. Anal. Calorim. 2006. 84. 271–278.
6. Verevkin S.P., Zaitsau Dz.H., Emel’yanenko V.N., Ralys R.V., Schick C. // Thermochim.
Acta. 2012. 538. 55–62.
MOLECULAR THERMODYNAMICS FOR SOFT SELF-ASSEMBLING SYSTEMS

COTAINING IONIC AMPHIPHILES
Victorov A.I., Smirnova N.A.
Department of Chemistry, St.Petersburg State University, St.Petersburg
E-mail: victorov_a@yahoo.com
Soft self-assembling systems often show surprising structure-property relations and find
growing application in various fields, particularly in medicine, cosmetics and food industry.
Self-organization of amphiphilic molecules on the mesoscale leads to a rich variety of
structures that include singly dispersed aggregates such as micelles, membranes and vesicles
or connected structures such as networks of wormlike micelles or physically entangled
copolymer gels. These soft gentle structures may rearrange profoundly in response to a mild
external stimuli such as changing temperature, salinity or acidity of the environment. The
concomitant change in system’s macroscopic properties may be dramatic. This sensitive
response of many soft mesoscopic materials has been widely exploited in the design of smart
materials, e.g., in drug delivery or in chemical sensors.
For soft mesoscopic systems, there are important questions yet to be answered:
- How the morphology on the mesoscale affects thermodynamic properties?
- How to manipulate self-assembly and design the response?
Chemical engineers need tractable practice-oriented models with a solid molecular
background. Although fast computers and extensive force fields do provide means of
simulating fascinatingly complex structures, they can suggest practical solutions only to a
limited extent. Traditional molecular thermodynamics of bulk phases do not reflect fluid’s
non-uniformity that is very important on the nanoscale. Simplified methods based on the
advances in polymer physics and surface science are rapidly progressing for mesostructured
systems. This work summarizes our efforts to contribute to the development of such
molecular thermodynamic approaches. We report the results of theory, experiment and
computer simulation studies for several classes of soft self-assembling systems, including
polyelectrolyte gels and amphiphilic membranes swelling in selective solvents, micellar
solutions of ionic diblock copolymers, solutions of classical ionic surfactants, ionic liquids
and their mixtures, microemulsions, etc. Among these are systems of a biomedical relevance
and those related to biofuels. Both strongly and weakly charged ionic amphiphiles (e.g., a
diblockcopolymer contining weak polyelectrolyte subchain) are considered. The effects of pH
and salinity on the stability and properties of self-assembled structures have been described.
Spatial networks in solutions of ionic micelles and in solutions of associating polymer chains
have been modeled.
Consideration of nanoscale morphology gives rise to interesting structure-property
relations reflected by relatively simple models. The models predict thermodynamic and
structural characteristics of mesoscopic systems (equilibrium size and stability of different
morphologies, equilibrium swelling, the uptake of salt, elasticity, etc.) in terms of molecular
characteristics and few adjustable parameters. Results of modeling the specific effect of ions
on aggregation are briefly overviewed. Perspectives are given for future work on the
development of molecular thermodynamics for soft self-assembling ionic systems.
The authors thank RFBR (projects 12-03-00977-a, 10-03-00419-а) and Saint-
Petersburg State University (projects 12.37.127.2011, 12.38.76.2012) for financial support.
Section 1
The general issues

of chemical
thermodynamics
THE CONCEPTS ABOUT INITIAL COMPONENTS AND PHASES,

DETAILED COMPONENTS AND CHEMICAL FORMS
TO INTERPRETATION OF COLLIGATIVE SOLUTIONS PROPERTIES
Belevantsev V.I., Ryzhikh A.P.
Nikolaev Institute of Inorganic Chemistry SD RAS,
Novosibirsk, Russia, e-mail: L311@niic.nsc.ru
Together with the fundamental equation [1]:
Σ
k*
k*, (1)
i =1 (µi
*
dG = -SdT + VdP + dni*),
written in terms of initial (independent according to Gibbs [1]) components (ni*, µi*), it was
suggested [2] take up two more equations:
Σ
l
l ≥ k*,
i =1 (µidni),
dG = -SdT + VdP + (2)
Σ
k
Σ j =1 (A dς ),
l -k
l≥ k≥ k*,
i =1 (µidni ) –
’* (3)
dG = -SdT + VdP + j j
written in terms of detailed components (ni, µi) and affinity (Aj) for the set of (l – k)
independent reactions between species inside the phase. The superstructure (2, 3) to (1) and its
utility were repeatedly examined, e.g. [3]. This report amplifies the consequences from (1–3)
with formalization which are directed to the understanding and use of colligative solution
properties. Here we first consecutively present (taking into account all necessary limitations)
the derivation of the equations:
l −1 k *−1
– 〈C*A〉 ∆µ*A = – 〈C*A〉 ∆µA ≅ RT ( ∑ CBi) ≡ RT CΣ = i RT ∑ C*Bj, (4)
i =1 j =1
where i – van’t Hoff factor; A and Bj – notations of stoichiometric formula for initial
components, which are bringed in the concerned solutions during their formation from the
solvent and dissolved matters; Bi – notations of such formula for detailed components and
species corresponding to them. For using (4) the equilibria molar concentrations of detailed
components (CBi) are calculated by the resolution of chemical equilibrium problem [3] on a
basis of data about the solution analytical composition, which are represented in terms of
molar concentrations of initial components (C*A and C*Bj). One schould note, that deduction
of (4) demands to rest upon the matter and correlation of conception on initial and detailed
components, so on the van’t Hoff foundation. The last demands to include in the deduction of
equaition (4) the well-known approach:
µBi (T, P, solvent, CBi) ≅ µ0Bi, C (T, P, solvent) + RT lnCBi, (5)
The proposal additions (4) to the consequences from fundamental equations (1–3) can
raise the quality of the new and available data on any equlibria with species participation. We
also believe that they can become usefull both in the field of secondary medium effects
insignificance and on the outside of the field (of course by introduction of superstructure to
(4)).
References:
[1] The Scientific Papers of J. Willard Gibbs, Vol.1: Thermodynamics. Ox Bow Press,
1981.
[2] V.I. Belevantsev, Russ. J. Phys. Chem. A, 2002, 76, 524–530.
[3] V.I. Belevantsev and A.P. Ryzhikh, Russ. J. Phys. Chem. A, 2011, 85, 745–748.
[4] V.I. Belevantsev, Dokl. Akad. Nauk SSSR, 1991, 320, 1147.
Section 1 — The general issues of chemical thermodynamics ♦ 25
THERMOTOOL – SOFTWARE PACKAGE FOR CALCULATION

OF THERMODYNAMIC PROPERTIES OF SUBSTANCES
Belov G.V.1, Iorish V.S.2
1
Moscow State University, Chemistry Department, Moscow, Russia
e-mail: gbelov@yandex.ru
2
Joint Institute for High Temperatures RAS, Moscow, Russia
Thermodynamic modeling tools are widely used now for theoretical analysis of complex
chemical equilibrium states. One of the most important part of thermodynamic model is
information on thermodynamic properties of individual substances, such as thermodynamic
functions and enthalpy of formation. The models of thermodynamic systems under
investigation contain often hundreds of species, so the database on thermodynamic properties
is an inherent part of the modeling tool. It should be stressed that the results of modeling can
be meaningful only when the model is reasonable and its parameters are reliable and mutually
consistent from thermodynamic laws point of view. It is desirable also to have information on
uncertainties of thermodynamic functions and thermochemical data. Besides, it is often
desirable to know the sources of information in database.
This concept was used for the development software package THERMOTOOL. The
information model has been developed to create the database structure. The database contains
information on molecular constants, energetic and structure properties of particles (atoms,
molecules and ions), thermochemical properties – enthalpy of formation, heat effect of
reaction of dissociation (atomization, ionization), computed values of thermodynamic
functions, information on uncertainties of the data.
The database contains more than 30 tables, values of about 300 parameters are stored in
database. We have used an open source database Firebird (www.ibphoenix.com) for the
development of the package.
The work on the package lasts more than ten years. The current state of the package is
presented.
The work was supported by RFBR, grant 11-03-00499-a.
MODELING OF CU(II) IONS SOLVATION IN ACETONITRILE/WATER SYSTEM:

THE INFLUENCE OF COUNTERIONS
Boldyrev M.I., Shapovalova A.A., Sizov V.V.
St.Petersburg State University, St.Petersburg, Russia
e-mail: Maxquiz@yandex.ru
In the present work the influence of acetonitrile/water mixed solvent composition on the
structure of first solvation shells of ions in Cu(II) salts solutions has been studied. The
GROMACS 4.5 package was used to perform molecular dynamics simulations of 0.76 M and
0.29 M solutions of CuCl2, CuBr2, and Cu(ClO4)2 in acetonitrile/water mixtures containing
20, 40, 60, and 80 mol.% of acetonitrile, as well as in pure water and acetonitrile. The
simulations were carried out under isothermo-isochoric conditions at 298 K. All-atom
molecular models were chosen for the components of simulated systems: a six-site model [1]
for acetonitrile, one-site model [2] for copper ions, and five-site model [3] for perchlorate
anions; the four-site TIP4P/2005 model [4] was used for water.
Radial distribution functions (RDF) were obtained from the simulated trajectories of
particles to describe the distribution of various species around ions. Integration of the first
maxima of RDFs yield the number of particles of all types in the first solvation shells of
cations and anions. As a result, we obtained the dependences of the numbers of water and
acetonitrile molecules, number of counterions, as well as the first-shell total coordination
number of Cu2+ ions on the molar fraction of acetonitrile in the mixed solvent. To set up a
reference system for the analysis of simulation results, the contents of water and acetonitrile in
the solvation shell of cations were estimated for a hypothetical system in which the interaction
energies Cu2+–water and Cu2+–acetonitrile are equal.
The analysis of simulation data has shown that in Cu(ClO4)2 solution the Cu2+ ions are
preferentially solvated by acetonitrile since the calculated fraction of acetonitrile in the first
solvate shell is higher than for the aforementioned hypothetical system. For the CuBr2 solution
an opposite trend is observed: the copper ions are preferentially solvated by water. Thus, the
molecular dynamics simulation results demonstrate the important role of counterions in the
formation of copper ion solvation shells in water/acetonitrile solutions of Cu(II) salts.
References
[1] A.A.Shapovalova, S.V.Burov, V.V.Sizov, E.N.Brodskaya. Determination of
molecular mobility of liquid acetonitrile by molecular dynamics method. Zhurnal Obshchei
Khimii, Vol. 82, p. 1094 (2012).
[2] M.S.Santosh, A.P.Lyubartsev, A.A.Mirzoev, D.K.Bhat. MD Investigation of
Dipeptide-Transition Metal Salts in Aqueous Solutions. J. Phys. Chem., Vol. 114, p. 16632
(2010).
[3] V.V.Sizov, A.A.Shapovalova, S.V.Burov. Molecular dynamics simulations of
solvation and association of ions in water-acetonitrile solutions of lithium perchlorate.
Zhurnal Obshchei Khimii, Vol. 82, p. 1057 (2012).
[4] J.L.F.Abascal, C.Vega. A general purpose model for the condensed phases of water:
TIP4P/2005. J. Chem. Phys., Vol. 123, p. 234505 (2005).
THERMODYNAMIC MODELING OF THE PHASE DIAGRAMS

OF BINARY SYSTEMS OF APATITE
Bulanov E.N., Knyazev A.V., Korokin V.J., Plesovskyh A.S.
N.I. Lobachevsky State University of Nizhni Novgorod,
Nizhni Novgorod, Russia
e-mail: bulanoven@yandex.ru
Three binary systems of apatite, including Pb5(PO4)3F - Pb5(PO4)3Cl (System 1),
Pb5(PO4)3Cl - Pb5(VO4)3Cl (System 2), Ca5(PO4)3Cl - Pb5(PO4)3Cl (System 3), were selected
for the modeling and plotting construction of phase diagrams. During the study the
peculiarities of isomorphism in all three positions of the apatite structure (M, A and L) were
determined. These systems can be the model for the study of geochemical and biochemical
processes.
XRD investigations showed that systems 1 and 2 are characterized by unlimited
miscibility in the solid phase. In the System 3 the formation of individual compound
Ca7Pb3(PO4)6Cl2 was observed, That is why the phase diagram divided into two parts, with
unlimited miscibility (Pb10(PO4)6Cl2-Ca7Pb3(PO4)6Cl2) and limited isomorphism
(Ca7Pb3(PO4)6Cl2-Ca10(PO4)6Cl2) in the solid phase. Phase transition temperatures and
features of structural transformations in them were determined by a combination of methods
of differential scanning calorimetry and high-temperature XRD. In addition, the latter method
allows to calculate the thermal expansion coefficients of all compounds and determine the
effect of the chemical composition of apatite on their values, and the relationship of the
expansion coefficients of solid solutions with the coefficients of the individual compounds.
The standard enthalpy of formation of the compounds, the enthalpy of mixing, and a model
isomorphous miscibility were determined from thermochemical studies using reaction
adiabatic calorimetry. The studied systems were described by the model of regular solid
solutions.
For Pb5(VO4)3Cl the heat capacity was measured in the temperature range 7-370 K.
Standard thermodynamic functions of the compound were calculated from the data obtained.
On the example of Pb5(VO4)3Cl the analysis of synthesis thermodynamics of apatites was
done.
The phase transition temperatures and the standard enthalpy of mixing of all studied
compounds were used for the thermodynamic modeling of the phase diagrams. It’s including
the following steps: 1 - calculation of the Becker curve; 2 - the definition of the functional
dependence of temperature on the composition of the polymorphic transition; 3 - calculation
the solidus and liquidus temperatures, based on the “crystal – liquid”. The modeling was
based on the experimental evidence of the phase boundaries. The values obtained are used to
build the dependence of the Gibbs function of the liquid and the crystal from the composition.
Based on the resulting thermodynamic data the phase diagrams of the studied systems were
constructed plotted. Comparative analysis of the phase diagrams of systems 1 – 3 leads to the
following conclusions. The deviation from the ideality in the systems studied is determined
not only by the ratio of the radii of the ions being replaced, but the equivalence of substitution
sites in the structure.
ASSESSMENT OF THERMODYNAMIC PROPERTIES ON THE BASIS

OF COMPARISON OF THERMODYNAMIC FUNCTIONS
FOR THE PURPOSE OF CALCULATION OF THERMODYNAMIC POTENTIALS
AND PARAMETERS OF PHASE TRANSITIONS
Bychinsky V.A., Mukhetdinova A.V., Chudnenko K.V., Tupitsyn A.A.
Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences,
Irkutsk, Russia
e-mail: val@igc.irk.ru
At the analytical description of thermodynamic functions as basic function it is offered
to use dependence of a heat capacity on temperature. Other thermodynamic functions can be
easily calculated based on known integral dependencies. Karpov equation combined with
approximations of the simplex method of Nelder-Mead describes the dependence of the
temperature with high accuracy, in most cases without the need for partitioning complex
forms depending on several intervals. In case of need such splitting (for example, joining of
polynoms at the Тс = 298,15 K) Karpov's equation allows to provide in knots of joining a
small rupture of function of the heat capacity, not influencing by sight integrated
thermodynamic functions. Low degrees composed Karpov's equations guarantee obtaining the
steady decision and high reproducibility of tabular data. Data of thermodynamic properties of
substance in different phase conditions in separate forms, i.e. the separate description of
polymorphic modifications, a glassy, liquid and gaseous state, allow to describe on the basis
of a minimum of energy of Gibbs both phase transformations of individual substance, and its
condition in difficult systems.
Partite forms of thermodynamic properties of substance in different phase conditions
and search of a minimum of energy of Gibbs demand extrapolation of thermodynamic
functions out of limits of an equilibrium interval of existence. Offered methods of
extrapolation guarantee absence of thermodynamic paradoxes. Found physically and
thermodynamically based correlation can not only choose the numerical value of the
thermodynamic parameters of the recommended or determined experimentally interval, but
also enable reliable evaluation of the thermodynamic properties of unknown substances.
The regression analysis based on an additive assessment with use of correlations of
thermodynamic properties of substances, in combination with the critical analysis of
thermodynamic properties of the substances used as basic properties for an assessment of
isostructural not studied substances, allow, with high degree of reliability to estimate property
of not studied substances, and to coordinate inconsistent data on basic substances.
Comparison of integral thermodynamic functions of individual substances in the proposed
system of representation allows to estimate the temperature and the heat of phase
transformations unexplored substances with reasonable accuracy.
Approaches proposed review and approval of thermodynamic information in relation to
the physical-chemical modeling allows a high degree of confidence to explore the state of the
real systems.
THE FORMING OF MULTIFRACTAL AND COHERENT STRUCTURE AT VAPOR–GAS

CONDENSATION OF TRANSITION METAL CLUSTERS (Ni, Pd, Cu)
IN DEPENDING ON GAS-COOLING TREATMENTS
Chepkasov I.V.1 ,Kurbanova E.D.1, Polukhin V.A.1, Gafner Yu.Ya2
1
Institute of Metallurgy of Ural Division of RAS, Ekaterinburg, Russia
2
Khakassian State University, Abakan, Russia
With an MD simulation realizing the computer analog of real processes we studied the
nucleation and grows of nanoclusters and crystallites and also the thermal evolution (during
steplike heating from 300 to 1500 K at a step of 50 K) of perfect transition-metal nanoclusters
(NiN, CuN and PdN; 561 ≤ N ≤ 2869) having various initial structures (fcc, bcc, Ih). The
temperature-dependent rate of filling of faces with atoms is an important factor that
determines not only the final size but so the regularity, shape and morphology of nanoclusters
(crystallites) in real cluster formation processes on its initial study of condensation and at the
following relaxation heat treatment. So the nanoclusters forming could offered two possible
scenarios depending on the complete or not relaxation processes for concerning nanoclusters
especially with using low-temperature inert gases (taking into account, that kBT < Ea –
activation energy of diffusion processes determined of relaxation rate). Based on the
temperature range under study, the kinetic energy of joined atoms (fragments), and the barrier
spectrum, we determine the growth kinetics, the details of joining, the geometrical laws of
structure formation, and the deviation from the regular configurations of formed clusters for
joining events. The metastable processes of nucleation and growth nanoclusters include such
important stages as agglomeration with conserving the inner structures of gluing parts and
forming mutual incoherent boundary and coalescence with remelting glued parts into the
single sample. Information on all factors affecting the cluster growth and shape is presented
for some substances in the form of well known Nakaya diagrams. The process of shaping can
be efficiently controlled by temperature of cooling inert gases (helium or argon) and using
surfactants, which affect the adsorption kinetics, supersaturation, joining acts, the chemical
activity of aggregation with the formation of spheroid polyhedra, and their coherent (along
joined coordinations) hybridization. As alternative the coherent and regularly bulk structured
nanoparticles were formed realizing the process of coalescence if kBT > Ea that essentially
activated rearrangement of atom positions with changing state of system to one corresponding
to a global thermodynamic minimum. However inside of nanoparticles there was more than
one of energetically and by size equivalent centers of structuring. For example, between two
such centers for whole particle an incoherent interface have been occasionally formed with
following particle dividing along the formed boundary into isolate parts with perfect shell
structures. Practically due to the sharp decreasing of gas cooling temperature and
nonequilibrium and metastability of condensation processes there was an agglomeration as
dominating and so the nanoparticle structure was mostly multifractal deeple one as have been
noted above. Thus it was revealed that nanoscale effects was appeared in clusters during the
relaxation. Moreover in the metallic clusters, as nanoobjects with strong density fluctuations,
the mentioned defects have manifested themselves as structural–isomeric transitions through
the mutual process of continuous process of coordination transformations (i.e., isomerization)
with the simultaneous redistribution of the kinetic and potential energies. However these
thermoscale effects have been noted not only in the temperature dependences of the
characteristics that are controlled during the MD simulation (pressure, internal stress) but also
in anomalous behavior of heat capacity.
The work is supported of Division of Chemical Science of RAS (Project No 12-T-3-
1022).
SOLID SOLUTIONS IN THERMODYNAMIC MODELS

OF NATURAL MINERAL FORMATION
Chudnenko K.V.1, Avchenko O.V.2, Bychinsky V.A.1
1
Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences,
Irkutsk, Russia, e-mail: chud@igc.irk.ru
2
Far East Geological Institute RAS, Vladivostok, Russia, sirenevka@mail.ru
The method of physical and chemical modeling on the basis of approach of the convex
programming, developed in IGC of the Siberian Branch of the Russian Academy of Science
and realized in the universal Selector program complex (PC) [3], possesses new opportunities
for an assessment of external conditions of mineral formation, compared with method of
phase compliance traditionally being applied in mineralogy [2]. PC Selector is a universal
software tool with the implementation of methods for the calculation of heterogeneous fluids
in various conditions, and TR-unit building models with the redistribution of matter - for
various aspects of interaction of a fluid (gas or electrolyte solution) with a particular breed,
transfer, dissolution and redeposition mineral matter in the process. Extremely important role
for the correct solution of these problems by minimizing play mutually model of solid
solutions of minerals.
Each mineral of variable composition is modeled in the "Selector" from of specific
minals for which thermodynamic properties are known. [1] The total energy of Gibbs mineral
Gk, consisting of n minals is expressed as:
n
Gk = ∑ xi (Gi0 + RT ln aiideal + RT ln γ i ) ,
i =1
where Gk - mole Gibbs energy of a mineral consisting of n minals, xi - the number of
minal in the mineral (mole fraction), Gi0 - Gibbs energy of pure minal, a iideal – i-minal activity in
the mineral with ideal mixing, γ i – activity coefficient minal i, RTlnγi - partial excess Gibbs
free energy, reflecting the degree of deviation of the component in an ideal solution from the
real, is calculated mainly on experimental or empirical data. The partial Gibbs free energy
component in an ideal solution RT ln a iideal for monostatic of solid solutions is determined
based on the molecular model of the solution, where the activity of a component in an ideal
solution is equal to its mole fraction: ai = xi. The considerable part of natural minerals has
difficult structure and structure and treats multiposition firm solutions. Thus, if mixture of
atoms in a mineral happens in structural positions more than one type; configuration entropy
can't be exact estimated within molecular model at any choice of formula units.
The multiposition model of firm solution on the basis of the device of a symmetric
formalism served us as basic for calculation of ideal activities of components; models for 19
rock-forming minerals are created.
References
[1] Avchenko O. V., Chudnenko K.V. Aleksandrov I.A. Bases of physical and chemical
modeling of mineral systems. M: Science. – 2009. – 229 p.
[2] Perchuk L.L., Ryabchikov I.D. Phase match in mineral systems. M: "Nedra". – 1976.
– 287 p.
[3] Chudnenko K.V. Thermodynamic modeling in geochemistry: theory, algorithms,
software, appendices. - Novosibirsk: Academic publishing house "Geo", 2010. – 287p.
CLOSURE MODELLING OF ANALYTICAL THERMODYNAMICS

LENNARD-JONES FLUID
Dyakonov G.S., Dyakonov S.G., Kazancev S.A., Klinov A.V., Dinmukhametova R.A.
Kazan National Research Technological University, Kazan, Russia
e-mail: rezdin29@gmail.com
At the 18th International Conference on Chemical Thermodynamics closure of chemical
thermodynamics was considered by some of the authors mentioned. Based on some additional
assumptions about relations between the functionals of repulsion and attraction it was proved
that closure of chemical thermodynamics can be accurately carried out using the virial
theorem and Maxwell relations. Besides, analysis of the virial structure of intermolecular
forces made additional relation between pressure and entropy of system possible. In this
particular research a set of physical models considering statistic and dynamic properties of
virial forces according to the similitude principles of nonlinear dynamics is carried out under
conditions of thermodynamic equilibrium and approximate self-similarity of the
thermodynamic state along the zones of the phase diagram. It is suggested that closure of
chemical thermodynamics should be performed on the basis of coherent zones the boundaries
of which were obtained for the explicit asymptotic solutions based on the seven types of
mathematical models that reflect the specific qualitative features of molecular motion
dynamics in the relevant areas of the phase diagram. Temporary averaging of dynamic
functions is used and theory of Gibbs ensemble is not employed here.
It is proved that closure of chemical thermodynamics is possible with an accuracy of 10-
15% along the whole phase diagram considering information only about pair potential of
intermolecular interaction between molecules.
THERMODYNAMIC MODELLING AND EXPERIMENTAL INVESTIGATION

OF REACTOR GRAPHITE “INCINERATION” IN NONORGANIC SALTS MELTS
Karlina O.K., Ojovan M.I., Klimov V.L., Pavlova G.Yu., Manyukova N.N.
GUP MosNPO “Radon”, Moscow, Russia
e-mail: manyukova@radon.ru
Flameless “incineration” in salt melts (molten salt oxidation) is one of promising
method of irradiated reactor graphite treatment [1].
In the present investigation, performance evaluations of graphite oxidation in salt melts
have been performed using thermodynamic modelling as well as experimentally. As a basis
for salt melts was accepted sodium and potassium carbonates, and as oxidant additives were
used sodium sulphate and potassium chromate.
The software TERRA [2] was used for thermodynamic simulation. It was assumed in
calculations that incineration process occurs at constant pressure in half-closed volume. The
long persistence of the process (the hours) suggests a homogeneous and quasi-equilibrium
spatial distribution of components in both the melt and gas phase over them at each instant of
time. Equilibrium composition of melts and off gases has been calculated under a variety of
graphite content in the source mixtures in the range from 1100 to 1700 K in argon
atmosphere.
According to the calculations, by using sodium sulphate as oxidant additive the melt
consists of Na2CO3, K2CO3, K2SO4 and K2S mainly. Calculation of volume gas phase
composition over the melt shows that carbon dioxide CO2 prevails (90–95 vol.%) in the gas
phase by interaction under 5 mass % graphite with the melt. At greater carbon contents in the
melt carbon oxide CO prevails in the gas phase. Content of all the sulphur-bearing gases
prevails 0.001 vol.% at of only about 7 mass% of graphite content in the melt.
The actinide impurities inherent in reactor graphite interact with salt melt forming
proper chemical compounds.
According to the thermodynamic calculations, potassium chromate offers oxidizing
properties that are analogous to sodium sulphate. The melting temperature of K2CrO4 is
higher by near 100 K than that of K2SO4, decomposition of K2CrO4 with the oxygen release
occurs also by higher temperature, and those both are close to the temperature of carbon active
oxidation. Moreover, decomposition products of K2CrO4 are free from acidic compounds like
those of K2SO4.
After graphite oxidation, the cooled pieces of melts were analyzed by standard XRD
method. The outcomes of experiments and analyses correlated satisfactorily to the
thermodynamic modelling.
References
1. Romenkov A.A., Tuktarov M.A., Menkin L.I., Pyshkin V.P. Flameless burning of
radioactive waste in molten salts // Environmental Safety. – 2006. – No. 3. – P. 44–47.
2. B.G. Trusov // III Intern. Symp. “Combustion and Plasmochemistry”. Almaty:
“Kazak University”, 2005. – P. 52–57.
THERMODYNAMIC SIMULATION OF EXOTHERMIC REACTION PRODUCT

COMPOSITIONS IN THE NONSTOICHIOMETRIC Al–TiO2–C SYSTEM
Klimov V.L., Karlina O.K., Ojovan M.I., Trusov B.G., Manyukova N.N.
Moscow SIA "Radon", Moscow, Russia
e-mail: okarlina@radon.ru
The system Al–TiO2–С is important for the treatment of irradiated reactor graphite
containing biologically-active long-lived radioisotope of 14C [1, 2]. The research of this
system has been extended in this work. Titanium carbide is formed in the Al–TiO2–С system
while using the exothermic reaction [1, 2]
4Al + 3TiO2 +3C = 3TiC + 2Al2O3 (*)
Thermally and chemically stable titanium carbide retains 14C. However investigations
[1, 2] have shown that deviations from stoichiometric composition determined by reaction (*)
in the system Al–TiO2–C can lead to formation of unstable chemical compounds. It is also
possible formation of solid solutions of various compositions. Because of that it has been
suggested to investigate further the system Al–TiO2–C for initial compositions different from
stoichiometric ones.
The computer code TERRA with module TRIANGLE [3, 4] has been used to
thermodynamically model the phase composition of reaction products in the system Al–TiO2–
C. As resulting from modelling experiments a detailed phase diagram has been obtained
which gives the composition of condensed reaction products in the system Al–TiO2–C
accounting for formation of oxycarbide phases and solid solutions.
It has been shown that the main components in the gaseous phase are carbon monoxide
and dioxide, and furthermore the content of carbon dioxide is several orders of magnitude
lower compared with that of carbon oxide. The effect of initial composition impurities on gas
formation has been investigated. Conditions have been determined which minimise the yield
of gaseous phase.
References
1. Klimov V.L., Karlina O.K., Trusov B.G., Manyukova N.N. // XVII Intern. Conf. on
Chem. Thermodyn. in Russia, Kazan, 2009. Abstracts. Vol. 1. – P. 282.
2. Karlina O.K., Klimov V.L., Trusov B.G., Manyukova N.N. // ibid. – P. 393.
3. Trusov B.G. // XVI Intern. Conf. on Chem. Thermodyn. in Russia, Suzdal, 2007.
Abstracts. Vol. II. – P. 451.
4. Trusov B.G., Karlina O.K., Klimov V.L., Manyukova N.N. // Trudy GUP MosNPO
«Radon». Iss. 14. 2008. – P. 16–19.
METHOD OF DETERMINATION OF INTERMOLECULAR INTERACTION

POTENTIAL PARAMETERS BY ZENO LINE
Klinov A.V., Anashkin I.P.
Kazan National Research Technological University, Kazan, Russia
e-mail: anashkin.ivan@gmail.com
The key issue of the use of molecular-statistical methods to determine the
thermodynamic properties is the correct description of the intermolecular interaction. In
practice, used the model potentials, such as Lennard-Jones, Buckingham, etc. In this case the
purpose is to define the parameters of the potential for the real substance.
At the base of proposed method is the using the line Zeno and properties at the critical
point to determine the parameters of the intermolecular interaction potential. The essence of
Zeno line is that the temperature density dependence at compressibility factor equal to unity is
nearly linear. This feature allows us to use any two points on the Zeno line to determine the
parameters.
The advantage of using Zeno line is that the parameters that characterize the depth of
potential well (ε) and molecular size (rm or σ), defined independently of each other, which
reduces the required computational resources. Parameter ε is estimated by comparison of
experimental Boyle temperatures with the calculated values obtained from the second virial
coefficient. Parameter characterizing the size of the molecule is determined by comparing the
experimental and calculated Boyle density.
For single-site model fluids with modified Lennard-Jones potential and Karr-
Konowalow potential [1] obtained an expression relating the values of the potential
parameters with Boyle temperature, Boyle density and critical temperature. These correlations
allow us to define the parameters without additional simulation. It was shown that the
parameters found in this way allow us to describe thermodynamic properties with sufficient
accuracy for the substances, the molecules of which are slightly different from spherical. [2]
For an accurate description of the properties of real substances intermolecular
interaction describing by single site is not enough. The proposed method was tested in the
description of the intermolecular interaction of hydrocarbons by anisitropic united atom model
and the Karr-Konowalow potential. Using estimated parameters allow us to calculate the
properties of the single-phase region [3], and the properties at the coexisting line [4] with high
accuracy.
References
[1] I.G. Kaplan, Introduction to the theory of intermolecular interactions, M.
Science.Physical and mathematical literature main editorial office, 1982. 312 p. (in Russian).
[2] I.P. Anashkin, A.V. Klinov, Herald of Kazan technological university, 8, p. 273-276
(2012) (in Russian).
[3] I.P. Anashkin, A.V. Klinov, G.S. D'yakonov, Herald of Kazan technological
university, 11, p. 18-23 (2010) (in Russian).
[4] I.P. Anashkin, A.V. Klinov, Herald of Kazan technological university, 11, p. 84-85
(2012) (in Russian).
CONTRIBUTION OF THE IRREVERSIBLE PROCESSES

ON THE THERMODYNAMICS OF NANOCOMPOSITES
BASED ON EPOXY RESINS AND CARBON NANOTUBES
Korskanov V.V.1, Karpova I.L.1, Dolgoshey V.B.2, Zhygir О.N.1,3
1
Institute of Macromolecular Chemistry, National Academy of Sciences of Ukraine
e-mail: korskanov_V@mail.ru
2
Kiev’s National University of Construction and Architecture
3
NTUU “Kiev’s Polytechnical University”
The polymer nanocomposites (NC) based on epoxy polymer (EP) and multiwalled
carbon nanotubes (MCNTs) as filler in the temperature interval 253-443 К at a heating rate of
5 K/min were investigated by the method of temperature modulated calorimetry. The weight
content of filler in the polymer matrix w ranged from 0.05% to 1.00%.
The NC, which cured at a temperature of 293 K during 24 h and thermal postcured
materials at a temperature of 473 K during 4 h were investigated.
Contributions were found reversible and irreversible heat capacity (Cp’ and Cp ",
respectively) to the total heat capacity. To further the thermodynamic analysis, the total
enthalpy of formation at each stage NC was calculated as:
T2
∆H =∫ ∂Q = ∫ C p (T )dT ,
T1
T2
∆H =∫ ∂Q =∫ C p ' (T )dT ,
' '
T1
T2
∆H =∫ ∂Q =∫ C p" (T )dT .
" "
T1
Here: ∆H – total enthalpy change, ∆H’ – contribution of reversible processes, ∆H”– the
contribution of irreversible processes.
It is shown that most of the irreversible thermal energy is used for thermal post cure
thermoset systems, resulting in a higher glass transition temperature and the degree of
crosslinking of NC. These effects are accompanied by a narrowing of the temperature range of
the glass transition and to reduce the heat capacity jump at the glass transition.
The process of formation of systems reduces the entropy and Gibbs free energy by
increasing their degree of crosslinking. It was found that the maximum heat loss occurs when
weight contain w = 0,1%.
It was found that the maximum energy of the interaction of EP- MCNTs is reached at
weight contain of the nanofillers w = 0,1%.
THE PREDICTION OF VAPORIZATION ENTHALPY FOR ACYCLIC

OXIGEN COMPOUNDS BY USE QSPR-METHOD
Krasnykh E.L., Portnova S.V.
Samara State Technical University, Samara, Russia
e-mail: kinterm@samgtu.ru
Vapor pressure and vaporization enthalpy are ones of the most important
thermodynamic properties of compounds. Without these data it is impossible to calculate
rectification columns, evaporators and condensers. And the fact that the "great chemistry"
involved an increasing number of new compounds, the preparation of these data is an
important task now. This is especially necessary for acyclic oxygen compounds since their
environment friendly nature, which allow using them for production of various chemicals:
oxygenates, plasticizers, etc.
However, to obtain precision data for vapor pressure and vaporization enthalpy is very
expensive and sometimes impossible operation. Therefore the actual direction for research
now is the development of methods for predicting of vaporization enthalpy at 298K that allow
you to avoid expensive experiment.
In this work the QSPR - method for predicting vaporization enthalpy at normal
conditions for certain classes of organic compounds was proposed. This method is based on
the modified scheme of Randich using connectivity indices from 0 to 3 orders by the equation
n 3 1
χ 2χ 3χ
n
χ = ∑1 / Ln( ∏ δi ) and their subsequent summation 0−3 χ= 0 χ + + +
1 0 2 3 4
The valuesof descriptors ( δ i ) corresponding to the primary, secondary, tertiary and
quaternary carbon atoms were calculated by the least squares method by the training set of
alkanes with different structures (39 compounds) by using linearization of dependence of
experimental vaporization enthalpy on the total index. After optimization following equation
was obtained:
ΔH v ,298 K = 1,6883∗0−3 χ + 2,0781 (r2 = 0,9999) (1)
The correctness of the calculation has been tested on a set of alkanes (65 compounds, r2
= 0,9999; s = 1,1).
The next step was the using of resulting equation to calculate the vaporization enthalpy
for ethers and esters, aldehydes, ketones, acids and alcohols. To do this, descriptors for ether
(-O-), ester (-COO-), aldehyde (-COH), keto group -(C=O), acid group (-COOH) and
hydroxyl group(-OH) were identified like for the carbon atoms of alkanes.
In the calculations was considered that acids and alcohols form hydrogen bonds, but the
mono-carboxylic acids form dimers in the gas and liquid phases, and during the alcohol
evaporation hydrogen bonds are tearing. In this connection, the descriptor (-OH) was
calculated without taking into account the hydrogen bonds, and they was taken as the
individual terms. In the case of esters was showed that they form intermolecular interactions,
which were also included in the scheme.
UNIFORM NONANALYTIC EQUATION OF STATE

AND THERMODYNAMIC TABLES R218
Kudryavtseva I.V., Rykov A.V.
National Research University of Information Technologies, Mechanics and Optics,
St. Petersburg, Russia
e-mail: togg@mail.ru
At drawing up of thermodynamic tables State system for ensuring the uniformity of
measurements of individual substances usually use uniform analytical equations of state
which qualitatively and quantitatively truly feature the regular part of a thermodynamic
surface. However at calculations in a wide neighbourhood of a critical point now use scale
equations of state as uniform analytical equations of state do not satisfy the scale theory
critical phenomenas. In the given operation the uniform not analytical equation of state which
according to requirements of the scale theory features area of strongly developed fluctuations
– a neighbourhood of a critical point is developed for calculation of thermodynamic tables
R218. Instead of a rule of Maxwell (which cannot be used because of a disrupture of
isotherms in two-phase field on a line of pseudo-critical points) the original procedure of the
coordination of values of density and pressure on a line of phase equilibrium, and also
performance of the requirement of equality of chemical potentials on steam and liquid
branches of a line of saturation is used. It is shown that offered uniform not analytical
equations of state it can be recommended for calculation of exact tables of thermodynamic
properties R218 on a line of phase equilibrium from a threefold point (125.45) to critical and
in uniphase field in a gamut of temperatures from 125.45 K to 470 K and pressures from 0.01
to 70 MPa, including a wide neighbourhood of a critical point. Comparison of an equation of
state of the given operation with known equations of state and thermodynamic tables R218 is
with that end in view spent. In particular, it is shown that diversions calculated on an equation
of state of the given operation and the observational values of density in a gamut of
temperatures 130 K ÷ 200 K in the field of a fluid and in a wide neighbourhood of a critical
point lie within 0.05 % and 4 %, accordingly, while the calculations executed on an equation
of state of Lemmon and Span (2006) have shown that these diversions are in limits of 1.5 %
and 35 %, accordingly. In our case on a line of saturation from a threefold point to critical
equality of chemical potentials is carried out with satisfactory accuracy (the peak value
fugacity does not exceed 0.4 %). Values fugacity, calculated on an equation of state [1], in the
field of temperatures more low 160 K start to grow and near to a threefold point reach 40 %,
i.e. is intolerable great values.
As a whole, standard deviation calculated on not analytical equation of state of the given
operation and experimental data have made: on density in uniphase field of 0.32 %; isochoric
heat capacity, including a wide neighbourhood of a critical point of 0.6 %; densities on a
liquid branch of a line of saturation of 0.14 %; densities on a steam branch of a line of
saturation of 0.7 %; "apparent" heat of vaporization, including near-critical region, 0.38 %;
heat capacities of a saturated fluid of 1.1 %; an isobar heat capacity of 2.4 %; velocities of a
sound of 2.2 %.
Reference
[1] Rykov V.A., Ustjuzhanin E.E., Popov P.V., Kudryavtseva I.V., Rykov S.V. R218.
Density, enthalpy, entropy, isobar and isochoric heat capacities, speed of sound in a gamut of
temperatures 160 … 470 K and pressures 0.001 … 70 MPa // State system for ensuring the
uniformity of measurements 211-05. 2005.
EFFECTS ON THERMIC EVOLUTIONS OF CLUSTERS OF TRANSITION

METALS DEPOSITED ON SUBSTRATES (Si-OXIDE, GRAPHENE)
Kurbanova E.D.1, Polukhin V.A.2, Chepkasov I.V.1
1
Institute of Metallurgy of Ural Division of RAS, Ekaterinburg, Russia, e-mail: pvalery@nm.ru
2
Institute of Material Science and Metallurgy of Ural Federal University, Ekaterinburg, Russia
Basing on Voronoy-Delone statistical geometry analysis of MD simulation data concerning
the elementary acts at the structure interfaces forming of transition metal atoms on G (graphene)
and SiO2 substrate planes were carried on. Using the available database of potential version
varieties and the quantum estimations the precision and well parameterized functions were
chosen to fit correctly the interactions in metal cluster surface (111) plane/mono layered graphene
interface of transition metal atoms (TMe: Ni, Cu, Pd) with C atoms of adjoin G or SiO2 layers,
taking into account the strong couplings between the open TMe d-orbitals and G or quartz
orbitals and the following the atomic re-coordination in the interface. The analysis of G-band
structure modifications caused by the electrons of Ni and Pd contacted (111) planes was carried
on so as the specificity of graphene and SiO2 substrate effects on thermodynamic properties,
atomic tangential and radial component diffusion, structure stabilities and thermal profile of 2D-
spacers, as two dimensional systems of regularly deposited metal nanoclusters also their
evolutions under heating were studied.
It was found, that at the heating the primary mechanism of diffusion in PdN, CuN, NiN
nanoclusters (561 ≤ N ≤ 2869), due to the absence of such defects as vacancies and dislocations,
has been initiated by thermal activated tangential displacements in a surface shell with the
appearance of pair structural defects, as vertex atoms rejected to the surface and the formed
vacancies drifted along the upper shell edges and involving other atoms of adjoin grains. It has
been revealed, that in depending on Fermi level closing to the crossing graphene π и π ∗ bands
the quantities of charge transfer between graphene and metal orbitals were determined so as
cohesive energy and binding properties, the tensile strength and geometry of ring-cluster polygons
(“stars”). The simplest of them had Ni or Pd centered hexagonal associated (two-dimensional)
forms with six surrounding carbon atoms.
It was also revealed, that under stabilized effect of G and SiO2 substrates on FCC-
coordinations the limiting temperatures of stability loss of regular morphologies (as the
isomerization and “quasimelting”) and was detected melting-freezing hysteresis of caloric curves
(for isolate and deposited on the graphene or SiO2 substrates) PdN, CuN, NiN clusters. As to the
application also 2D-spacer excellent catalyzers with Fe-amorphous nanoparticles there are some
limitations for their using at choosing of supposed reagents due to the oxidation problems. It
should be noted that the investigation of the effect of a substrate on the electron charge
distribution on a cluster surface (including long range profile of near surface electron density ρ(R)
and kF=2π/λ) and the conditions of appearance of a tunneling current in a system of spaced
(1nm~d=λ/2) 2D spacers requires other quantum statistical methods for estimating electron states.
It is the retained state of charging that results in the drift of the nanoparticles located on a
substrate with respect to each other so that they become equidistant and uniformly distributed in a
hexagonal structure. So basing on statistical geometry analysis the complex classification of
elementary acts of geometry interface configuration re-formings has been carried out and the
specifically different plane configurations, identified as ring-clusters of mutual contacted metallic
polyhedral facets and monolayer hexagonal graphene planes. So basing on the well parameterized
potential functions the MD simulation has been delivered and important for optic-electronic and
2D-spacer catalyze applications information about a new band structure rehybridization forming
and atomic nanostructuring in transition metals/graphene interface of functional heterostructure
layers has been obtained.
The work is supported Division of Chemical Science of RAS (Project No 12-T-3-1022).
INVESTIGATION OF THERMOCHEMICAL PROPERTIES OF THE

PHOSHORYL-SUBSTITUTED SALICYLAMINE COMPLEXES OF Li, Sc AND Zn
Lazarev N.M., Petrov B.I., Abakumov G.А., Balashova T.V.
G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences,
Nizhny Novgorod, Russia
e-mail: nikolai-lazarev@mail.ru
Known coordination compounds of metals having the electroluminescent properties
contain O, O-, O, N-, N, N-chelating ligands. Such complexes are one of the most promising
classes for making organic electroluminescent diodes (OLED). These compounds are part of
the OLED - devices as thin nanoscale films that are often produced by the method of vapor
deposition (MO CVD).
The aim of this study was investigation of the thermochemical properties and vapor
phase composition of L, L*, Zn(L)2Phen and LiL* (2-[[3-[(diphenylphosphoryl)methyl]
phenyl]imino]methyl]phenol (L) and 2-[[3-[(diphenylphosphoryl)methyl]phenyl]imino]
phenol (L *)).
These complexes of Li, Sc and Zn were first synthesized in our Institute. The
composition and structure of the complexes was confirmed by elemental analysis, IR -
spectroscopy, as well as X-ray diffraction study was carried out. The composition of the vapor
phase was investigated by mass spectrometry.
The vapor pressure of these complexes studied by the Knudsen effusion method in the
temperature range 125-251°C and the thermodynamic parameters of the processes of
vaporization determined:
Compound ∆Т, °С lg [p, mm Hg] = A – B/T ∆Hs (Т), ∆Ss(Т),
А В х 10-3 кДж/моль Дж/(моль·К)
L 170-205 13.53±0,61 6.93±0,43 132.7±2,0 203.8±3,1
Zn(L)2Phen 125-138 29.79±0,82 12.73±0,51 243.8±3,4 515.0±5,6
L* 181-215 16.67±0.71 8.41±0.41 160.9±2.1 263.9±3.8
LiL* 211 - 251 10.59±0.89 6.29±0.45 120.41±3.6 147.57±4.5
These is no other process in the investigated temperature interval, but the process of
vaporization. Moreover, according to mass-spectrometry data there is no aggregation of
molecules following the vaporization of compounds. Consequently, the calculation of vapor
pressure was performed for the process of sublimation to monomeric vapour.
ENERGETIC SCHEMES OF FORWARD AND BACKWARD AND EXCHANGE

FAVORSKY REACTION
Litvinenko G.S., Iskakova T.K., Praliyev K.D.
JSC «Institute of Chemical Sciences by name of A.B.Bekturov», Almaty
e-mail: tynyshtyk53@mail.ru
Favorsky reaction is an interaction of carbonyl compounds with acetylene and its mono-
substituted derivatives in the presence of KOH powder. It is exothermal and at low
temperature the reaction with unhindered ketones proceeds to completion. According to the
Le Chatelier’s Principle the reaction rate decreases with the temperature increase.
Performed Researches have allowed illustrating energy schemes of occurring processes:
_
HN C CR
_ H3C
R1 (+) ( ) O
C O_ HN
R2 H3C
C CR e
E0 q
e ax _ O
E q
n En C CR
ax
E0
En Eo HN
R1 40% 22% H3C C CR
R1 HN + HC CR
OH H3C
C O + HC CR C 78% OH
R2 O 60%
R2 C CR
HN
Scheme 1b H3C OH
Scheme 1а C CR
HN
_ O
H3C C CR HN _
H3C C CR
e
e ax E0 q O
E q
n En ax
E0
93% HN
HN 25% C CR
+ HC CR
O 75% CH3 OH
CH3
7% HN
OH
Scheme 1c H3C C CR
Energy schemes of forward and exchange Favorsky reactions, where

Еneq, Еnax, Е0eq, Е0ax– activation energies of synthesis and exchange (isomerisation) of
equatorial and axial acetylene alcohols
Energy scheme 1а corresponds to the simplest case, when process is not complicated by
the formation of isomers of acetylene alcohols. Schemes 1b and 1c are in agreement to more
complex cases, when acetylene alcohols are formed as spatial isomers, herewith scheme 1b
corresponds to the case of ketones with unhindered carbonyl group (α-axial and α-equatorial
β-equatorial and γ-axial and γ-equatorial substituted six-membered carbo- and heterocyclic
ketones), and scheme 1c illustrates the case of ketones with hindered carbonyl group (β-
axially substituted cyclic ketones).
It is shown, that at low temperature (below 20°С) extremely forward Favorsky reaction
proceeds and stereochemistry of the acetylene alcohols synthesis is determined only by kinetic
factors. At 40−80°C fast exchange reaction (isomerisation) proceeds and after 0.5−2 hours the
equilibrium, which corresponds to thermodynamical control of the reaction, establishes. At
intermediate temperature (∼20°С) fast forward reaction and slow isomerisation proceed, that
is why in this temperature range steric result of the reaction may reflect combined action of
both kinetic and thermodynamic factors. However, in all circumstances the question which
factors determine stereochemical result of the reaction (isomers ratio) can be definitely solved
by means of analytical control of the reaction pathway.
METHOD OF CALCULATION FOR TEMPERATURE DEPENDENCE OF VISCOSITY

AND DENSITY OF FLUID THROUGH THE DENSITY DISTRIBUTION OF CLUSTERS
Malyshev V.P., Turdukozhaeva A.M., Kazhikenova A.Sh.
Chemical and Metallurgical Institute, Karaganda, Kazakhstan
e-mail: eia_hmi@mail.ru
Previously, the authors have developed a cluster and associate models of dynamic (η,
Па⋅с), kinematic (ν, м2/с) viscosity and density (ρ, кг/м3), based on the Boltzmann’s
distribution and uniform in shape [1]
η = η1 (Т1 Т )а=а (Т
2 2 Т )b
, or η = η1 (Т 1 Т )
а 2 (Т 2 Т ) b
, (1)
ρ = ρ 1 (T1 T )a 2 (T2 T )b
, (2)
ν = ρν = ν 1 (T1 T )a (T T )
b
2 2
(3)
using reference points η1, ρ1, ν1, Т1; η2, ρ2, ν2, Т2; η3, ρ3, ν3, Т3.
In the identification of dependencies (1)-(3) by the reference value has been established
that the exponent а = f(T) has the meaning of the degree of association of clusters is equal to
the average number in the associate in the whole temperature range.
This was confirmed in the determination of the activation energy of viscous from the
equation Frenkel flow in the coordinates lnη−1/T resulting in the activation energy divided by
the degree of association, was in all cases within the energy of the Van der Waals attraction,
which corresponds to a similar value between clusters found by the method of molecular
dynamics. In turn, the indicator a itself the temperature rises but slowly, but naturally falls in
line with a decrease in the number of clusters in the associate by accelerating their
decomposition when heated melt.
The concept of randomized particle viscous flow is considered as the destruction of the
associates by overcoming the forces of Van der Waals attraction between clusters, which in
principle does not contradict the existing ideas of how to overcome the viscous flow of the
same forces of internal friction, but not limited to compliance stratified laminar fluid flow.
In order to harmonize the three most-studied characteristics of the melt can be a
combination of the two expressions for the temperature dependence of the third, preferably for
the kinematic viscosity through density of a dynamic.
The accuracy of the proposed semi-empirical models viscosity based on their adequate
extrapolation to the region of the critical temperature, and despite the limited number of
points used exceeds the known approximating dependence, requiring for their construction of
a much larger number of points, not less than the number of members in the approximating
polynomial.
The proposed cluster and associate model dynamic, kinematic viscosity and density
allowed to summarize disparate experimental data and calculated according to the
identification of false positives for a number of substances and found to be suitable for a
holistic description of the temperature dependence of the viscosity of the full range of the
liquid state.
Reference
[1] V.P. Malyshev, N.S. Bekturganov, A.M. Turdukozhaeva. Viscosity, fluidity and density
of substances as a measure their chaotization – Moscow.: Nauchnyi mir, 2012. – 288 p.
DIAGRAMS OF PHASE EQUILIBRIUMS WITH CALCIUM AND BARIUM

IN MELTS ON THE BASIS OF OXYGEN-CONTAINING IRON
Mikhailov G.G., Makrovets L.A., Vydrin D.A.
Southern Ural State University
e-mail: ph-ch-susu@mail.ru
In connection with high intensification of high-test metal production processes,
processes carrying of steel alloying and refining to special aggregates of complex refining the
role of highly active substances such as alkaline-earth metals in the processes of express steel
refining from oxygen and sulfur has increased. All alkaline-earth metals have low solubility in
iron, have characteristics of high pressure of saturated vapor under the temperatures of steel
production and have high affinity to the oxygen and sulfur dissolved in iron. It allows
considering alkaline-earth metals as a means of deep iron refining from oxygen and sulfur as
well as modification of nonmetallics, structure of cast steel and cast iron. Complex alloys Si–
Ca, Ca–Al, Ca–Si–Al, Si–Ba, Mg–Ni are commonly employed. Application of above
mentioned alloys enables to reduce the pyrothermality processes of insertion alkaline-earth
metals to steel and to increase the efficiency of their usage. In spite of large-scale
implementation of refining into practice, organization of special refining processes such as
liquid metal blowing by noble gases with alkaline-earth metals and slag-forming mixtures,
batch insertion of alkaline-earth metals, application of pinch roll, the thermodynamic aspect of
the problem of alkaline – earth metals application in metallurgical engineering has not been
studied.
In this article for the analysis of the refining processes the method of building diagrams
of states in which densities of the components in the liquid metal conjugated to oxide
equilibrium system is offered. As a result of processing of a large number of literary and
reference data, analysis of technological results the database on ∆G refining processes, values
of equilibrium constants for particular reactions has been formed, parameters of the phases of
variable composition, oxide and metal, have been assorted. Surfaces of the components
solubility in liquid metal for the systems Fe–Ca–O–C, Fe–Ca–Al–O–C, Fe–Ca–Si–O–C, Fe–
Ca–Al–Si–O–C, Fe–Ва–O–C, Fe–Ва–Al–O–C, Fe–Ва–Si–O–C, Fe–Ва–Ca–Al––O–C have
been structured. The diagram shows that when the concentration of Ca and Al is changed for
thousandths of a percent the equilibrium composition of the metal oxide phases may
significantly change from oxide melt to corundum and gas phase. Considering the behavior of
Ba in the metal it is found that the solubility of Ba is less than 0.001 wt. %. Taking into
account that the atomic weight of barium is 137 and oxygen 16, the one-thousandth percent of
barium can bind only 0.0001 wt. % of oxygen and, therefore, barium as a metal deoxidizing
agent is ineffective. Diagrams of the surface of the components solubility in liquid metal for
systems Fe-Ba-O, Fe-Ca-Ba-O, Fe-Ba-Al-Ca-O indicate the possibility of non-metallic
inclusions with barium but in the limit of possible density with barium.
Analysis of surface properties of Ba in the metal showed that this element is a surface
active element and reduces the critical radius of the nuclei of nonmetallic inclusions in the
steel, increases their number but reduces their sizes. According to the latest data barium also
facilitates the homogenization of the liquid melt and the improvement of the structure of cast
metal.
On the basis of calculations and plotting of solubility the conclusions have been made
about the depth of refining capacity alloys with alkaline-earth metals, the composition of
generated nonmetallic inclusions in the metal and the possible mechanism of the influence of
alkaline-earth metals on the quality of the metal.
FREE-VOLUME VISCOSITY MODEL FOR LIQUID METALS

Mousazadeh M. H.
Nuclear Science Research School, Nuclear Science & Technology Research Institute
(NSTRI), Tehran, Iran
e-mail: mousazadeh@yahoo.com
Values of the viscosities of liquid metals are important in the prediction of fluid flow in
many metallurgical manufacturing processes. In this work the free-volume and friction
viscosity model is presented versus pressure and temperature. This model involves only three
adjustable parameters for each pure compound. The model has been successfully applied to
liquid metals (Li, Na, K, Rb, Cs, Mg,Ca, Sr, Ba, Hg, In, Ag, Ni, Au, Al). This model has been
shown to provide satisfactory results for the modeling of the viscosity of liquid metals over
wide range of temperature.
THERMODYNAMIC MODEL AS THE APPROACH OF DEFINITION

OF THE VALENT CONDITION OF IRON IN ROCKS
Mukhetdinova A.V., Bychinsky V.A., Chubarov V.M.
Vinogradov Institute of Geochemistry Siberian Branch of the Russian Academy of Sciences,
Irkutsk, Russia
e-mail: mukh@igc.irk.ru, val@igc.irk.ru
Possibility of definition of iron oxide (FeO) in silicate and carbonate rocks by means of
thermodynamic modelling is estimated. Iron most often determine by volume methods from
which the greatest distribution was received by bichromated and permanganatny methods [1,
2]. In the process of test decomposition iron (II) can be oxidized before titration that brings a
considerable error in result of the analysis. Thus the accuracy of results of the analysis is
influenced also by high contents of manganese (from 0.1 to 2.7%), and sulfides which also
often are present at carbonate breeds. As this technique not always considers influence of
these factors, for the carbonate breeds having rather high concentration of FeO, this error can
distort results of the analysis considerably. Also for definition of the maintenance of FeO the
technique in which the method of the double return titration is applied is used, thus all iron
oxide is oxidized at once surplus of an oxidizer which titrates, thus, is excluded then the error
mentioned above [3].
To an assessment of correctness of the specified techniques applied the theoretical
device of the chemical thermodynamics, allowing estimating real forms of existence of
elements and the probable direction of their transformation, based on a method of
minimization of free energy [4, 5]. Thermodynamic models for definition of the content of
iron in rocks by two techniques are constructed. Ions and compounds of iron and manganese
in solution are established. Possible influence of manganese on results of the analysis is
investigated. According to results of modeling in solution (pH=0.3-0.8) in balance the
following ions and compounds of iron and manganese prevail: Fe2+, Fe3+, FeF+, FeOH2+,
FeSO4, FeSO4+, Mn2+, MnF+. It is established that manganese is present at a type of MnF+ that
has no stirring impact on iron definition as it is possible to estimate quantity of this form
precisely. In the chemical analysis by means of a permanganatny method we can estimate only
iron and manganese sum that at high contents of manganese (from 1%) can make the
significant contribution to an analysis error.
References
[1] Ponomarev A. N. Methods of the chemical analysis of silicate and carbonate rocks.
M.:Publ. Academy of Sciences of the USSR, 1961. 414 p.
[2] Andrade S., Hypolito R., Ulbrich H., Silva M. // Chemical Geology 2002.– V. 182.–
P. 85.
[3] Yokoyama T., Nakamura E. // Geochimica et Cosmochimica Acta. 2002. V. 66.– №
6.– P. 1085-1093.
[4] Karpov I. K., Chudnenko K. V., Kulik D. A., Bychinskii V. A. // Amer. J. Sci.
2002.– V. 302.– No. 4.– P. 281.
[5] Chudnenko K.V. Thermodynamic modeling in geochemistry: theory, algorithms, software,
appendices. - Novosibirsk: Academic publishing house "Geo", 2010. 287 p.
STRUCTURE OF PREREACTION CENTRES OF DIENE POLIMERIZATION

ON (TiCl3)n·Al(i-C4H9)3 CATALYSIS
Mustaev A.R., Borisevich S.S., Yanborisov V.M.
Ufa State University of Economics and Service, Ufa, e-mail: monrel@mail.ru
It is known [1] active catalytic centers (on the basis of titanium chloride (IV)) of
polymer chain are formed on the surface of catalysis solid phase during diene polymerization.
The true mechanism of polymer chain growth and the factor influencing stereoregular polymer
formation is still under discussion. Some researchers think [2] that polymer chain growth
takes place on the active catalytic centers of the octahedral structure of alkylated titanium
chloride (III) by Kossi monometallic mechanism. Other researchers don’t consider aluminum
organic compound (AOC) to be only an alkylating agent. They believe that TiCl3-crystal –
AOC interaction results in formation of so called prereaction centers (PC). The latter in
interaction with monomers forms the active catalytic centers (ACC) of diene polymerization.
According to [1] polymer chain growth takes place on 3-5 ACC of different types, which
probably differ according their structure and compound. PC is formed during the process of
TiCl4– AOC interaction (catalytic mixture preparation). As the result of the reaction, TiCl3-
crystal and AOC as well as its chlorine
substituted forms of AlR2Cl and AlRCl2
types (R – i-C4H9) are generated. TiCl3-
crystal surface contains “spare space” at the
ends of the crystal “needle”. Then the
interaction of the crystal surface with AOC
can be presented as parallel-sequential
reactions, in the result of which 7 types of
bimetallic PC of different structure and 3
types of monometallic PC (structure 1-10 in
the figure) can be generated.
PC structures were calculated with
using quantum chemistry methods in FireFly
programme. The thermodynamic parameters
of PC forming reactions were estimated. The
values of the enthalpy of such structures
formation don’t differ. So we can assume that ion-coordinating polymerization can run by
ACC and monometallic and bimetallic mechanisms.
References
[1] Monakov Yu.B., Tolstikov G.A. Kataliticheskaya polimerizatciia 1,3-dienov. М.:
Nauka, 1990. 211p. (In Russian).
[2] Encyclopedia of Polymer Science and Technology, V. 8. Ziegler-Natta Catalysts. –
N.Y.: Wiley InterScience, 2009. – P. 517–536.
Quantum-chemistry calculations were done on the cluster super computer of the

Institute of Organic Chemistry of USC of RAS.
APPLICATION INVERSE GAS CHROMATOGRAPHY TO DETERMINE

THE THERMODYNAMIC FUNCTIONS SORPTION OF VOLATILE COMPONENTS
OF NON-VOLATILE LIQUID IN THE SYSTEM OF CONSTANT VOLUME
Onuchak L.A.
Samara State University, Samara, Russia
e-mail: onuchak@samsu.ru
One of the main problems in the application of inverse gas chromatography for the
determination of standard thermodynamic functions of sorption of volatile components from
the gas phase non-volatile liquid (stationary phase) is the choice of the constants describing
the sorption redistribution in the «gas – liquid». Previously, it proposed to use a dimensionless
constant Pst / K H ( Pst – standard pressure, K H – Henry constant desorption) as the
adsorption constants, considering the redistribution of the volatile component in the system of
constant pressure. Quantity is easily determined from the gas chromatographic data, if exact
molecular weight of nonvolatile liquid is known.
The information about effective molecular weight is often missing when using
polymeric stationary phases. It is difficult to apply the above approach. In this case, it is
expedient to examine the redistribution of volatile components between the liquid and gas
phases in the system of constant volume by analogy with the adsorption equilibrium of the
system «gas – solid adsorbent». Applying for the chemical potentials of the components of the
system asymmetrical frame of reference standard state, we find that, based on 1 mole of the
adsorbed substance ( V , T = const ) was obtained for the change in the Helmholtz free energy:
Δsp FV,T = − RT lnK C + RT ln (Cl / C g )+ RT , (1)
where the distribution constant is the ratio of the concentration of the volatile component in
the liquid and gas phases.
Standard Change Helmholtz free energy obtained from equation (1) with Cl = 1 and
C g = 1 (eg, 1 mkmol/sm3):
Δsp F V,T = − RTlnK C + RT = − RT (lnK C − 1) .
0
(2)
To change the standard entropy and the internal energy can be written:
 ∂Δsp FV,0T 
Δsp S = −  = RlnK C + RT  ∂lnK C  − R ,
0
 ∂T  (3)
 V  ∂T V
 ∂lnK C 
ΔspU V,0T = RT 2   . (4)
 ∂T V
For a small range of temperatures obtained:
ΔspU V0 Δsp SV0
lnK C = − + +1 , (5)
RT R
and ΔspU V,0T = QV .
SOME THERMODYNAMIC ASPECTS OF SUGARS

Ovchinnikov V.V., Kulakov A.A., Lapteva L.I., Naiman M.O.
A.N. Tupolev Kazan National Researching Technical University, Kazan, Russia
e-mail: chem_vvo@mail.ru
Thermodynamic characteristics of the majority of sugars are known now. Earlier it was
informed [1] on the sizes of free energy of combustion (∆Gocomb) and formations (∆Gof) in the
standard conditions α-D-galactose (I, С6Н12О6), α-D-glucose (II, С6Н12О6), α-D-lactose (III,
С12Н22О11), α-D-sacharose (IV, С12Н22О11) and D-fructose (V, С6Н12О6) (Table 1). Also it
has been shown [2], that heat of combustion (∆Hоcomb) the majority of organic connections
including sugars, can be calculated on the equation (1) in which i and f are stjichiometric
factors, factor N corresponds to the general number valence electrons except for a number (g)
of a lone electron pairs of heteroatomes
∆Hоcomb = i - f (N - g) (1)
In view of it, the equations (2-5), specifying that circumstance, have been calculated,
that not only heat of combustion, but also free energy of combustion and formation processes,
entropy (∆Sо) [3-5] and the heat capacity (Ср) of sugars [6] are characterized by the similar
excellent dependences, connecting them with parameter (N - g) too.
∆Gocomb = (66.7±2.1) – (122.4±0.6) (N-g); r 0.999, So 15.3, n 5 (2)
∆G f
o
= (-303.9±20.8) – (25.6±0.6) (N-g); r 0.999, So 15.3, n 5 (3)
∆So = (22.2±4.6) + (7.8±0.1) (N-g); r 0.999, So 2.7, n 3 (4)
Cp = (19.6±16.2) + (8.4±0.4) (N-g); r 0.996, So 11.9, n 5 (5)
Table 1. Thermodynamic parameters (kJ mol-1 and J mol-1 K-1) some sugars in
condensed phase at 298 K
Compound, (N – g) I, 24 II, 24 III, 48 IV, 48 V, 24
comb 2865.9 2872.2 5826.5 5789.9 2874.1
-∆Go form 923.5 917.2 1515.2 1551.8 915.4
∆So
205.4 209.2 392.4
Ср 217.0 235.9 417.6 424.3 208.0
References
[1] Metzler D. Biochemistry. Mir, Moscow. (1980) 407 p.
[2] Ovchinnikov V.V.. Doklady of Physical Chemistry, 443 (2012) 69.
[3] Boerio-Goates, J. J. Chem. Thermodynam., 23 (1991) 403.
[4] Jack G.W., Stegeman G., J. Am. Chem. Soc., 63 (1941) 2121.
[5] Putnam, R.L.; Boerio-Goates, J., J. Chem. Thermodynam., 25 (1993) 607.
[6] Domalski E.S. and Hearing E.D., J. Phys. Chem. Ref. Data, 19 (1990) 881.
ON SINGULAR POINTS OF INTERMOLECULAR CURVES AND CONNECTIONS

OF THEIR COORDINATES WITH PROPERTIES OF FLUIDS
Petrik G.G.
Institute for Geothermal Research of the Dagestan Scientific Center of RAS,
Makhachkala, Russia
e-mail: galina_petrik @mail.ru
The new results obtained in our last years’ works related to the problem of the
description and simulation of thermophysical properties of substances (one-parametrical
families of the equations of state based on the model of interacting point centers; the control
parameters of the model) deduced us to the problems of adequate intermolecular interaction.
As a prospective informative model it was chosen the model of spherical shells. The first
results for it were received by us a quarter of the century ago. The study is based on a simple
idea – an adequate intermolecular potential curve and the associated force curve
F (r ) = −dU / dr should keep the “genetic information” about the properties of molecules
reflected in specific properties of substances. That was the rationale for finding correlations
between the “fundamental” properties of substances and the coordinates of “fundamental”
features of the intermolecular curves. In this paper as such a property serves a critical molar
volume VC.
The analytical and calculation capabilities of the model of spherical shells are realized in
the work in the following way. Three formulas for calculation the r-coordinate for the
inflection point of potential curve are given in a form of polynomials of the factor gS - the
most general characteristic of a spherical model object – its “rigidity”, forming the “genetic”
curve. As a research object we chose molecules-globes (CCl4, SF6 type). Values of factor gS
for them are close to one. The correlation found between the critical molar volume VC and
elementary critical molecular volume (rpu ) 3 gives opportunity to build hierarchy of
connections between VC and the effective intrinsic volumes of the model objects,
corresponding to the singular points of potential curve (zero, minimum, inflection):
Vc=2.85b(r0)=2.3215b(rm)= 1.91b(rpu ) . (At a specific forecast these significances will be vary
in dependence on the value of the factor gS). It is shown that the series can be extended by
correlation VC = 1.51b(rpf ) . Such a form takes the known L.P.Phylippov’s empiric correlation
1.08Vc1 / 3 = (d + r*) (in parentheses – the diameter of model molecule, Å) after involving a
new singular point – an inflection point of the force curve F(r). An attempt is made to enlarge
the structure and to include other supposedly singular points for which the similarity
coefficient takes values close to significances connecting the critical molar volume and the
parameter b of the known equations of state: Redlich – Kwong (3.847), Peng – Robinson
(3.95) and others.
Obtained in the framework of a simple model results are of obvious interest and require
further research. Many of our papers on the issues discussed are available at www.csmos.ru.
Some of the results have been obtained with the support of the RFBR grant (project
09-08-96521а).
FORMATION OF MOLECULAR COMPLEX BETWEEN TRIGLYCINE

AND 18-CROWN-6 ETHER IN H2O–DMSO MIXTURES
Pham Thi Lan, Usacheva T.R., Sharnin V.A.
Ivanovo State University of Chemistry and Technology, Research Institute
of Thermodynamics and Kinetics of Chemical Processes, Ivanovo, Russia
e-mail: oxt@isuct.ru
The investigations of interactions between amino acids and peptides with crown ethers are
useful for understanding the nature of host-guest complex formation and for elaborating a model
of the influence of solvent composition on equilibria in solutions. Studies of the molecular
complexes formation reaction between triglycine (glycylglycylglycine, 3Gly) and 18-crown-6
ether (18C6) in water-dimethylsulfoxide (H2O-DMSO) solvent are a continuation of a series of
works to reveal regularities and peculiarities of the influence of mixed solvent composition on
complex formation [1-4]. Calorimetric titrations were used for the study of the interaction
between 18C6 and 3Gly in H2O-DMSO solvents at XDMSO= 0.00÷0.15 mol. fr.:
3Glysolv +18C6solv ↔ [3Gly18C6]solv (1)
The standard thermodynamic parameters of the reaction (1), ΔrG0, ΔrH0, TΔrS0, were
calculated from calorimetric measurements carried out using the calorimeter TAM III (TA
Instruments, USA) at T = 298.15 K. The lgK0 and ΔrH0 values were obtained by mathematical
processing of the experimental data on the program «HEAT» [5], which allows calculating the
enthalpy of reaction and equilibrium constants in systems with an arbitrary stoichiometry.
The increase of DMSO concentration in solvent lead to a monotonic increase the stability
[3Gly18С6] from lgK0 = 1.10 to lgK0 = 1.66 and increasing exothermicity of the reaction (1) from
-5.9 kJ/mol to -11.5 kJ/mol.
A comparative analysis of the thermodynamic parameters of the reaction (1) and reagent’s
solvation in H2O-EtOH and H2O–DMSO solvents was given. An analogous influence of H2O-
EtOH on the thermodynamic parameters of the equilibrium (1) was observed previously [4]. The
enthalpy contribution to the Gibbs energy of the reaction (1) prevails over the entropy
contribution in both H2O-EtOH and H2O–DMSO mixed solvents. However, the increase the
stability [3Gly18K6] at XDMSO = 0.15 mol. fr. is more significant than in the analogous
composition of H2O-EtOH solvent [5]. In contrary, the enthalpy values of the reaction (1) are
more exothermic in H2O-EtOH than in H2O–DMSO.
The previous studies of 18C6 complex with amino acids (AA) [3] in water - organic
solvents have shown that, as in the case of reaction (1), the increase of the concentration of non
aqueous component in the solvent leads to increase in the stability of the molecular complexes
[AA18C6] and increases the exothermicity of their complexformation.
This work was supported by the program “Research and scientific-pedagogical personnel
of innovative Russia for 2009-2013 years”, state contract 14.B37.21.0801.
References
[1] Shormanov V.A, Sharnin V.A. / Achievements and problems of solvation theory:
structure – thermodynamical aspects/ Ed. by Kutepov A.M. М.: Nauka, 1998. p. 172.
[2] Sharnin V.A. // Zh. Obshch. Khim. 1999. V 69. № 9. p. 1421.
[3] Usacheva T.R. , Sharnin V.A., Chernov I.V., Matteoli E. //J. Therm. Anal. Calorim. DOI
10.1007/s10973-012-2625-7.
[4] Pham Thi Lan, Usacheva T.R., Sharnin V.A./ Abstracts VII Russian Conference of
Young Scientists "Theoretical and experimental chemistry of liquid-phase systems" (Krestovsky
readings) 12-16 November 2012, Ivanovo, p.38.
[5]Borodin V.A., Kozlosky E.V., Vasil’ev V.P. // Zh. Neorg. Khim. 1982. V. 27. № 9.
P.2169.
PRACTICE AND PROBLEMS OF THERMODYNAMIC PROPERTIES CALCULATIONS

OF ORGANIC COMPOUNDS ACCORDING TO MOLECULAR DATA
Pimerzin A.A.
e-mail: pimerzin@sstu.smr.ru
The development of molecular modeling and quantum-chemical calculations really
opens a wide possibilities for prediction the thermodynamic properties of polyatomic organic
compounds. Today however, these opportunities are not used always fully. The accuracy of
the result of calculation depends on several conditions that must be performed if we are
looking forward to a positive outcome. First and foremost, it is the observance of the
assumptions underlying the statistical calculations of thermodynamic properties of
compounds.
Among them:
- the principle of independence of the different types of motion and the additivity of
their contributions to thermodynamic functions;
- approximation of "rigid rotator - harmonic oscillator".
However, the complex structure of polyatomic molecules, the conformational
heterogeneity of the compounds, the appearance of intramolecular degrees of freedom with
high-amplitude movement, an harmonic character of the vibrational frequencies are very often
don’t fit into a framework of the established assumptions.
This presentation analyzes the reasons for the differences between the forecast of the
thermodynamic properties (entropy, enthalpy and heat capacity) and experiment. The analysis
is performed on the example of the thermodynamic properties of aliphatic, alicyclic, aromatic
hydrocarbons, alkylphenols, alkylhalogenbenzenes and reactions with their participation.
Some of the raised issues have been decided. For other problems the methods, which
allow detecting their emergence and making estimates, have been proposed. For some
problems have yet to find a solution.
BOIL POINT OF HYDROCARBONS BY CORRELATION GAS

CHROMATOGRAPHY
Pimerzin A.A., Vishnevskaya E.E., Tsvetkov V.V.
e-mail: pimerzin@sstu.smr.ru
The normal boiling point (Tb) is an important physical property of the hydrocarbon
compounds. Boiling point used as the reference data in predicting the saturated vapor
pressure, enthalpy of vaporization, and other of the characteristics phase transitions.
Experimental methods for determination Tb very laborious and require high-purity
samples of compounds. The development of methodologies for calculating Tb to give high
accuracy results are of considerable interest.
The normal boiling points of hydrocarbons were determined using the correlation of the
temperature dependence of the logarithm of the reciprocal adjusted retention times above the
non-polar phase. Tb prediction algorithm consists of two processes. The first of them -
includes temperature dependence of approximation adjusted retention time studied
compounds by the equation ln(1/ t 'R ) = a + b ⋅ (1/ T ) (*). As the analysis of data, dependence
ln(1/ t 'R ) = a + b ⋅ (1/ T ) (show figure) is analogous to the logarithm of the vapor pressure of
the reciprocal temperature.
-4 1 2 3
4 5 6
-6
ln(1/tR')
1- Metylbutylbenzene,
2 - 1,3-di-tert-Butylbenzene,
ln(1/ t R ')
-8
3 - 3,5-di-tert-Butyltoluene,
-10
4 - 1,3,5-tri-tert-Butylbenzene,
5 – penta-Ethylbenzene,
-12 6 - hexa-Ethylbenzene.
-14 The dotted line denotes the hypothetical isobar

0.0023 0.0025 0.0027 0.0029 0.0031 0.0033
1/T equal ln(1 / t ' R ) .
Next, for every compounds is necessary to solve linear equation (*) and find the value of
the effective boiling point Тb,i,eff at a definite value ln(1 / t ' R ) simulating the pressure. The
value of the hypothetical isobar [ ln(1 / t ' R ) ] is chosen to minimize the extrapolation to
determine Тb,i,eff .
The effective boiling point is the chromatographic parameter that correlates well with
the Tb compound. Second process is determining the coefficients of the linear equation
Tb ,i (101.325 / kPa) = Tb ,i ,eff ( P ) ⋅ b'+ a ' from the known values of reference compounds. This
equation relates normal boiling point and Тb,i,eff: As reference substances chosen compounds
by class of the studied compounds having exact values of Tb.
The proposed method was tested of n-alkanes, alkylbenzenes, and chlorobenzenes
alkyldiphenylmethanes. For the test set consisting of 63 alkylbenzenes the average absolute
deviation between the literature and this work Tb values was 1.7K.
THE BOND NATURE AND PROCESSES OF ATOMIC RECOORDINATION

AT THE INTERFACES FORMING OF GRAPHENE AND TRANSITION METALS
G/TM: Ni et al. ACCORDING TO RESULTS OF MD-SIMUTATION
BASED ON AB INITIO POTENTIALS
Polukhin V.A.1,2, Kurbanova E.D.1
1
Institute of Metallurgy of Ural Division of RAS, Ekaterinburg, Russia, e-mail:kurbellya@mail.ru
2
Institute of Material Science and Metallurgy of Ural Federal University, Ekaterinburg, Russia
The studies of graphene (G)/metal interfaces of heterostructures are very important for
advancing and designing the optoelectronic devises taking into account the unique electro- and
heat conductivities of metal-carbon composites with two-dimensional G crystals, as substrates.
There are especially interested the hetero structure materials with the interfaces formed layer-by-
layer superposition of hexagonal G-planes on (111) planes of transition metal (TM: Ni, Co, Cu,
Pd, Au, Ir) crystalline substrates. As it was revealed from the quantum mechanics estimations the
description of cohesive energy dispersion in dependence on G-TMe layer interdistance using only
Lennard-Jones potential functions was imposible. Therefore in a present work it was a successful
using of combined approach for heterostructural model, basing on the molecular dynamic
simulation (MD) with accurately parameterized results of AB-initio estimations of many-particle
interactions to obtain correct and useful prognosis of required properties for real designing
functional G/TM interface prototypes elaborated in nanoelectronics. So in the available database
of various versions especially for computer simulation of isolated TM (Ni, Pd, Cu, Au, Ir)
nanocluster structures and atomic dynamics in the transition metalsurface interlayers of hetero
composite systems, the interatomic interaction potentials were calculated using various
approximations, which differ in the complexity and accuracy of taking into account multiparticle
effects.
Therefore, when choosing techniques for transition metals, we took into account the
specific features of clusters to be MD simulated, the presence of an open surface, the regularity of
the cluster, and the interaction with an immobilizing substrate. To this purposes, we have
analyzed the available multiparticle interaction potential of transition metal atoms in the case of
isolated clusters located on a substrate in contact with other phases. After testing calculations for
estimating the binding energies, we chose the Sutton–Chen embedded atom model to calculate
the multiparticle potential for Ni clusters. But for Pd and Cu clusters there were applied the
Cleri–Rosato tight-binding approximation (TBS) to calculate atom interactions of the concerning
metals.
So MD simulation of heterostructure materials with the interfaces formed layer-by-layer
superposition of hexagonal G- planes on (111) planes of transition metal (TM: Ni, Cu, Pd, Au, Ir)
crystalline substrates was carried out and the detailed analysis and comparing of obtained
physico-chemical properties were delivered. It was taking into account the specifities of
concerning metals as lattice parameters and difference of TMe-graphene interface cohesive
energies: Ni and Cu for example, having almost the same TMe-C interatomic parameters (aNi-C
=0.2018 nm, aCu-C = 0.2243 nm at aC-C =0.142 nm and a0=31/2aC-C = 0.246 for constant of
hexagonal graphene lattice ) along with the essential varieties of cohesive energies (ENi-C =
91.33·102meV/nm2 ECu-C = 24.81·102meV/nm2). Moreover taking into account the value of aCu-C
it’s necessary to be noted that at the interatomic distances about dCu-C = 0.326 nm and weaker
orbital pz-dz hybridization of carbon (pz) and metal (dz) the electron charge transportation realized
from metal bands to graphene ones of interface layers in comparison with the different situation
when the value dCu-C closed to 0.2243 nm and the charge transfer could be reversible.
The work is supported of Division of Chemical Science of RAS (Project No 12-T-3-1022).
THE USE OF THE BUFFER CAPACITY THEORY FOR THERMODINAMIC

ASSESSMENT OF THE NATURAL CONTROL OF HEAVY METAL CONTENTS
IN POLLUTED ECOSYSTEMS
Povar I., Spinu O.
Institute of Chemistry of the Academy of Sciences of Moldova, Chisinau, Moldova
e-mail: ipovar@yahoo.ca
The ecosystems possess buffer properties to absorb significantly the pollutants but their
presence or appearance in large quantities cumulatively overloads the systems and as a result
they cannot be absorbed. The main focus in our research is the way by which the ionic
pollutants move and transform within the environment, their distribution in ecosystems, and
their deposition and cycling in the terrestrial environment.
The problem of controlling the ion concentrations in natural systems may be formulated
as: what is the response of the system when changing the thermodynamic parameters that
govern the pX (negative logarithm of ion activity)? In other words, what is the pX buffer
capacity of the system? At elevated concentrations when the influx of pollutants exceeds their
buffer capacity toxic effects may occur. Any buffer system has a certain potential reserve,
which controls the equilibrium and keeps one of the thermodynamic parameters (as the
equilibrium concentration or temperature) constant. The lack of information about the
pollutant buffer properties of ecosystems can be explained by the absence of the quantitative
theory based on the thermodynamic approach that may predict their buffer behaviour. The low
buffer capacity of ecosystems, that are unable to preserve a constant pX, can lead to disastrous
environmental consequences.
In this work we have been developed a number of theoretical relationships for the main
buffer characteristics, based on the thermodynamic calculations of the mineral stability and
complex chemical equilibria in heterogeneous multicomponent systems “natural mineral-
saturated aqueous solution”. For the calculation of the equilibrium composition by the
thermodynamic modelling of complex chemical processes in natural heterogeneous systems,
the original equations of mass balance, taking clearly into account the contribution and
stoichiometric composition of solid phases (minerals), have been deducted. Under the real,
non-standard, conditions, for determining the mineral thermodynamic stability, the equation
for the variation of Gibbs energy, ΔGtot, in which the residual and analytical (initial)
concentrations of mineral components appear explicitly, has been deduced. It has been
established that the buffer capacity of the two-phase buffer system is considerable greater than
that of a single-phase buffer one in the pM range around their maximum values.
The thermodynamic approach within the developed buffer theory offers the possibility
to: (a) extend our mechanistic comprehending of natural processes and their acceleration that
may attenuate and control the content of a number of contaminants in soils and groundwater
by the complex formation (chelating) and precipitation reactions, (b) forecast the long-term
effects in suppression of heavy metals in the polluted waters, (c) predict and identify the real
conditions and to what extent these processes are reversible and (d) improve basic
understanding of ecological mechanisms and processes. Overall, the proposed approach is
intended to identify the dominant processes that are responsible for observed changes in
contaminant concentrations and provides the knowledge needed for researchers to set reliable
limits of ion (metal) levels in the environment.
UNIVERSAL THERMOCHEMICAL BASICITY SCALE OF SOLVENT.

ADVANTAGES AND DISADVANTAGES
Rakipov I.T., Varfolomeev M.A.
Department of Physical Chemistry, Kazan (Volga region) Federal University, Kazan, Russia
e-mail: ilnaz0805@gmail.com
Intermolecular interactions are of particular interest because they appear only in certain
systems and can lead to a significant change in the properties of the interacting molecules, as
well as have a significant influence on realization of various physic-chemical and biological
processes. For the quantitative estimation influence of solvation effects on the reactivity of the
molecules necessary determination thermodynamic parameters of hydrogen bonding solute -
solvent. One method of determining these quantities is the thermodynamics of solvation.
In the present work we have carried out a calorimetric study of hydrogen bonding of
methanol, chloroform and pyrrole with proton acceptors. Based on the data analyzed the
influence of the structure and properties of interacting molecules on the enthalpy of the
hydrogen bonds.
In this work, we measured the enthalpies of solution at the limit dilution of methanol,
chloroform and pyrrole in 40 solvents belonging to different classes of organic compounds.
Based on experimental and literature data by the method [1] were calculated of enthalpy of
specific interaction in various systems solute - solvent. Comparing the enthalpies of specific
interaction OH, NH and CH groups in the aprotic solvents, were found linear dependence,
suggesting that additivity of the thermodynamic parameters of hydrogen bonding in the
complexes 1:1. On the basis of found regularities between the enthalpy of specific interaction
introduced a scale of basicity aprotic solvents (SHBA). The proposed parameter was tested to
describe the enthalpy of hydrogen bonding of phenol and amides with aprotic solvents. In all
cases, observed linear correlation of good quality, indicating about correct description of the
properties of solvents by this parameter. A comparative analysis of the proposed scale of
basicity and the published parameters of the solvent.
It is known that the formation of hydrogen bonds can be determined from the shift of the
absorption frequencies in the infrared spectra. The value of the frequency shift is proportional
to the strength of hydrogen bonding.
In the present work we have compared the frequency shifts of the absorption of O-H and
N-H groups of methanol, phenol, pyrrole and diphenylamine with proton acceptors in
complexes 1:1 in the environment carbon tetrachloride on the parameter basicity SHBA. It was
found that the spectral characteristics are well described by this parameter.
Reference
[1] Solomonov B.N., Novikov V.B., Varfolomeev M.A., Mileshko N.M. A new method
for the extraction of specific interaction enthalpy from the enthalpy of solvation. Journal
Physical Organic Chemistry, 2005. V.18. № 1. Р.49-61.
METHOD OF BUILDING OF THE FUNDAMENTAL UNSYMMETRICAL EQUATION

OF STATE
Rykov V.A., Rykov S.V.
National Research University of Information Technologies, Mechanics and Optics,
St. Petersburg, Russia
e-mail: rykov-vladimir@rambler.ru
The problem of working out of an equation of state which on the one hand would meet
the requirements shown to uniform equations of state of virial type, and with another to the
scale equations of state considering asymmetry of a thermodynamic surface concerning a
critical isochore, all becomes more actual. It and working out crossover models within the
limits of the parametric approach, and attempt to modify a fundamental equation of state in
physical variables. In the given operation the second approach to this problem is discussed.
First of all it is caused by that the regular component of a Helmholtz free energy is expressed
as density and temperature function. Therefore it is natural to solve this problem in the same
variables. As the scale functions of a free energy developed for model of the lattice gas in
physical variables [1], under the qualitative and quantitative performances do not yield to the
scale functions developed within the limits of the parametric approach. As a result the
uniform not analytical equation structurally including these functions, last decade has found
the application for calculation of tables SSSRD of some technically important substances.
However thus asymmetry concerning a critical isochore was not to the full considered. Now it
was possible, using the design procedure of unsymmetrical components of a free energy in
physical variables offered by us (in the co-authorship from Kudryavtseva I.V.), to solve this
problem [2]. At the heart of the offered approach to the account of asymmetry of a liquid
concerning a critical isochore the method of pseudo-critical points [3] lies. On purpose to
approve the offered approach to build-up of the uniform equation of state considering
asymmetry of system a liquid-gas, argon equations of state, R23 and R134a are constructed.
Thus the particular interest represents an argon as on it there is the considerable file of the
precision data as thermal, and калорических, gained and in the regular part of a
thermodynamic surface, and in a neighbourhood of a critical point. For all three substances
there is also a trusty observational information on a line of phase equilibrium, including a
neighbourhood of a critical point. Detailed tables of equilibrium properties of these substances
in wide field of state variables, including critical and metastable parts of a thermodynamic
surface are calculated. So, for an argon this field makes on density from 0 to 3,3 ρс, on
temperature from a threefold point to 1000 К.
On the basis of the analysis of the available observational information it is shown that
the approach viewed in operation allows not only to transmit qualitatively truly features of a
thermodynamic surface, but also quantitatively to meet the requirements shown to
thermodynamic tables SSSRD.
References
[1] Rykov V.A. The description of a wide neighbourhood of a critical point by means of
scale function of a free energy // Russian Journal of Physical Chemistry A. 1985. 59, № 9. – P.
2349–2350.
[2] Kudryavtseva I.V., Rykov V.A., Rykov S.V. Asymmetric uniform equation of state
R134a // Vestnik of International Academy of Refrigeration. 2008. – № 2. – P. 36–39.
[3] Rykov V.A. About a hypothesis «pseudo- spinodal » curve // Russian Journal of
Physical Chemistry A. – 1986. – 60, № 3. – P. 789–793.
MOLECULAR DYNAMICS SIMULATION OF THE CONFORMATIONAL

TRANSITION OF PNIPAM POLYMER IN POROUS MEDIA
Shapovalova A.A., Brodskaya E.N., Gotlib I.Yu.
e-mail: shapovalovaaa@mail.ru
The development of various composite materials consisting of a porous matrix and a
‘smart’ polymer is now a rapidly developing field of research. Such materials can reversibly
respond to the changes in external conditions, such as temperature or pH of the medium.
Polymer molecules act as a ‘valve’, which, depending on the conditions, can be either ‘open’
(i.e., substances can freely move in and out of the porous space) or ‘closed’ (the substance is
retained by the adsorbent). Poly-N-isopropylacrylamide (PNIPAM) is frequently used to
modify adsorbent surfaces to control the transport of aqueous molecular solutions in porous
materials. PNIPAM belongs to one of the most well-studied classes of temperature-sensitive
polymers. Aqueous solutions of PNIPAM possess a lower critical solution temperature
(LCST) at 32°С. At temperatures below LCST the polymer exists in helix conformation and is
water-soluble. Above LCST the polymer assumes the non-soluble globular form. The
transition to globular form of the polymer would facilitate the diffusion of the substance (e.g.,
a drug) contained in the pores and will allow its transfer out of the porous space.
There are several experimental studies (see, for example, [1–4]) of mesoporous
silicate/PNIPAM/water systems under various conditions. These studies prove the possibility
of controlled transport of solutions in composite pores. However, the conditions of PNIPAM
conformational transition and the molecular mechanism of this process have not yet been
studied in sufficient detail.
In this work canonical ensemble molecular dynamics simulations were used to
determine the mechanism of the effect of temperature on the diffusion of water in cylindrical
siliceous mesopores grafted by PNIPAM. The conformational analysis of the polymer has also
been carried out. It is shown that transitions from swollen to collapsed form occur in an
interval of temperatures near 305 K rather than at a specific temperature value. At lower
temperatures the polymer displays weakly hydrophilic properties, and the diffusion coefficient
of water turns out to be lower than in a bulk system under the same conditions. On the
contrary, at temperatures above the transition point the diffusion coefficient of water increases
due to the weakening of the interactions of polymer chains with water.
This work was supported by the Russian Foundation for Basic Research (grant No. 12-
03-31761 MOL_A).
References
[1] Q.Fu, G.V.R.Rao, L.K.Ista, Y.Wu, B.P.Andrzejewski, L.A.Sklar, T.L.Ward,
G.P.López // Adv.Mater. 15, 1262 (2003).
[2]S.-W.Song, K.Hidajat, S.Kawi // Langmuir 21, 9568 (2005).
[3] Y.-Z.You, K.K.Kalebaila, S.L.Brock, D.Oupicky // Chem.Mater. 20, 3354 (2008).
[4] B.-Sh.Tian, Ch.Yang // J.Phys.Chem.C 113, 4925 (2009).
COMPETITIVE ADSORPTION OF GASES IN WET POROUS MATERIALS:

A COMPUTER SIMULATION STUDY
Shapovalova A.A., Sizov V.V., Brodskaya E.N.
e-mail: sizovvv@mail.ru
The goal of this work was to study the influence of pressure and composition of gas
mixtures, as well as the nature and structural properties of adsorbents on competitive
adsorption of gases in wet porous materials. The materials considered were activated carbons
with pores of different width and amorphous siliceous materials MCM-41 and SBA-15. The
simulation of CH4/CO2 gas mixture adsorption was performed using the Grand Canonical
Ensemble Monte Carlo method for porous adsorbents with a fixed content of water. All-atom
molecular models OPLS-AA, TraPPE, and TIP4P/2005 were used to describe intermolecular
interactions. Monte Carlo simulation results provide adsorption capacities (both total and
partial) and selectivities for wet adsorbents.
Fig.1. Slitlike pore of a wet

carbonaceous adsorbent containing
microclusters of preadsorbed water.
For model activated carbons with hydrophobic surface it was shown that preadsorbed
water forms microclusters (Fig.1) modifying the adsorption energy field of the porous
material. It is demonstrated that for a certain combination of conditions the adsorption
capacity for the components of the gas mixture can increase with increasing water content.
This effect is due to the increase of the partial capacity of the adsorbent for carbon dioxide
caused by the presence of preadsorbed water molecules favoring the adsorption of the more
polar component of the mixture. For amorphous silicates MCM-41 (mesoporous) and SBA-15
(micro/mesoporous) the influence of pore space morphology on the adsorption of water and
the consequent adsorption of CH4/CO2 mixture was studied. Due to the hydrophilic nature of
the adsorbent surface the water molecules do not combine into microclusters, but form
nanosized layers on the pore walls. As a result, the access of gas molecules to the pore surface
is blocked, and the adsorption properties of the wet porous material and determined by the
interactions between gas molecules and preadsorbed water.
03-31761 MOL_A).
LOCAL COMPOSITION FOR A BINARY MIXTURE

OF PARTICLES PLACED ON AN ISING LATTICE
Simonin J.P., Marry V.
CNRS - Université Paris 6, France
e-mail: jpsimonin@gmail.com
Local composition is an important concept in chemical engineering thermodynamics for the
description of fluid phases. The most popular theories using it are the quasi-chemical theory of
Guggenheim, and the Wilson, the non-random two-liquid (NRTL) and the UNIQUAC equations.
Also some models have been derived from statistical mechanical considerations. However, it may
be noticed that the accuracy of the models published in the literature has not been systematically
tested by comparison with exact or simulation results. In this respect, the equivalence between a
binary mixture of particles on a lattice and the original Ising problem of spins [1] has not been
used up to now in order to obtain exact results for the local composition in such systems.
In this work, the local composition in a binary mixture of particles A and B placed on an
Ising lattice was studied as a function of the fraction of A, xA, and of the reduced interchange
energy, ∆. The particles were supposed to interact through pairwise interactions between nearest
neighbors, Eij. It is known that the statistical distribution of particles then depends solely on xA
and on
∆=(2E - E - E )/k T .
AB AA BB B
The local composition was first determined analytically in one dimension (1D) by using the
analogy with the Ising spin problem [1]. The probability of finding a particle of a given type, A
say, in the close neighborhood of a particle A, denoted by x1, was calculated exactly. It turns out
that it is equal to the approximate formula proposed by Guggenheim and Rushbrooke nearly 75
years ago [2,3]. To the knowledge of the present authors, this exact result has not been reported
previously in the literature. The average composition beyond the first neighbor (for the second,
third,... site) was also found analytically. Besides, an approximate model presented in 1996 by
Aranovich and Donohue [4] to calculate x1 was examined in 1D. This analysis showed that the
method proposed in Ref. 4 requires a different interpretation for the quantities involved in the
model.
Next, results from Monte Carlo (MC) simulations are reported for a binary mixture on a 3D
cubic Ising lattice [5]. The MC results were used to assess the accuracy of analytical theories
proposed in the literature [2-4,6]. It was observed that these theories give satisfying results for ∆
values in the range -0.5 to +0.5. They rapidly break down completely outside this range. Besides,
for sufficiently large negative values of ∆ the local mole fraction, x1, was found to exhibit a
non-monotone variation as a function of the composition. For large positive values of ∆, x1 varies
monotonically but has an inflection point accompanied by a sudden rise. The local composition
was shown to obey an ex-act limiting law at high dilution of one component, x1 ≈ xA e∆, thus
providing a simple expression for the limiting activity coefficients of A and B. The activity
coefficients of the species, and the excess entropy per particle, were computed from the MC data
for any composition.
References
[1] G.F. Newell, E.W. Montroll, Rev. Mod. Phys., 25 (1953) 353.
[2] E.A. Guggenheim, Proc. Roy. Soc. A, 148 (1935) 304.
[3] G.S. Rushbrooke, Proc. Roy. Soc. A, 166 (1938) 296.
[4] G.L. Aranovich, M.D. Donohue, J. Chem. Phys., 105 (1996) 7059.
[5] J.P Simonin, V. Marry, Ind. Eng. Chem. Res. 51 (2012) 15497.
[6] Q.L. Yan, H.L. Liu, H.L., Y. Hu, Fluid Phase Equilib. 218 (2004) 157.
SIMULATION AND CALCULATION OF PHASE-CHEMICAL

TRANSFORMATIONS AS A SOLUTION OF CONDITIONAL EXTREME PROBLEM
Slobodov A.A., Sibirtsev V.S., Trenina M.V., Voronina T.V., Kremnev D.V.
St.Petersburg Research National University ITMO,
St.Petersburg State Institute of Technology, St.Petersburg
e-mail: aslobd@gmail.com
Let’s considered equilibrium state of arbitrary, with phase and chemical transformations,
m-component system - in conditions of isolation (constancy) on one or another, set of its state
variables, unequivocally determining this condition. It’s shown that the state is described by one
of interconnected (with Legandre conversions, i.e., actually, equivalent among themselves)
problems of conditional extreme (minimum) for corresponding (to these variables) characteristic
thermodynamic function of the system: internal energy U - at a constancy of system’ general
analytical composition yo, volume V, entropy S; Gibbs energy G - constancy for yo,
temperature T, pressure P; etc.
All of them are reduced to minimization, instead of characteristic, corresponding LaGrange
functions L, that has allowed all conditions of isolation to exclude from explicit consideration and
to keep only “natural restrictions” (non-negativity of quantities for each of components). And
these problems, in turn, are reduced to equations and inequalities systems, common (independent
on minimized function) “kernel” of which - determined only by internal state variables (i.e.
phase-chemical composition) of the system – is a subsystem (relative only to composition
variables {y 1( k ) , … , y (k )
n }, k = 1..r) of form:
m
µ i( k ) = ∑ aij µ j , (i,k) ∈ I0 : y i(k ) >0 (1)
j =1
m
µ i( k ) ≥ ∑ aij µ j , (i,k) ∉ I0 : y i(k ) =0 (2)
j =1
r n
∑∑ a
k =1 i =1
ij y i( k ) = y oj j = 1..m (3)
where r - number of possible phases; n - number of the different chemical forms of a

system, which are determined on m source components by means of stoichiometrical matrix {aij};
I0 - required set of system’ phase-chemical forms realized (among all possible ones) in
equilibrium.
These relationships express properly conditions of isolation on composition (material
balance (MB)) – of type (3), and corresponding to them differential conditions (1), (2) of
minimum L (generalized law of acting masses (LAM)). It’s shown, that the specificity of different
(on external state variables - S, V, P, etc.) problems can be taken into account without reduction
of consideration’ generality - directly in (1)-(3).Proposed methodology of iterative solution for
this system is based on solution of two subproblem of (1)-(3).
They are “phase” (determination of qualitative composition of I0) and “chemical”
(quantitative account of I0 composition) ones. The first subproblem is defined by inequalities in
(1), (2), second one - by equations: (3) and in (1), (2). General criterion, “manager” of iterative
process, is the condition of “descent” (decreasing) for function L. Procedures are offered, which
realize each of the problem’ stages and the phase-chemical problem as a whole. Their efficiency
and correctness are illustrated by results received for a row of inorganic and water-inorganic
systems with different nature.
Received theoretically and by calculation way the results are not only well agreed with
known experimental data, but also give qualitatively and quantitatively more rich information on
chemical-technological processes mechanisms of different compositions and purposes.
CALCULATION OF VIBRATIONAL STATES AND THERMODYNAMIC PROPERTIES

OF BARIUM-THULIUM BISMUTHATE HAVING THE STRUCTURE OF PEROVSKITE
SmolenkovYu.Yu., Taimassova Sh.T., Bissengaliyeva M.R., Gogol D.B., Knyazev A.V.
The Institute of Problems of Complex Development of Mineral Resources, Karaganda,
Kazakhstan, e-mail: mercaptan@mail.ru
The systems of ternary oxides based on rare-earth elements (REE) and transition metals
possess a number of properties being in demand in the modern industry and therefore their study is
of great interest. This paper presents the results of the calculation of thermodynamic properties of
barium-thulium bismuthate Ba2TmBiO6. A previous paper [1] determines that the sample has a
perovskite structure (space group Fm¯3m) and the coordinates of atoms in a unit cell of the
compound are identified. These data were used in modeling of the compound using the program
LADY [2] that makes calculations on the basis of the theory of crystal lattice dynamics.
At the first step of calculations a unit cell of the compound was built and interatomic
distances were determined. At the second stage vibrational states in the crystal structure of the
compound were calculated in accordance with the model of interatomic potentials. As a
criterion for the correctness of the calculation made the correspondence between the
calculated spectra and the experimental ones was used.
The experimental IR spectrum of barium-thulium bismuth is measured in an infrared
spectrometer Shimadzu 8400S. An absorption band of a complex structure is observed in the
spectrum over the range of 400-800 cm-1. Selection of individual components of this band
(Fig. a) is performed using the programme PeakFit v.4.12 [3]. The peaks that are small in their
intensity correspond to the absorption bands of the unreacted phases.
40 300
35
a b
250
30
200
Cp (S), J/mol·K
25
Intensity
20 150
15
100
10
50
5
0 0
300 400 500 600 700 800 900 1000 1100 1200 1300 0 50 100 150 200 250 300 350
ν, cm-1 Cp (exper) Cp (calc) S (exper) S (calc) T, K
The calculation of vibrational states of the compound in accordance with the model of
interatomic potentials resulted in a good agreement between theoretical and experimental
spectra (Fig. a). On the basis of the obtained vibrational states the density of phonon states is
calculated as well as thermodynamic functions – the heat capacity and entropy. The resulting
design values (Cp298.15=211.45 J/mol·K, S298.15=280.27 J/mol·K) agree well with the
experimental data (Cºp298.15=214.26±0.23 J/mol·K, Sº298.15=277.78±0.73 J/mol·K) [4] (Fig. b).
References
[1] Bissengaliyeva M.R., Knyazev A.V., et al. Structural and thermal investigations of the
synthesized sample of Ba2TmBiO6 composition // 22nd International Conference on Chemical
Thermodynamics ICCT 2012. - Búzios, Brazil, 2012. - P. 288-289.
[2] Smirnov M.B., Kazimirov V.Yu. LADY: Software for lattice dynamics simulations.
Communication of the Joint Institute for Nuclear Research. - Preprint JINR E14-2001-159. -
Dubna, 2001. - 34 p.
[3] http://www.seasolve.com.
[4] Bekturganov N.S., Bissengaliyeva M.R., et al. Experimental determination of the heat
capacity and thermodynamic properties of barium-thulium bismuthate // 22nd International
Conference on Chemical Thermodynamics ICCT 2012. - Búzios, Brazil, 2012. - P. 290.
CALCULATION OF EMBEDDED-ATOM MODEL POTENTIAL FOR IRON

Starukhin V.A., Mirzoev A.A.
South-Ural State University, Chelyabinsk, Russia
e-mail: victor_staruhin@mail.ru
Effective interparticle potential is a main part of a classical molecular dynamics
simulation. For metals embedded atom model potential (EAM) is considered to be a most
adequate one. EAM potential consists of the three functions. The first one is a pair potential;
the second function is an embedding energy and the last one is an effective electron density.
So the total energy of a system is the sum of pair interaction between the atoms plus the sum
of embedding energies of the all atoms. And embedding energy depends on a summary
effective electron density of a particular atom.
However, method for calculation of such potential is not complete. In the present work
we propose the method for calculation EAM potential which is based on the two common
principles. Those are Henderson theorem [1] and universal relation for binding energy (UBE)
of a crystal at absolute zero temperature [2]. Henderson theorem consists in the statement that
there is the one-to-one relation between the effective pair potential and the structure of a
system. But in the work [3] it was shown that numerical calculation of an effective pair
potential on basis of a pair correlation function (PCF) is not unique. But it does not conflict
with Henderson theorem since we can compute a range of the pair potentials which reproduce
the same PCF with very high but not equal precision. In the work [4] we proposed a method
which takes off this ambiguity.
And now we can calculate a pair part of EAM potential on basis of a PCF by means of
the method [4]. Besides it this method gives ability for correcting a pair potential thus a model
PCF does not change. PCF of liquid iron we took from ab initio simulation work [5].
Embedding energy of EAM potential we calculated directly from UBE [2]. Effective electron
density we can calculate on basis of the elastic constants which are known from ab initio
calculations.
Several experimental and calculated properties of the iron are shown in the table. The
first one is a lattice parameter of bcc iron, the second one is cohesion energy, the third fourth
and fifth parameters are elastic constants [6]. All the first five characteristics correspond to
absolute zero temperature. The sixth parameter is an atomic density [7], and the last property
is a self-diffusion coefficient of the iron. Atomic density and self-diffusion coefficient
correspond to 1833 K temperature.
-Ecoh,, D, 10-5
Parameter a0, Å C11, GPa C12, GPa C44, GPa n, Å-3
eV/at. cm2/sec
Literature 2,8553 4,316 243,4 145,0 116,0 0,0756 2,9
Calculation 2,8553 4,316 243,4 145,0 116,0 0,0760 2,6
References
[1] Henderson R.L., Phys. Lett. A, 49, 197, (1974)
[2] Rose J.H., Smith J.R., Guinea F., Ferrante J., Phys. Rev. B, 29, 2963, (1984)
[3] Belashchenko D.K., Russian J. Phys. Chem., 78, №9, 1621, (2004)
[4] Starukhin V.A., Belashchenko D.K., Mirzoev A.A., Vorontsov A.G., Russian
Mettalurgy (Metally), 2012, №8, 705, (2012)
[5] Sobolev A.N., Mirzoev A.A. Fazovye perekhody, uporiadochennye sostoianiia I
novye materialy. 2009. Vol. 12. Pp. 1–4. (in Russ.).
[6] Ackland G.J., Bacon D.J., Calder A.F., Harry T., Phil. Mag. A, 75, 713, (1997)
[7] Waseda Y., The Structure of Non-Crystalline Materials. – New York: McGraw-Hill,
(1980).
MULTI-TEMPERATURE THERMODYNAMIC РROPERTIES

OF REAL MOLECULAR GASES
Stolyarov A.V.
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
e-mail: avstol@phys.chem.msu.ru
To probe the fundamental energy exchange processes between the internal degrees of
freedom in highly non-equilibrium heated medium the thermodynamic and transport
properties of real gases at the translation and/or electronic temperatures up to 100 000K are
necessary. The relevant statistical calculations should apparently account for both interatomic
and intramolecular (so-called non-adiabatic) interactions taking place between the constituent
particles.
We examined the simplified classical and semi-classical theories for multi-temperature
molecular partition sums by comparing with the result of tedious quantum-mechanical
calculations. Our eventual goal was to study whether the classical theory allows one to quickly
calculate molecular thermodynamic and transport properties without compromising accuracy.
It was numerically proved that at low temperatures the calculation should be carried out
by the pure quantum method and non-adiabatic interaction must be often taken into account.
At high temperatures the calculation could be carried out with acceptable accuracy in the
framework of classical mechanics while at intermediate temperatures (ωe~kT) a semi-classical
correction is necessary to imply. The full form of the interacting-particle partition function is
found to be essential to complete and correct calculation of the thermodynamic functions of
the systems. The conventional statistical methods which include only the bound-state sum in
the internal partition function become infeasible since it introduces discontinuities into the
thermodynamic-state function at those points where the bound-state levels pass into the
continuum.
The work has been partially supported by the RFBR grant 11-03-00307а and 7th
European framework program, grant 242311.
CALCULATION OF PHASE EQUILIBRIA IN THE MULTICOMPONENT

POLYMER SYSTEMS
Surikov P.V., Kuleznev V.N.
Lomonosov Moscow State University of Fine Chemical Technologies,
Moscow, Russia
e-mail: surikov@.mitht.ru
The report presents the results of calculations the areas of thermodynamic stability and
phase equilibria in multicomponent polymer systems in the framework of the theory of Flory-
Huggins. A method was used for calculate of phase equilibrium is the construction of the
convex hull that covers function of the free energy mixing of components. This method was
proposed by prof G.F. Voronin. [1].
The results of computer simulation presented:
Diagrams of the thermodynamic stability multicomponent polymer systems bounded by
spinodal curve;
Areas of the homogeneous and heterogeneous phase states restricted by coexistence
curve.
A phase diagrams was obtained for two-and three-component polymer systems,
including solutions of polymers. The good agreement was obtained between the calculated
values and the experimental data on the example of a ternary mixture of polymers (PS -
PMMA - copolymer SAN) [2], which confirms the correctness of the application of the Flory-
Huggins theory for description of phase equilibrium in multicomponent polymer systems
The calculations were shown that the introduction of a third polymer component into the
mixture of the other two polymers can lead to both an increase their mutual solubility and
decrease solubility initial homogeneous solution.
It was demonstrated that systems with three components, in addition to the expected
occurrence of the thermodynamically stable regions near the pure polymer with dissolved
therein another two different polymers, may cause the metastable region in the middle part of
phase diagrams. This area is shifted by varying the molecular weight of the polymer in the
direction corresponding to the excess of the lower molecular weight components of the
polymer mixture. Thus, it was shown that in multicomponent polymer systems the probability
of metastable states is higher than in binary systems.
References
1. Voronin G.F.// Russian Journal of Physical Chemistry, 2005, V. 79, p. 2126.
2. Kuleznev V.N., Surikov P.V. // Polymer Science, Ser. A, 2012, Vol. 54, № 11, p. 833.
FRACTAL DIMENSION OF A NATURAL STRONTIUM SULFATE OF CELESTINE

BASED ON EXPERIMENTAL DATA OF ADIABATIC CALORIMETRY
Taimassova Sh.T., Smolenkov Yu.Yu., Gogol D.B., Ulzhabayev K.M.,
Bissengaliyeva M.R., Bekturganov N.S.
The Institute of Problems of Complex Development of Mineral Resources, Karaganda,
Kazakhstan, e-mail: shynar.taimassova@mail.ru
A multifractal model for describing the heat capacity of crystalline substances [1,2] allows
reproducing the experimental results more accurately in comparison with the Debye model for the
heat capacity and getting data on the structural properties of compounds. The values of fractal
dimensions of a natural mineral - strontium sulfate of celestine have been calculated by this
model based on the experimental data on the heat capacity [3] obtained by means of low-
temperature adiabatic calorimetry.
The smoothed experimental values
of the heat capacity of celestine were used
4
to obtain the calculated values according
3.5
to the equation of multifractal description
3
of the heat capacity at a given value of the
Debye temperature Θ. The fractal 2.5
D
dimension D is determined by the point of 2
convergence of the temperature 1.5
dependence curves found for different 1

0.5 100
Debye temperatures when extrapolated to 300
5
8
12
500
16
25
absolute zero. The fixed values of the 700 Θ

40
55
70
85
100
130
Debye temperature were varied from 160
900
190
220
250
T
280
100 К to 1000 К using a pitch of 50 K.
310
The curves of temperature dependence of the fractal dimension of celestine have a tendency
to convergence at value of D = 3, testifying that a compound has the spatially ordered structure.
The figure shows a conventional surface displaying the value of the fractal dimension over the
range 1<D<4. The values are the solutions of equation of the multifractal model of the heat
capacity for the case of experimental temperature dependence of the heat capacity of celestine.
The value of the characteristic Debye temperature for celestine: Θ = 870 К has also been
determined on the basis of the obtained sets of curves of fractal dimension calculated using a
smaller pitch (10 К). Thus, celestine proves itself as a compound having three-dimensionally
ordered structure and it is characterized by covalent type of bonding in the structure.
References
[1] Izotov A.D., Gavrichev K.S., Lazarev V.B., Shebershneva O.V. The temperature
dependence of the heat capacity of substances with multifractal structure // Inorganic
materials. - 1994. - V. 30, № 4. - P. 449-456 (in Russian).
[2] Lazarev V.B., Izotov A.D., Gavrichev K.S., Shebershneva O.V. Fractal model of heat
capacity for substances with diamond-like structures // Thermochimica Acta. - 1995. - Vol.
269/270. P. 109-116.
[3] Bissengaliyeva M.R., Gogol D.B., Bekturganov N.S., Taimassova Sh.T. Experimental
determination of thermodynamic characteristics of natural strontium sulphate // XVIII
International conference on chemical thermodynamics in Russia RCCT 2011. - Samara,
2011. - Vol. 1. - P. 47-48.
ANALYSIS AND APPROXIMATION OF THE DATA ON MEMBRANE

MASS-TRANSFER PROCESSES ON THE BASE
OF NONEQUILIBRIUMTHERMODYNAMICS APPROACH
Toikka А.M.
Saint-Petersburg State University, Department of Chemical Thermodynamics and Kinetics,
Saint-Petersburg, Russia, e-mail: alexander.toikka@chem.spbu.ru
Membrane processes are well-known and practically significant objects of physical
chemistry. The description of membrane systems is a classical task of general and
nonequilibrium thermodynamics. Among membrane systems one should distinguish
membrane equilibrium (e.g. osmotic equilibrium) and nonequilibrium states. Nonequilibrium
membrane systems have more significance because of numerous practical applications. In the
case of osmotic phenomena it could be osmosis and reverse osmosis. In both cases there are a
pressure and concentration gradients in membrane. Accordingly these processes should be
considered as nonequilibrium ones.
Nonequilibrium approach for the thermodynamic analysis of membrane process is well-
known. Kedem (1986) was one of the first who introduce some elements of nonequilibrium
thermodynamics in the theory of pervaporation (evaporation through membrane, PV). First of
all the theory was applied for the description of the coupling between fluxes. Unfortunately
the further development of the thermodynamic theory of PV was not so intensive and only few
works of last decade were based on nonequilibrium thermodynamic approach. The PV usually
is considered on the base of “solution-diffusion model” [1]. The same model applies to gas
permeation and reverse osmosis in polymer films.
In this lecture some problems of the consideration of membrane processes on the base of
nonequilibrium thermodynamics approach are discussed. The main object is a case of mass-
transfer in PV process: some examples with the use of experimental data are presented. For
the fluxes in PV we apply classical phenomenological equations (linear laws). For the small
fluxes (usual for the PV) the feed solution can be considered as a system in an equilibrium
state. Accordingly the equilibrium data on thermodynamic properties of feed could be used.
The sorption (as the initial stage of PV) can be also considered as an equilibrium process if the
rate of diffusion through membrane is low. For the approximation of the dependence of
permeate composition on feed properties the limited set of pervaporation data should be
involved in calculation procedure, first of all for the determination of kinetic coefficients
values. The coupling between fluxes is taken into account. The conception of driving forces in
mass-transfer in PV process is discussed. Some additional assumptions concerning
thermodynamic forces in PV are also considered.
For general case of membrane systems some results may be also obtained with the use
of classical methods of thermodynamics, such as stability conditions or thermodynamic
inequalities. The opportunities and advantages of the use of thermodynamic inequalities for
the description and analysis of membrane systems in general are presented. Particularly the
inequalities for the analysis both equilibrium and nonequilibrium stages of membrane
processes will be presented.
This research was supported by Russian Foundation for Basic Research (grant 12-03-
00522a). Author is also grateful to colleagues in pervaporation study, Galina Polotskaya,
Anastasia Penkova and Alexandra Pulyalina.
Reference
[1] Baker R.W. Membrane Technology and Applications. N.Y.: McGraw-Hill, 2000.
814 p.
INFLUENCE OF COMPOSITION OF WATER-ETHANOL SOLUTION ON STABILITY

OF COMPLEXES OF D-METALS WITH ANIONS OF MALEIC AND SUCCINIC ACIDS
Tran Thi Dieu Thuan, Tukumova N.V., Usacheva T.R., Sharnin V.A.
Ivanovo State University of Chemistry and Technology,
Institute of Thermodynamics and Kinetics of Chemical Processes, Ivanovo, Russia
e-mail: oxt@isuct.ru
In this article , acid-base properties of maleic and succinic acids ,as well as composition
and stability of coordination compounds of the copper (II), nickel (II) and kobalt (II) ions with
them have been investigated by potentiometric titration at 298 K and I=0.1M (NaClO4) in
water-ethanol solutions with composition mole fraction of alcohol X= 0÷0,4.
Mathematical processing of the experimental data, which was carried out by the
standard program "pHMETR"[1], showed that copper (II), nickel (II) and kobalt (II) ions with
succinic anion form particles ML and MHL in the all mole fraction of the alcohol , but with
maleic anion only particles ML. It is found that the increase in the constant dissociation pK1
and pK2 of maleic and succinic acids occurs under the increase in ethanol content in solution.
Composition of the water -ethanol mix similar affects on both pK1 and pK2 dissociation of
acetic acid [2] and on pK1 amino-acetic acid [3]. The values of the stability constants of
complexes between Cu2+, Ni2+ and Co2+ ions with maleic acid in water-ethanol solutions the
first were obtained.
In water ion Cu2+ form with anions of succinic and maleic acids complexes more stable
than ions Ni2+ , Co2+, which corresponds to the conventional Irving-Williams series
(Zn2+ < Cu2+ > Ni2+ > Co2+). In studied compositions of solvent H2O-EtOH the ratio remains.
The increase in ethanol content in solution leads to an increase in the stability of
complexes Cu2+,Ni2+ and Co2+,as a consequence ,to an increase in negative values of energy
Gibbs for the reactions of their formation. In studying reactions of complex formation of
acetate and glycinate nickel (II) in water-ethanol solutions were found [4,5], that the main
contribution to shift balance in the complex makes ligand desolvation with increasing
concentrations of ethanol and for thermodynamics reactions of amine and carboxylate
complexes of transitive metals in water- organic solutions. It is assumed that solvation
effects of the ligands plays a similar role in the formation of complexes Cu(II) and Co(II)
with maleic and succinic acids.
References
[1] V.А.Vorodin, Е.V.Kozlowski, V.P.Vasiliev// J. Inorg. Chem. 1986. 31. P.10.
[2] V.А.Ysaeva, V.A. Sharnin, V.А.Shormanov// J. Phys. Chem. 1997. V.71.№8. P.
1371.
[3] V.А.Ysaeva, V.A. Sharnin, V.А.Shormanov, I.А. Baranova // J.Phys.Chem. 1996.
V.70.№8. P. 1421.
[4] V.А.Ysaeva, V.A. Sharnin, V.А.Shormanov // J. Phys. Chem. 1998. V.72.№12. p.
2182.
[5] V.А.Ysaeva, V.A. Sharnin, V.А.Shormanov // Coor. Chem. 1999. V.25.№12. P. 912.
The work was supported by the Federal Program "Scientific and scientific-pedagogical
personnel of the innovation Russia" for 2009 - 2013 years, the agreement № 14.B37.21.0801.
МOLECULAR COMPLEXATION IN AQUEOUS–ORGANIC SOLUTIONS

OF CROWN ETHERS AND AMINO ACIDS
Usacheva T.R.
Ivanovo State University of Chemistry and Technology, Research Institute of
Thermodynamics and Kinetics of Chemical Processes, Ivanovo, Russia, e-mail: oxt@isuct.ru
In this abstract we discuss the influence of water-ethanol (H2O-EtOH), water-
dimethylsulfoxide (H2O-DMSO) and water – acetone (H2O-MeAc) mixed solvents on the
molecular complex formation between some amino acids (AA) such as glycine (Gly), D,L-alanine
(Ala), L-phenylalanine (Phe) and 18-crown-6 ether (18C6):
AAsolv + 18C6solv ↔ [AA18C6]solv (1)
Analysis of the interdependence between the thermodynamic reaction parameters (Gibbs
energy, enthalpy and entropy) of complex formation and the thermodynamic parameters of
reagent solvation is employed to reveal regularities and peculiarities of the influence of solvent
composition on formation of [AA18C6]. An increase of lgKo([AA18C6]) and of exothermicity for
∆rH°([AA18C6]) with increasing the non-aqueous component mole fraction in mixed solvents is
observed as a common effect for all studied media.
The discussion and interpretation of this phenomenon is based on the solvation
thermodynamic approach [1], according to which the influence of solvent composition change
can be quantitatively described by the thermodynamic transfer functions of reaction (∆trY°r) and
of reagents (∆trY°(Z)):
∆trY°r =∆rY°(sol)-∆rY°(H2O) (2)
∆trY°(Z)=∆Y°(Z)(sol)-∆Y°(Z)(H2O) (3)
where ∆rY° are the thermodynamic reaction parameters of reaction ore solvation of reagents
(∆G°, ∆H°, T∆S°) in mixed solvent (sol) and in water.
The analysis of the solvation enthalpy contributions of AA, ∆trH°(AA), 18C6, ∆trH°(18C6),
and [AA18C6], ∆trH°([AA18C6]), to the reaction enthalpy transfer, ∆trH°r, shows that the
strengthening of the desolvation of 18С6 and AA with increasing of the concentration of EtOH,
DMSO or MeAc in the mixed solvent favors the increase of the reaction exothermicity. The
thermodynamic ratios αdif [2] are used for estimating the enthalpy changes for [AA18C6]
formation reaction of in the studied solvents:
∆trH°r, calc= (αdif– 1)∆trH°(18C6) (4)
The good agreement between ∆trH°r.calc and ∆trH°r in the examined composition range of the
mixed solvents allows to estimate the influence of Н2О-EtOH, H2O-DMSO, Н2О-МеАс solvent
composition on the energetics of [AA18C6] formation reaction at the solvent compositions with
high concentration of non-aqueous components where the very low solubility of amino acids
makes impossible the experimental determination of the reaction enthalpy.
The relationship between the solvation contributions of the reagents for the Gibbs energy
change of reaction transfer from water into Н2О-EtOH and H2O-DMSO solvents is essentially
different from those corresponding for the enthalpy change and reveals the prevailing role of the
desolvation contribution of AA, ∆trGo(AA), in determining the Gibbs energy of transfer of
reaction from water in water-organic solvents.
This work was supported by the program “Research and scientific-pedagogical personnel
of innovative Russia for 2009-2013 years”, state contract 14.B37.21.0801.
References
[1] G.A. Krestov. Ionic Solvation //Ellis Horwood, New-York-London- Toronto-Sydney-
Tokyo-Singapore, 1994, 347 p.
[2] V.A. Sharnin // Russ. J. Gen. Chem. 1999, V. 69, p. 1421.
3D COMPUTER MODELS OF T-X-Y DIAGRAMS FOR LEAD-FREE SOLDERS

Vorob’eva V.P., Lutsyk V.I., Shodorova S.Y., Nasrulin E.R.
Institute of Physical Materials Science SB RAS, Ulan-Ude, e-mail: vluts@ipms.bscnet.ru
Different methods of thermodynamic calculation (CALPHAD, convex hull method, …) and
experimental investigation of phase diagrams may produce different results. For instance, the T-x-y
diagram section 300оС of the system Au-Bi-Sb=A-B-C with compounds Au2Bi=R1, AuSb2=R2
includes the homogeneous region of Bi(Sb)=B(C) solid solution near the binary system Bi-Sb
(Figure, b, c) or 2-phase region Bi(Sb)+AuSb2=B(C)+R2 (Figure, a, d). Contradictions like this can
be settled by 3D computer model. Firstly it represents only a prototype of phase diagram (PD).
Later it is possible to get more perfect model with the improved characters of the surfaces.
However even the PD prototype serves as a tool of PD topological accuracy, because
thermodynamic rules are fulfilled in these variants of PD. So, 3D computer model of the Au-Bi-Sb
T-x-y diagram (Figure, e) shows, that 2 surfaces of solidus and solvus, which serve as borders
between the region B(C) and L+B(C) & B(C)+R2 regions, have been lost [1, 3]. In the same way
3D computer model [5] had found out mistake in the isothermal section 221oC and some errors in
the isopleth Ag-Cu18Sn82 of the system Ag-Cu-Sn [1].
Figure. Isothermal section 300оС: [1] (а), [2] (b), [4] (c), [3] (d), 3D computer model (e);
solidus and solvus, missed by [1, 3], are shown by red color (e).
References
[1] Atlas of Phase Diagrams for Lead-Free Soldering compiled by Dinsdale A., Watson A.
et al. COST 531. ESF, Brno, Czech Rep.: Vydavatelstvi KNIHAR, 2008. V. 1. 289 p.
[2] Wang J., Meng F.G., Liu H.S. et al //J. Electron Mater. 2007. V. 36. No 5. P. 568.
[3] Manasijevica D., Minicb D., Zhivkovica D. et al //J. of Physics and Chemistry of Solids.
2008. V. 69. No 4. P. 847.
[4] Prostakova V.A., Goryacheva V.I., Kutsenok I.B. //MSU Vestnik. Chemistry. 2011. V.
52. No 2. P. 83 (http://td.chem.msu.ru/?page_id=638) (In Russian).
[5] Lutsyk V.I., Vorob’eva V.P. Reasons for Contradiction of T-x-y Diagram Au-Bi-Sb
//Scientific Journal “Proceedings of the International Conference NANO Materials:
Applications & Properties”. 2012. Vol. 1. No 4. P. 04NMEEE02-1 - 04NMEEE02-4.
UNIVERSAL METHOD FOR DESCRIPTION OF THERMODYNAMIC PROPERTIES

OF SOLIDS BY HARMONIC OSCILATOR FUNCTIONS
Voronin G.F., Kutsenok I.B.
Lomonosov Moscow State University, Moscow, Russia
e-mail: voronin@td.chem.msu.ru
Universal formulas for the analytical description of the standard thermodynamic
functions СPo(Т), So(T), Ho(T) – Ho(Tref) of solids with accuracy corresponding to the accuracy
of their experimental measurements have been proposed. The description is based on the
usage of a linear combination of thermodynamic functions of the harmonic oscillator (Planck-
Einstein functions) unadjusted to the difference between isobaric and isochoric values of the
heat capacity.
The expression for approximation of the temperature dependence of the molar isobaric
heat capacity is the following:
m
CP (T ) = ∑ αi CE ( θi / T ),
i =1
where CE(x)=3Rx exp(x)/[exp(x)−1]2 is the molar heat capacity of the 3D harmonic

2
oscillator in the Planck-Einstein model; x=θ/T; αi and θi are the approximation parameters.
The physical significance of αi is the statistical weight of the i-th mode in the vibrational
spectrum of a crystal, θi is the characteristic temperature of the i-th oscillator. The temperature
dependencies of other thermodynamic functions can be derived from this expression by using
well-known thermodynamic relations.
The unknown approximation parameters were calculated by the solution of
simultaneous nonlinear equations by the least square method. The objective functions in the
calculations were the relative and absolute deviations of estimated values from experimental
data. The obtained results were characterized by the standard, average and maximum errors of
the calculated values as well as by the errors of the approximation parameters (αi and θi).
The reliability of the proposed approach was tested on numerous examples of different
types of compounds from solid argon and metals to complex multicomponent oxide phases,
minerals and organic substances. In all cases, the adequate description of experimental and
tabular data within the whole temperature range was received even if there were some
peculiarities on the curves of the temperature dependences of the corresponding
thermodynamic properties. At that, the number of the αi and θi approximation parameters did
not exceed 12.
The physical validity of the proposed functions used for experimental data
approximation gives the opportunity to extrapolate them beyond the limits of the temperature
range where they were studied. It enables to estimate for example the thermodynamic
properties of phases in the absence of the low temperature data.
The possibility of joint description of different thermodynamic properties of compounds
by a unified set of parameters facilitates the mutual consistency of these functions and the
compact storage of the thermodynamic information in data bases and reference books.
ESTIMATION OF THERMODYNAMIC PROPERTIES OF ALUMINOSILICATES

BY A GROUP CONTRIBUTION METHOD
Voronin G.F., Kutsenok I.B., Makarov P.Y.
Lomonosov Moscow State University. Moscow, Russia
e-mail: ibk@td.chem.msu.ru
The purpose of this work is to develop a new approach for estimating thermodynamic
properties of individual aluminosilicates based on their structure and composition. The
approach allows to estimate unknown thermodynamic properties, namely the temperature
dependency of the isobaric heat capacity Cp(T), standard entropy (S0298.15), standard enthalpy
of formation (ΔfHо298.15) and molar volume (V298.15) of complex multicomponent compounds
in the wide temperature range and to evaluate the errors of these values.
A group contribution method based on summing up the contributions of the structure
fragments of a compound multiplied by corresponding stoichiometric coefficients was used.
The method permits to take into account the chemical composition of compounds and their
crystal structure. For instance, it is possible to consider in calculations to the presence of
structural polyhedra with the interatomic positions exchange and forming of ordered and
disordered phases. The neutral and charged atomic groups corresponding to Na2О, K2О, CaО,
MgО, FeО, Fe2O3, SiO2, Al2O3 (Al both in tetrahedral and octahedral surrounding) oxides, as
well as H2O, ОН-, SO42-, CO32- и Cl- were selected as increments. One of the features of the
developing approach is the use of a linear combination of Einstein functions for accurate
approximation of the temperature dependence of the heat capacity in a wide temperature
range.
The method was implemented in the form of a MATLAB software complex consisting
of 3 program modules. The first modue is the data base contains the thermodynamic
properties (ΔfHo298,15, So298,15, Cp(T), V) of aluminosilicates known from the literature sources.
At the present time the thermodynamic information for about 165 compounds is included in
the data base. The second module is the computer program calculating the optimal group
contributions by the linear regression method using the information from the data base. The
values of group contributions and the standard errors of these values are the results of these
calculations. The third module enables to calculate the thermodynamic properties of
compounds under investigation and to estimate the errors of these properties. The correctness
of the method was proved on a number of substances (tetranatrolite, paranatrolite, heulandites,
gmelinite etc.). The thermodynamoc properties of cancrinite, mordenite, mesolite, natrodavine
and hydromagnesite were calculated for the first time in the temperature range from 0 to 1200
K. The errors of estimated heat capacity values do not exceed 4% at Т≥250 К. At lower
temperatures, the errors increase up to ~10%. It is due to the lack of sufficient number of
reliable low temperature heat capacity values in our data base.
The developed incremental approach might be effectively applied for obtaining an
internally consistent thermodynamic dataset of solid compounds in the wide temperature
range. These data are required for the phase equilibria calculations in hydrated aluminosilicate
systems.
This work was supported by RFBR (grant # 13-03-00328).
THE INFLUENCE OF THE REAGENTS SOLVATION ON THE REACTION

OF MOLECULAR COMPLEX FORMATION BETWEEN 18-CROWN-6
AND L-PHENYLALANINE IN Н2О–EtOH AND H2O–DМSО SOLVENTS
Voronina S.I., Usacheva T.R., Sharnin V.А.
Ivanovo State University of Chemistry and Technology, Ivanovo, Russia, e-mail: oxt@isuct.ru
The influence of the reagents solvation on the enthalpy changes of the molecular
complex formation reaction between 18-crown-6 (18C6) and L-phenylalanine (Phe),
Phesolv + 18C6solv ↔ [Phe18C6]solv, as well as on the stability of the molecular complex
[Phe18C6] in Н2О-EtOH and Н2О-DМSО mixed solvents was analyzed.
The analysis of interdependences of the thermodynamic parameters of reagents
solvation and the reaction was based on the solvation thermodynamic approach [1]. The
transfer thermodynamic functions (∆trY0 ≡ ∆trG0, ΔtrH0) of the reagents solvation and of the
reaction were applied for revelation the solvation contributions that determine the reaction
enthalpy change and the complex stability at the transfer from water into water-organic
solvents. The analysis of the reagents solvation contribution into ∆trG0r revealed the dominant
influence of the changes in the solvation state of Phe, (∆trG0(Phe)), in the Н2О-EtOH solvents
(fig.1a). The changes in the solvation state of [Phe18C6], (∆trG0([Phe18C6])), are close to the
∆trG0(18C6) values, it is points to the determining role of 18C6 in the formation of the
solvation shell of [Phe18C6]. The solvation contributions interrelation into the reaction
enthalpy change, (∆trН0r), (fig. 1b) is different from their ratio into ∆trG0r: ∆trН0r is determined
by the change in the solvation state of 18C6 in both Н2О-EtOH and Н2О-DМSО solvents.
а 4
∆trG0, кJ/mol
60
b
∆trH0, кJ/mol
10 1 40 1
5
2 20 5 2
0
3 0
-5 -20
4 6 3
-10 -40
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0
X(EtOH), mol.fr. X2, mol.fr.
Fig.1 а,b. The thermodynamic transfer functions of the reagents solvation and the reaction
of [Phe18C6] complex formation. а):1-∆trG0(Phe) [2]; 2-∆trG0(18C6) [3]; 3-∆trG0([Phe18C6]);
4-∆trG0r [2]. b)1,4-∆trН0(18C6) [4]; 2,5-{∆trН0([Phe18C6])-∆trН0(Phe)}; 3,6-∆trН0r [2,5];
1,2,3- H2O-EtOH; 4,5,6- H2O –DМSО.
This work was carried out at the Research Institute of Thermodynamics and Kinetics of
Chemical Processes and was supported by the program “Research and scientific-pedagogical
personnel of innovative Russia for 2009-2013 years”, state contract 14.B37.21.0801.
References
[1] G.A. Krestov. Ionic Solvation //Ellis Horwood, New-York-London- Toronto-Sydney-Tokyo-
Singapore, 1994, 347 p.
[2] T.R. Usacheva, V.A. Sharnin, I.V. Chernov, et al. // Chem.Phys.Lett., 2012, V. 543, p.155.
[3] T.R. Usacheva, I.A Kuzmina, М.О. Dzumasheva, et al. // Izv. Vyssh. Uchebn. Zaved. Khim.
Khim. Tekhnol., 2010, V. 53, N. 12, p. 51.
[4] V.A. Sharnin, S.F. Ledenkov, T.R. Usacheva, et al. // Izv. Vyssh. Uchebn. Zaved. Khim. Khim.
Tekhnol., 2000, V.43, N. 5, p. 87.
[5] T.R.Usacheva, I.V. Chernov, V.A. Sharnin, et al. // J. Therm. Anal. Calorim.
DEVELOPMENT OF THE CONVEX HULL METHOD FOR CONSTRUCTION

OF PHASE DIAGRAMS OF MULTICOMPONENT SYSTEMS
Voskov A.L., Maksimov A.I., Kutsenok I.B., Belov G.V.
Lomonosov Moscow State University, Moscow, Russia
e-mail: alvoskov@gmail.com
Assessment of phase diagrams of multicomponent systems is an actual problem of
chemical thermodynamics. The convex hull method that became widespread in recent times
has several important advantages: it provides a reliable detection of the Gibbs energy global
minimum and doesn't require an initial approximation [1]. This method was implemented
earlier in PhDi and TernAPI program complexes for binary and ternary systems respectively in
the Laboratory of Chemical Thermodynamics of MSU [2,3].
Recently a significantly revised and extended version of the TernAPI software complex
was created. In comparison to the previous version it doesn't require bulky runtime libraries of
MATLAB environment, consumes significantly less system resources and contains several
new features:
• increased reliability of the ternary phase diagram regions recognition near special points
(eutectic, peritectic etc.) based on the improvements of the convex hull projection analysis
algorithm;
• transition to phase diagrams in intensive thermodynamic coordinates, e.g.
composition—chemical potential etc;
• improved user interface and phase diagrams visualization
• extended database containing thermodynamic models of ternary systems and separate
phases
The developed software complex exists in three variants: an educational demo-version,
full version and demonstration on-line version for installation on a WEB-server.
In this work, a task for the physical chemistry students’ laboratory course at the
Chemistry Department of MSU was developed specially for the educational version of the
TernAPI program. It consists of theoretical and experimental parts. The experimental part
includes constructing the ethylacetate-2-propanol-water and ethylacetate-2-butanol-water
phase diagrams by turbidimetric titration; the theoretical one includes its calculation based on
existing thermodynamic models and is used for planning experiments.
This work was financially supported by the Russian Foundation of Basic Research
(Projects No. 11-03-00499a and 12-03-31069-mol_a).
References
[1] Voronin G.F. // Russ. J. Phys. Chem. A. 2003. V. 77(10). P. 1685-1694.
[2] Belov G.V., Emelina A.L. et al. // J. Alloys Comp. 2008. V. 452. P. 133-135.
[3] Voskov A.L., Voronin G.F. // Russ. J. Phys. Chem. A. 2010. V. 84(4). P. 525–533.
МАТЕМАТИЧЕСКОЕ И ФИЗИЧЕСКОЕ МОДЕЛИРОВАНИЕ ЗАЖИГАНИЯ СЛОЯ

ЛЕСНЫХ ГОРЮЧИХ МАТЕРИАЛОВ СФОКУСИРОВАННЫМ
СОЛНЕЧНЫМ ИЗЛУЧЕНИЕМ
Барановский Н.В., Кузнецов Г.В.
Национальный исследовательский Томский политехнический университет
Томск, Россия
e-mail: firedanger@narod.ru
Причины возникновения лесных пожаров достаточно разнообразны [1] и могут
иметь как антропогенное, так и природное происхождение. Однако, в статистических
данных заметная доля пожаров фигурирует с формулировкой “причина возникновения
не установлена” [1] или “по вине человека”. Причем последний вариант используется
достаточно часто, если истинная причина возгорания не установлена. Например,
нередко в средствах массовой информации все причины пожаров разделяют на две
группы: “следствие грозовой активности” и “по вине человека”. При таком подходе к
оценке причин возникновения пожаров трудно разрабатывать конкретные мероприятия
по предотвращению лесных пожаров. В тоже время, согласно правилам пожарной
безопасности в лесах запрещается разбрасывать стеклянные бутылки [2], так как они
или их осколки могут сфокусировать солнечное излучение и вызвать возгорание ЛГМ.
До настоящего времени теоретический анализ условий возгорания ЛГМ под
действием солнечного излучения не проводился. В частности, нет достоверных оценок
минимальных значений радиационных тепловых потоков, при которых возможно
зажигание, например, сухой хвои. Для мониторинга и прогноза лесных пожаров по
таким неочевидным причинам, как сфокусированное солнечное излучение, следует
разработать соответствующие методики прогноза на основе детерминированных
моделей зажигания ЛГМ радиационным тепловым потоком.
Цель исследования – численное моделирование условий зажигания слоя ЛГМ в
результате воздействия сфокусированного потока солнечного излучения.
Процесс воспламенения слоя ЛГМ сфокусированным потоком солнечного
излучения описывается системой одномерных нестационарных нелинейных уравнений
теплопроводности и диффузии с соответствующими начальными и граничными
условиями. Численная реализация проведена с использованием конечно-разностного
метода. Многомерные уравнения решены локально-одномерным методом. Разностные
аналоги одномерных уравнений теплопроводности и диффузии решены методом
прогонки в сочетании с методом простой итерации.
На основании результатов выполненных теоретических исследований можно
сделать вывод о целесообразности учета рассмотренного в данной работе фактора в
системах прогноза лесной пожарной опасности. Решение поставленной задачи имеет
важное значение для развития теории зажигания ЛГМ. Полученные результаты
создают базис для дальнейшего развития физико-математических моделей зажигания
ЛГМ и других пожароопасных материалов.
Литература
[1] Кузнецов Г.В., Барановский Н.В. Прогноз возникновения лесных пожаров и их
экологических последствий. Новосибирск: Изд-во СО РАН, 2009. 301 С.
[2] Об утверждении Правил пожарной безопасности в лесах : постановление
Правительства РФ от 30 июня 2007 г. № 417 // Пожарная безопасность. 2007. № 4.
ТЕРМОДИНАМИЧЕСКИЕ ПАРАМЕТРЫ АДСОРБЦИИ ОРГАНИЧЕСКИХ

МОЛЕКУЛ НА МОДИФИЦИРОВАННЫХ ПРОИЗВОДНЫМИ
УРАЦИЛА СОРБЕНТАХ
1
Гайнуллина Ю.Ю., 1Гуськов В.Ю., 2Иванов С.П., 1Кудашева Ф.Х.
1
Башкирский государственный университет, Уфа
2
Институт органической химии УНЦ РАН, Уфа
e-mail: umashkova@mail.ru
Некоторые гетероциклические соединения способны образовывать ассоциаты
сложного строения – супрамолекулярные структуры. В зависимости от количества
водородных связей , образуемых мономером , такие структуры могут быть двух типов:
ленточные и сетчатые. Последние представляют интерес в связи с наличием в их
структуре полостей определенного размера и полярности. Это делает возможным
создание на их основе стереоселективных сорбентов, способных выборочно
абсорбировать определенные органические молекулы. Следовательно, представляет
интерес разработка сорбентов на основе сетчатых супрамолекулярных структур. В
настоящей работе исследованы сорбционные термодинамические свойства сорбентов с
нанесенными сетчатыми структурами урацила, 6-метилурацила и 5-гидрокси-
6метилурацила.
В качестве исходного сорбента был выбран пористый полимер на основе
стирола и дивинилбензола с удельной поверхностью 800 м2/г. и средним диаметром
пор 25 Е. Модифицирование осуществлялось из водных растворов при температуре при
600С путем отгона растворителя . Исследование проводилось на хроматографе
«CHROM 5» с детектором по теплопроводности в интервале температур 180-2000С. В
качестве сорбатов были выбраны органические вещества различной породы. Пробы
вводили в виде разбавленных паровоздушных смесей объемом 10 мкл. Полученные
значения удерживаемых объемов были равны константе адсорбционно-десорбционного
равновесия - константе Генри. Из зависимости логарифма удерживаемого объема от
обратной температуры были рассчитаны мольные изменения внутренней энергии и
энтропии адсорбции.
Установлено, что значения удерживаемых объемов на модифицированных
сорбентах будут больше чем на исходном образце. Это свидетельствует о том, что
супрамолекулярная структура не забивает поры полимера, а располагается по
поверхности и вносит дополнительный вклад в удерживание. Показано, что вклад
специфических взаимодействий в свободную энергию адсорбции на
модифицированных образцах возрастает по сравнению с исходным сорбентом, в
первую очередь, за счет донорно-акцепторных связей между урацилами и молекулами
адсорбатов.
Была обнаружена зависимость энергии и энтропии адсорбции от размера молекул.
Показано, что наблюдаемые явления хорошо коррелируют с размерами полостей
соответствующих супрамолекулярных структур , определенных по данным
рентгеноструктурного анализа. Для конформационно жестких молекул реальный
размер полостей был меньше для тех супрамолекулярных структур , для которых
полости имели внутри различные функциональные группы. Установлено, что на
свойства получаемых сорбентов влияет количество модификатора.
Полученные сорбенты могут быть рекомендованы для селективного извлечения
токсикантов из атмосферного воздуха.
НЕДОУМЕНИЯ В ТЕРМОДИНАМИКЕ
Прохоренко Н.Н.
Московский государственный университет тонких химических технологий
им. М.В. Ломоносова, Москва
e-mail: rcct-13@mail.ru
Одна из проблем Гильберта – аксиоматика физики – в настоящее время так и не
решена. Термодинамика, как часть физики, не избежала этой участи. Основатели
термодинамики пошли путем феноменологии: «Я так вижу ситуацию и только
господин опыт мне судья.»
По аналогии с теоретической механикой вводится количественная мера
взаимодействия в виде произведения потенциала на дифференциал сопряженной
координаты. Далее по аналогии с записью полного дифференциала некоторой функции
многих переменных предлагается универсальная термодинамическая форма записи
первого закона термодинамики, т.е. закона сохранения энергии:
N
dU ∑
=
1
P ( x , x , x ,...x )dx .i
i 1 2 3 N i 1, 2,3,...N . Здесь U – внутренняя энергия ТС, Pi(…) –
потенциал i- го взаимодействия, xi – его сопряженная координата состояния, N – число

разных видов взаимодействия, число степеней свободы, размерность задачи. Функции
Pi (...) назвали уравнениями состояния. Получение явных функциональных
зависимостей Pi (...) не является проблемой термодинамики, это дело потребителей.
Если вдруг dU у потребителя окажется полным дифференциалом (а это легко
проверяется), то далее термодинамический метод анализа начинает корректно работать.
Вот это «вдруг» и составляет смысл первого недоумения. По закону вредностей
N
Паркинсона полученная линейная дифференциальная форма ∑ P (...)dx никогда
1
i i
не
будет полным дифференциалом. Термодинамика умерла! А на практике и в

технической термодинамике и в физической химии спокойно применяют аппарат
термодинамики с умолчанием о неполноте дифференциала внутренней энергии, не
подозревая о некорректности.
Многочисленная литература о применении термодинамики в каких-то
прикладных задачах демонстрирует удивительную «свободу» изменять число внешних
воздействий и умолчания о неполноте дифференциала. И это составляет смысл второго
недоумения. Можно строго показать, что эта «свобода» правомерна только при
специальном виде уравнений состояния. Кажется, в природе нет таких веществ с таким
видом.
Рассмотрим термо-деформационную ТС: dU = Tds − pdv. Можно строго показать,
что dU будет полным дифференциалом при T=const и для ТС с идеальным газом. Если
же T ≠ const , то для идеального газа полным дифференциалом будет dU ( s, v) / T ( s, v) , а
dU ( s, v) - нет. Тем не менее, техническая термодинамика, физическая химия
применяют термодинамический метод анализа, не подозревая о некорректности. И в
этом состоит смысл третьего недоумения.
Четвертое недоумение озвучил Опарин Е. Г. После тщательного анализа
предпосылок теоретического рассмотрения Клаузиуса и его вывода о существовании
энтропии автор очень засомневался: «А существует ли в природе такая ситуация, чтобы
все (7) предпосылок реально выполнялись?» Следовательно, энтропии не существует,
термодинамика умерла, второго закона термодинамики в природе не существует.
FOR NOTES
Section 2
Thermodynamics
of individual chemical
compounds
CORRELATION MODELS IN THE STUDIES OF ORGANIC AMIDES

Abramova G.V., Tulegenov A.S.
al-Farabi Kazakh National University, Almaty
e-mail: abramova_1954@mail.ru
Amides are one of the most abundant compounds in nature. Their properties make them
distinct in the row of organic molecules. Thus, amides may be considered as the prototypes of
bioorganic molecules, the CO-NH bond is the basic structural unit of proteins. The hydrogen
bonds between amide linkages are the cause of existence of secondary structure of proteins. Low
molecular amides, such as dimethylformamide are common solvents. Synthetically obtained
polyamides are widely used in the form of various resilient materials. Thus, the possibility of
prediction and theoretical prognosis of the structure and properties of amides of various classes of
hydrocarbons is important for technological and fundamental scientific applications. In present
work, the possibility of creation of extrapolation schemes for the prognosis of thermodynamic
properties of amides was explored.
The quantum-chemical computations of electronic structure of the row of amides
(HCONH2, CH3CONH2, C2H5CONH2, C3H7CONH2, C4H9CONH2) were carried out using PM3
(Parametrized Model 3), SCF (Hartree-Fock) and MP2 (Moller-Plesset second order perturbation
theory) methods. For ab-initio computations cc-pvdz basis set was. The molecular geometric
configurations were optimized at PM3 level and later used for ab-initio computations. The least
squares method was used in order to estimate the degree of correlation between various
measurable quantities. The degree of correlation was estimated by computation of correlation
coefficient. The linear formula was utilized y=K*x+b. Six parameters were used for building
(arguments,functions) pairs of properties: number of carbon atoms, PM3 energy, SCF energy,
MP2 energy, PM3 enthalpy of formation, experimental enthalpy of formation.
The correlation coefficients of obtained models are close to 1, which implies the linear
character of correlation and correctness of chosen model. In addition, the fact, that the values of
correlation coefficients are close to 1.0 implies that it is possible to carry out linear extrapolations
for every pair of properties.
Analysis shows that lowering of absolute value of ionization potential leads to the increase
of protonation energy. Protonation energy may be used as an indicator of adsorption properties, as
it characterizes the energy of interaction between the molecule and proton, and proton may be
considered as a simplest field point resembling a molecule.
Of primary interest for this work is the linear correlation between total electronic energies
of molecules and experimental enthalpies of formation of amides. Such linearity may allow the
prognosis of properties of unknown compounds based on the result of ab initio computations.
Another interesting dependence is between PM3 and SCF energies. This relationship opens new
possibilities for “intermethod” extrapolations, where the exact SCF energy is hard to find due to
complexity of the molecular system. The third important correlation observed is the linear
relationship between the electron correlation energy and the number of atoms and the linear
relationship between the electron correlation energy and SCF total electronic energy for the
homologous series of amides. Such linearity opens new possibilities for “intermethod”
extrapolations in the series of homologues. The fourth interesting correlation is the linear
relationship observed between the natural logarithm of the ionization potential and the
protonation energy. This correlation indicates the importance of intramolecular charge transfer
effects in determining the degree of protonation energy, and, hence, the strength of adsorption,
which can not be explained solely in terms of partial charges on interacting N-atoms.
Section 2 — Thermodynamics of individual chemical compounds ♦ 79
PHASE EQUILIBRIUM AND THERMODYNAMIC PROPERTIES

OF ETHERS OF CARBOXYLIC ACIDS
Agafonova L.E., Druzhinina A.I., Varushchenko R.M.
Lomonosov Moscow State University, Moscow
e-mail: varusch@thermo.chem.msu.ru
Esters of carboxylic acids are widely used in various fields of technology and science.
Esters of fatty carboxylic acids are used as components of biofuels. Esters of lower acids are
widely used in perfumery, medicine and food industry as a solvent and flavorings (fruit
essences).
The present work is devoted to the study of phase equilibriums crystal–liquid and
liquid–vapor of methyl and ethyl ethers of lower carboxylic acids C3-C5: methyl propanoate
(MPr), methyl butanoate (MBut), methyl pentanoate (MPen) and related derivatives of ethyl
EPr, EBut and EPen.
The heat capacities of esters were measured by vacuum adiabatic calorimetry in the
temperature region (5/7-372) K, using fully automatic set. The temperatures, enthalpies and
entropies of a solid phase transitions and melting and the purity of the substances were
determined. The saturated vapor pressures for EBut and EPen were determined by
comparative ebulliometry in the «atmospheric» pressure range of (4/9-101.6) kPa. The normal
boiling temperatures and vaporization enthalpies vs. temperature were obtained.
The set of the pT and Cp,m -data allowed to extrapolate the saturated vapor pressures of
esters on the whole area of the liquid phase from triple to the critical points. Extrapolation in
the region of the triple point, Ttp, was performed by the method of combined processing of
vapor pressure and differences in the heats capacities of ideal gas and liquid ΔСр,m= Cop,m(g)-
Cp,m(liq). Extrapolation of pT-data into the critical region was carried out according to the law
of corresponding States in the version of the LP. Filippov.
Table. Thermodynamic properties of ethers of the carboxylic acids C3-C5

Compound Purity, Ttp ∆fusHm Тc рtp
mol. % K kJ∙mol-1 K Pa
MPr 99.91±0.01 186.27±0.01 9.70±0.06 528.7 0.84
MBut 99.65±0.04 190.10±0.01 11.36±0.05 554.6 0.21
MPen 98.40±0.20 182.6 ± 0.5 11.72±0.06 - 0.0072
EPr 99.89±0.01 199.75±0.01 12.29±0.06 545.4 0.97
EBut 99.74±0.03 174.48±0.02 10.68±0.02 568.8 0.0022
EPen 99.44±0.06 181.29±0.02 12.97±0.37 594.2 0.00087
Тc – the temperature of critical point
.
The standard thermodynamic functions are calculated for the crystalline, liquid, and
ideal gas state basing on the data of heat capacities and saturated vapor pressures. The
contribution of entropy, attributable to the [C-(H)2(C)2] group in the acid residue of esters,
∆[C-(H)2(C)2] Som(g) = 39.4 J∙K-1∙mol-1, was obtained on the basis of absolute entropies of EPr,
EBut and EPen. The obtained value excellent agrees with that presented in the monograph
Poling B.E. et al (“The Properties of Gases and Liquids”, 2010), ∆[C-(H)2(C)2]So m(g) = 39.49
J∙K-1∙mol-1. This confirms the accuracy of the obtained thermodynamic parameters and all
experimental data used for their calculation.
DETERMINATION OF THERMODYNAMIC PROPERTIES

OF VOLATILE METALLOCOMPLEXES BY IN SITU METHOD
Alikhanyan A.S. 2, Dementiev A.I. 1, Kamkin N.N. 1, Kayumova D.B. 2, Malkerova I.P. 2,
Povalisheva D.V. 1, Yarishev N.G. 1
1
Moscow Pedagogical State University; 2Kurnakov Institute of General and Inorganic
Chemistry, Russian Academy of Science, Moscow
e-mail: nik.kamkin@gmail.com
The present paper deals with mass spectral thermodynamic research based on mass-
spectral methods using analytical equipment, which was not previously used for these
purposes. It was shown such a system with sample direct insertion is not open and can be used
as an analogue of the Knudsen cell. The interest in this studies is due to not only their
fundamental value, but also for solving practical problems, for example in the field of
metallic coating by chemical vapor deposition method (CVD-technology).
Volatile metal complexes such as β-diketonates and metal carboxylates are widely used
in CVD technologies. Whereas synthesis of these compounds is a significant problem, the
thermodynamic study of a number of β-diketonates and carboxylates was performed directly
in the process of synthesis in the direct insertion system, i.e. in situ.
Mass spectral method of evaluation standard formation enthalpies of β-diketonates, are
based on a study of hetero- and gas-phase equilibria in the direct insertion system. Synthesis
was performed during sublimation of two-component systems [metal - β-diketonate
manganese (III)] or [metal β-diketonates - β-diketonate manganese (III)]. Appliance of this
method was shown by the assessment and determination of the standard enthalpies of
formation of complexes of copper (II), zinc (II), iron (III), chromium (III) and lead (II).
Heterophase synthesis β-diketonates and pivalate metals, was implemented by joint
sublimation of metals or metal compounds with manganese (III) β-diketonates and silver
pivalate. In the process of mass spectrometric experiments were synthesized acetylacetonates,
dipivaloylmethanate copper (II), zinc (II), aluminum (III), chromium (III), lead (II), iron (III),
manganese (III) mixligand complexes and germanium (II, IV), tin (II, IV), lead (II), copper
(II), aluminum (III), gallium (III), indium (III), thallium (I) pivalates; gas phase over these
complexes consist mainly of monomeric molecules. It was found that not only metal pivalates
but also metal oxo-pivalates were formed in case of pivalate aluminum, gallium, indium. This
compounds sublimate as polymer molecules which consists of series mM(piv)3 • nMOpiv
(where m = 1-3, n = 1-5). For the first time, the study of dissociative ionization processes
allowed to calculate the average enthalpy of chemical bonding metal - oxygen molecules
pivalate gallium (III), indium (III), thallium (I), and their standard enthalpy of formation.
Enthalpy of chemical bonding metal - oxygen and standard enthalpy of formation of pivalate
aluminum and thallium (III) were evaluated by thermodynamic similarity.
This work was supported by RFBR grant № 12-03-31669.
HEAT STABILITY AND SORPTION CAPACITY OF MODIFIED CARBON

SORBENTS FROM WASTE SOFTWOOD
Amerkhanova Sh.K., Uali A.S.
E.A. Buketov Karagandy State University, Karagandy
e-mail: ualieva.84@mail.ru
It is known that from waste plant materials by carbonization and activation can be
prepared sorbents, which are characterized by a very high efficiency, environmental
friendliness, and others [1–3].
In this paper, the derivatografic investigation was been carrying out for determination of
the physical and chemical characteristics of sorbents based on dry weight of pine cones,
modified phosphoric acid followed by heat treatment in air access. Thermogram of the
original wood has shown that low-temperature portion of weight loss (30-150ºC) during the
decomposition of the wood due to the release of adsorbed moisture. Mass losses in this small
area are of 3 to 5%. This region corresponds to the first peak on the DTA curve; the analysis
showed that, in this temperature range the decomposition of wood exhibits clearly marked
endothermic effect.
To the next site is the temperature range 150-500ºC. In this part of the weight loss up to
70%, sharply increases the decomposition rate. Apparently, at this time there are processes
that are mainly due to the decomposition of cellulose and lignin. The formation, evaporation
and sublimation of the main degradation products of wood, proceeding with the rapid
evolution of heat, are occurred from 270 ºC to 450°C. There is a decrease in the rate of
decomposition of wood at temperature of 500ºC; the process is characterized exothermally,
the mass loss is due to remove residual volatiles, increased excretion of HCN and NH3. At
this stage of carbonation increases the number of aromatic rings.
Also, the derivatografic analysis of sorbents obtained by heat treatment at 105ºC and
800ºC was carrying out. In the case of the sorbent, heat treated from 105ºC to 200ºC, there is,
apparently, the allocation of adsorbed water. Judging from the thermograms, the
decomposition of surface functional groups of the sorbent is thermally treated almost
continuously with exotherm in the range 200-900ºC. As a result of the deep carbonization
mass loss in this temperature range up to 70%.Since phosphorus compounds are thermally
unstable at high temperatures (800ºC), apparently there is a removal of phosphorus
compounds in the form of volatile products, which contributes to the formation of a porous
structure of the sorbent.
Next these sorbents were used in the purification of waste water from the copper (II)
ions; the optimum conditions of sorption purification were established.
References
1. M.E. Argun, S. Dursun, C. Ozdemir, M. Karatas. Heavy metal adsorbtion by modified oak
sawdust: Thermodynamics and kinetics. Journal of Hazardous Materials. 2007, 141. 77-85.
2. E. Malkoc, Y. Nuhoglu. Potential of tea factory waste for chromium (VI) removal from
aqueous solutions: Thermodynamic and kinetic studies. Sep. Purif. Technol. 2007, 54. 291–
298.
3. Y. Orhan, H. Buyukgungur. The removal of heavy metals by using agricultural wastes,
Water Sci. Technol, 1993, 28. 247–255.
THERMODYNAMIC PROPERTIES OF REDOX-ISOMERIC COBALT COMPLEXES

WITH O-SEMIQUINONIC LIGANDS
Arapova A.V.1, Smirnova N.N.2, Bubnov M.P.1, Skorodumova N.A.1, Abakumov G.A.1
1
G.A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences,
2
Research Institute of Chemistry of Nizhny Novgorod State University,
e-mail: av_arapova@iomc.ras.ru
The redox-isomerism phenomena in solid state was discovered in o-semiquinonic cobalt

complexes. It was revealed that transformation of semiquinon-catecholate form of complex
into bis-semiquinonic one accompanied by phase transition
R R
O O
O N O N
Co Y Co Y
O N O N
O O
R R
Low-spin form High-spin form

Co(III), d6, S = 0 Co(II), d7, S = 3/2
DBSQ, S = 1/2 DBSQ, S = 1/2
DBCat, S = 0 DBSQ, S = 1/2
where R – substituent; DBSQ – anion-radical of о-quinone, DBCat – dianion of corresponding

о-quinone; Y – organic or elementoorganic bridge.
The heat capacity C op of o-semiquinonic complexes of cobalt with different neutral

ligands and substituents in o-semiquinonic fragment was studied in the range 7–350 K in an
adiabatic vacuum calorimeter with an uncertainty, mainly, of 0.2%. We have studied the
influence of ligand nature and acceptor properties of substituents in o-semiquinonic fragment
on thermodynamic parameters of phase transition related with redox-isomerism.
We are grateful to the RFBR (grant №№ 13-03-01022), Russian President Grant

supporting Scientific Schools (NSh-1113.2012.3) and Fundemental Research Programm of
Presidium of RAS (№ 8) for financial support.
THERMODYNAMIC PROPERTIES OF THE COPPER-THALLIUM CHALCOGENIDES

Babanly N.B., Salimov Z.E., Yusibov Y.A.
Azerbaijan Institute of Teachers, Gazakh branch
e-mail: babanly_mb@rambler.ru
Chalcogenides of copper-thallium attract more attention of researchers due to the fact
that they exhibit a semiconductor and thermoelectric properties, both in the solid and liquid
states.
In this work summarizes the results of experimental investigations on the the solid state
phase equilibria in the ternary systems Cu-Tl-X (S, Se, Te) and thermodynamic functions of
intermediate phases. Electromotive force (EMF) measurements were performed for the
reversible concentration chains
Cu (s) / Cu4RbCl3I2 (s) / (Cu-Tl-X) (s) (+) (1)
Using of a solid state electrolyte allowed to use metallic copper as the left electrode,
which is less active than the other metal components of the system - thallium. Equilibrium
alloys from different phase areas of these systems were served as right (positive) electrodes.
EMF was measured by the compensation method in the temperature range of 300–430 K.
EMF measurement results, besides with the control and refined of solid state phase
equilibrium diagrams Cu-Tl-X systems in the composition area Cu2X-Tl2X-X allowed us to
calculate the partial thermodynamic functions of copper in alloys. Based on phase diagrams
established potential-forming reaction which the standard integral thermodynamic functions
( ∆ f G 0 (298K ) , ∆ f H 0 (298K ) , S 0 (298K ) ) of ternary compounds were calculated by using
them (Table).
These results are in good agreement with literature data, that obtained by measuring the
EMF of the concentration chains in respect of thallium electrodes with liquid electrolyte.
Here, also discussed some of the features of the phase equilibriums of the phase
formation and thermodynamic properties systems of the Cu-Tl-X system.
Table. Standard integral thermodynamic functions of chalcogenides of copper-thallium

Compounds − ∆ f G 0 (298K ) − ∆ f H 0 (298K ) S 0 (298K )
kJ∙mol-1 J∙ mol-1⋅К-1
CuTlS2 94,3±0,7 93,6±1,4 172,7±2,8
CuTlS 90,3±0,7 88,3±2,1 132,4±6,2
Cu3TlS2 163,8±2,6 159,2±9,8 251,8±5,8
Cu9TlS5 373,8±3,9 371,8±21,4 529,0±19,0
CuTlSe2 96,29±0,16 97,91±0,95 176,1±5,1
CuTlSe 84,49±0,16 81,37±0,85 149,9±2,8
Cu2TlSe2 119,06±0,27 118,61±1,54 216,2±6,8
CuTlTe2 75,1±0,4 72,6±1,3 208±4
Cu2TlTe2 99,2±0,5 94,3±2,1 249±6
Cu3TlTe2 122,0±0,6 115,2±2,7 288±8
Cu9TlTe5 264,3±2,6 253,8±9,8 637±15
CuTl4Te3 201,4±1,4 203,8±2,6 433±9
DSC STUDY OF WATER CLUSTERS OF NATURAL POLYSACCHARIDES

AND SEPHADEX ON THEIR BASIS
Belopolskaya T.V., Tsereteli G.I., Grunina N.A., Smirnova O.I., Lapshina E.S.
St. Petersburg State University, St. Petersburg
e-mail: nagrunina@mail.ru
The thermal properties of the polysaccharide-water systems with different water content
in the range of the ice-water phase transition are investigated by differential scanning
calorimetry (DSC). Like all biopolymers, polysaccharides contain both free, freezable, and
bound, unfreezable while cooling down to low temperatures, water.
This work is a continuation of pre-existing studies [1, 2]. The objects of this study,
along with the various starches (Sigma-Aldrich Co.), having in their native state the different
crystal structures with significantly different content of the built-in hydratation water, were
used the microporous materials Sephadex G-10, G-25, G-100 (Pharmacia Fine Chemicals). As
well known, Sephadex is the material for a gel filtration of biopolymers and is made from
natural polysaccharides. Due to the special chemicals, despersed molecules form a three-
dimensional insoluble hydrophilic net. The pore size in these molecular nets is determined by
number of crosslinks.
As a result, for the studied systems was determined the quantity of unfreezable (bound)
water. It was found that at the transition from native to denatured state a boundary between the
content of the free and bound water in the starch changed. The quantity of bound water in
amorphous systems increased compared with the partially crystalline ones.
The parameters of melting of water clusters formed in the studied polysaccharides at
different degrees of hydration were determined. It was found that both in starch, and in
Sephadex the melting temperature of water clusters at a minimum freezable water content is
significantly below 0oC. For the Sephadexes was established a relation between the degree of
crosslinking, and accordingly, the pore size, and the melting temperature of water clusters.
It was shown that in the systems studied there was a range of concentrations in which
not only the temperature, but the heat of melting of water clusters depends on the degree of
hydration. The analysis of the data based on the equation Thomson-on-Gibbs, connecting
parameters of melting of nanocrystalline systems with their geometric sizes was carried out.
Overall, the results of this work are the directly manifestation of size effects in the thermal
properties of water clusters formed in the polysaccharide-water systems both in their partially
crystalline and amorphous states.
References
[1] Belopolskaya T.V., Tsereteli G.I., Grunina N.A., Rodriguez Castillo L.O. The thermal
properties of water clusters in native and denatured starches // Vestnik SPbSU (Russ),
Ser. 4, is. 2, 2012, P. 10–21.
[2] Grunina N.A., Tsereteli G.I., Belopolskaya T.V., Smirnova O.I., Rodriguez Castillo L.O.
The temperature and melting heat of small water clusters in water-starch systems // The
Abstracts of XIX International Starch Convention, Moscow, 2012, P. 54, 55.
THERMODYNAMIC PROPERTIES OF GRAPHITE OXIDE SOLVATES

Belyaeva L.A.1, Avramenko N.V.1, You S.2, Talyzin A.V.2, Korobov M.V.1
1
Department of Chemistry, Moscow State University, Moscow, Russia
e-mail: mkorobov49@gmail.com
2
Umea University, Umea, Sweden
In recent years graphite oxide (GO) has attracted wide attention as a precursor for
synthesis of graphene. The exfoliation of GO in certain solvents produces atomically thin
graphene oxide sheets that can be reduced to give graphene. In the present work the interaction
of GO oxide with the solvents was studied by means of Differential Scanning Calorimetry
(DSC) and XR Diffraction (XRD). GO prepared according to Brodie (B-GO) and Hummers
(H-GO) methods were used for measurements. The solvents examined were water, methanol,
dimethylformamide (DMF), thetrahydrofurane (TGF) and N-methylpyrrolidone (NMP). In
some of these solvents, full exfoliation of the GO material was achieved by sonication.
In some of the systems (B-GO – methanol, B-GO-DMF) formation of the “crystal” solid
solvates were observed. In these cases decomposition of the solvates occurred at certain
temperature similar to the first order phase transition. Solvates compositions, temperatures
and enthalpies of decomposition (incongruent melting) were determined by means of DSC.
Changes of interplane distances were followed by XRD. The decomposition temperatures
were close to ambient, the enthalpies measured were ~10 J/g of GO. In most of the cases the
GO/solvent interaction led to simple swelling. Typically two monolayers of the solvent were
incorporated in between neighboring GO layers at saturation.
The possible correlation between the ability of the solvent to form solid solvates with
GO and the ability to exfoliate GO is discussed. The thermodynamic properties of GO crystal
solvates were compared with those of the more stable С60 and С70 solvates.
This work was financially supported by the Swedish Research Council, grants 621-
2010-3732 and 621-2012-3654. T.A. thanks Ångpanneföreningens Forskingsstiftelse for
financial support. B.L.A., A.N.V. and K.M.V. were supported by the RFBR grant 12-03-
000653 and by the grant for Leading Scientific Schools in Russia.
THERMODYNAMIC PROPERIES OF ALKYL SUBSTITUTED DERIVATIVES

OF 4-NITRO-1,2,3-TRIAZOLE
Blokhin A.V., Kohut S.V., Kabo G.J., Stepurko E.N., Kabo A.G.,
Paulechka Y.U., Voitkevich O.V.
Research Institute for Physical Chemical Problems, Belarusian State University,
Minsk, Belarus
e-mail: blokhin@bsu.by
The comprehensive study of thermodynamic properties for 1-ethyl-4-nitro-1,2,3-triazole
(1ET), 1-methyl-4-nitro-1,2,3-triazole (1MT) and 2-methyl-4-nitro-1,2,3-triazole (2MT) in the
condensed and gaseous states was carried out by the following methods: the adiabatic and
bomb calorimetry, the integral Knudsen effusion method, the quantum-chemical calculations
and the statistical thermodynamic calculations from molecular and spectral data.
Heat capacity of the substances in the crystalline and liquid states in the range (5 to 370)
K and their enthalpies of phase transitions were determined in a TAU-10 vacuum adiabatic
calorimeter (Termis, Moscow, Russia). The uncertainty of the heat capacity measurements
was ±0.4% over the main temperature range of (20 to 370) K and did not exceed ± 2.0% near
5 K. The studied compounds had complex thermal behavior including solid phase transitions
and fusion. There are three anomalies in the temperature dependence of heat capacity of 1ET:
solid phase transitions crIII-crII (Ttr = 224 K; ΔtrH = 1350 J∙mol-1), crII-crI (Ttr = 260 K; ΔtrH
= 777 J∙mol-1) and fusion (Tfus = 349.04 K; ΔfusH = 16395 J∙mol-1). The only anomaly in the
temperature dependence of the heat capacity of 1MT was a solid-phase transition crII-crI (Ttr =
66.1 K; ΔtrsH = 334 J∙mol-1). On the temperature dependence of the heat capacity of 2MT two
heat capacity anomalies due to a solid-phase transition (Ttr = 351 K, ΔtrsH = 643 J∙mol-1) and
beginning of fusion (Tfus > 370 K) were observed. The standard thermodynamic functions of
the compounds in the condensed state in the range (5 to 370) K were calculated based on the
temperature dependences of heat capacity and the phase transition parameters.
The temperature dependences of saturated vapor pressure for crystalline 1ЕТ and 1МТ
were measured by the Knudsen effusion method in the temperature ranges (313 to 344) K and
(333 to 359) K, respectively, and the enthalpies of sublimation were found from these data to
be ΔsubH(329 K) = (93.6 ± 0.9) kJ∙mol-1 and ΔsubH(346 K) = (94.5 ± 1.0) kJ∙mol-1.
The standard enthalpies of formation at 298.15 K for crystalline 1ET ((128.2 ± 1.4)
kJ∙mol-1) and 1MT ((149 ± 4) kJ∙mol-1) were determined in a static bomb combustion
calorimeter. The standard gas-phase enthalpies of formation of 1ET and 1MT at 298.15 K
were (223.1 ± 1.7) kJ∙mol-1 and (243 ± 4) kJ∙mol-1, respectively.
A group of reactions was proposed to calculate the gas-phase enthalpies of formation of
substituted triazoles using the composite quantum-chemical methods G3MP2 and G3B3 with
the error comparable to the experimental one. Based on the obtained data and the data from
literature it was established that the gas-generating ability of 1,2,3 - and 1,2,4-triazole
derivatives is reciprocal to the specific energy of combustion.
Thermodynamic properties of the substances in the ideal-gas state were calculated in the
range (100 – 1000) K and verified on the experimental gas-phase entropies.
This work was supported by Belarusian State Program of Scientific Research
"Chemical reagents and materials" (grant 1.10).
THE HEAT CAPACITY OF LANTHANUM AND NEODYMIUM

ORTOPHOSPHATES WITH DIFFERENT PARTICLES SIZE AND MORPHOLOGY
Bryukhanova K., Ryumin M., Tyurin A., Nikiforova G., Gavrichev K.
Kurnakov Institute of General and Inorganic Chemistry RAS,
Moscow, Russia
e-mail: bryuhanova@igic.ras.ru
The lanthanum and neodymium orthophosphates belong to MIIIPO4 (MIII= La–Dy) group
with the monazite structure. These compounds have the very low solubility in water, high
chemical and thermal stability, what makes them promising for a design of new functional
materials. This work is devoted to the experimental study of the heat capacity of lanthanum
and neodymium orthophosphates with different morphology in a wide temperature range (by
hybrid adiabatic relaxation method at low temperatures and by differential scanning
calorimetry at high temperature), and to determination of the temperature dependence of
thermodynamic functions: heat capacity, entropy, enthalpy change and derived Gibbs energy.
Micro- and nano-scale samples of LaPO4 and NdPO4 were obtained by precipitation
from the solution (spherical particles) and by hydrothermal method (whisker-shaped
particles), respectively. Particle size was determined from the broadening of the diffraction
peaks by Scherrer formula, and by scanning electron microscopy.
Thus, the temperature dependences of the thermodynamic properties of lanthanum and
neodymium orthophosphate were obtained from the analysis of experimental data, which were
made at low and high temperature range. The dependence of thermodynamic characteristics
on the particles size and morphology for studied substances were detected.
This work has been carried out with financial support of the Russian Academy of
Sciences Research Program No 8P4.
VAPORIZATION STUDY OF 1-BUTYL-3-METHYLIMIDAZOLIUM CHLORIDE,

BROMIDE AND IODIDE IONIC LIQUIDS
BY THERMOGRAVIMETRY AND EFFUSION TECHNIQUES
Brunetti B., Ciccioli A., Lapi A., Vecchio S.
Since the discovery that ionic liquids (ILs) exhibit a sizeable, though very low, vapour
pressure [1] a number of studies were devoted to the experimental investigation of
vaporization of ILs belonging to the imidazolium class [2]. Most studies were aimed at
determining the vaporization enthalpy (ΔvapH) of the liquid by ln [f(T)] vs. 1/T correlations,
where f(T) is a measured property proportional to the vapour pressure. In other studies, based
on the Knudsen effusion technique or on the transpiration method the pressure values itself
were measured and ΔvapH derived by ln p vs. 1/T trend.
In spite of this, the literature on dialkylimidazolium halides is relatively scarce, and only
very recently ΔvapH values for few chloride and bromide ILs were reported, based either on
direct thermogravimetry/quartz crystal microbalance measurements and on the DSC
determination of reaction enthalpies of the IL combined with quantum chemical calculations
for the gas species [3]. The main reason for this scarcity and delay in the relevant literature is
probably due to the rather low decomposition temperatures of imidazolium halides, which
request high sensitivity tensimetric techniques, enabling one to perform measurements at very
low temperatures (150 °C or less). In particular, to the best of our knowledge, no absolute
vapour pressure data are available for the above ILs.
In this perspective, we have undertaken a research project aimed at investigating the
vaporization properties of the 1-alkyl-3-methylimidazolium chloride, bromide, and iodide ILs,
based on a multi-technique approach by combining thermogravimetry (TG), Knudsen
Effusion Mass Loss (KEML), Torsion-Effusion (TE), and Knudsen Effusion Mass
Spectrometry (KEML) experiments. In this contribution, we report our preliminary results on
1-butyl-3-methylimidazolium halides.
TG experiments were used to investigate the thermal stability of the studied compounds,
to determine the specific heats necessary to reduce to 298 K the measured vaporization
enthalpies, as well as to study the vaporization behaviour under open crucible conditions. The
effusion techniques were employed to measure vapour pressures and vaporization enthalpies.
The higher sensitivity of the KEMS technique, combined with its capability to identify the
effusing species or their fragments, allowed us to considerably extend the study to lower
temperatures. Furthermore, by combining the KEML and TE methods (the latter technique
allowing the measurement of the total pressure regardless the vapour composition), a direct
determination of the molar mass of the vapour species was attempted.
References
[1] Earle, M.J.; Esperança, J.M.S.S.; Gilea, M.A.; Canongia Lopes, J.N.; Rebelo,
L.P.N.; Magee, J.W.; Seddon, K.R.; Widegren, J.A., Nature, 2006, 439, 831-834.
[2] Zaitsau, Dz.H., Fumino, K., Emel’yanenko, V.N., Yermalayeu, A.V., Ludwig, R.,
Verevkin, S.P., ChemPhysChem, 2012, 13, 1868-1876, and references therein.
[3] Verevkin, S.P., Emel’yanenko, V.N., Zaitsau, Dz.H., Ralys, R., Schick, C., J. Phys.
Chem. B, 2012, 116, 4276-4285.
HEAT OF FORMATION OF CARBONYL-CONTAINING FREE RADICALS

Chernova E.M., Orlov Yu. D., Turovtsev V.V.
Tver State University, Tver
e-mail: chernova_elena_m@mail.ru
Standard heat of formation (ΔfH0) is one of key thermodynamic characteristics of
substances. However the number of free radicals (R●) characterized of ΔfH0 is much less than
its parent compounds. An experimental study of R● properties is very difficult, time
consuming and expensive because of their high reactivity and small lifetime, therefore
database on ΔfH0(R●) is very scarce. In this connection the methods of theoretical property
prediction of R● take the most important play.
At present time the quantum-chemical calculations of ΔfH0(R●) of big compounds aren't
often a source of reliable quantitative data. Increasing in number of atoms and/or taking into
account atoms of III and next periods of the Mendeleyev’s table decreases the predictive
ability of quantum-chemical methods, and that computation requires large resources.
In the such situation the phenomenological models are very productive and allow to
define new values of ΔfH0(R●) within an acceptable error. Among these models the additive
group approach gained the greatest popularity [1]. In the presented work the attempt on
expansion of opportunities of group additive by means of definition new and specifications of
already known parameters was made.
Within that model the auxiliary values of molecule enthalpies of formation (ΔfH0(RH))
were determined, and on the base ratio (1) and using of published data on enthalpy of bond
breaking D(R-H) [2] the heats of formation of 47 carbonyl radicals were computed.
D(R-Н) = ∆fН°(R•) + ∆fН°(Н) - ∆fН°(RН), (1)
where ΔfH0(H) = 218 kJ/mol is enthalpy of formation of hydrogen atom at 298 K.
In framework of group additivity the correlation "structure - property (heat of
formation)" for the corresponding radicals is considered. That relationship allows specifying
for exist and determine new parameters of model used (increments). By taking into account
found increments ΔfH0(R●) of 86 carbonyl radicals were calculated and well agreement with
experimental magnitudes were shown.
References
[1] Yu. D. Orlov, Yu. A. Lebedev, and I. Sh. Saifullin, Thermochemistry of Organic Free
Radicals (Nauka, Moscow, 2001) [in Russian].
[2] J.-R. Luo, Comprehensive handbook of chemical bond energies. L., N.-Y.: CRC Press,
Boca Raton. 2007.
WARMTH OF MELTING OF CONNECTION OF SrNdCuS3

Demchuk Zh.A. Ruseykina A.V. Zhernovnikova A.M. Andreev O. V.
Tyumen State University, Tyumen, e-mail: adeschina@mail.ru
At the first time by differential scanning calorimetry (DSC) methods with the Setsys
Evolution 1750 installation, where the PtRh thermocouple consists of 6%-PtRh of 30% was
used; warmth of incongruent melting of SrNdCuS3 and the thermochemical equation of phase
transformation (fig., the tab.) was defined.
Cast samples of difficult sulfide are received by alloyage of SrS, Cu2S, Nd2S3 when
heating in the TVCh generator of a graphite crucible with furnace charge, in vacuumized and
the filled argon the quartz reactor. Samples are annealed in the vacuumized and soldered
quartz ampoules at 1050 K during 480 h. Uniformity and homogeneity of samples is proved
by the MSA, RFA, DMA methods, the chemical analysis is carried out on a raster electronic
microscope with the power dispersive analyzer.
Experimental value of temperature and enthalpy of phase transformation are obtained by
carrying out three parallel experiments of DSK and by averaging of the obtained results (tab).
The conducted researches specify that incongruent melting reaction konode lies in the range of
40-95 pier. % of SrS (fig. B). Data host allowed to work out the balance equation of phase
transformation in the NdCuS2-SrS system being a quasibinary part of Cu2S system – Nd2S3 –
SrS.
Т,К
2590
2300
1900
SrNdCuS3 ж+ТР SrS
Nd2S3+ж
1500 1400К ТР
1465 8%
NdCuS2+ж 40% 95% SrS
31% 1310К ж+SrNdCuS3
1100
NdCuS2+SrNdCuS3 SrNdCuS3+ТР SrS

700
A NdCuS2 20 40 60 80 SrS
мол.% SrS B
Fig. A - differential thermal dependence of a sample probe of complex SrNdCuS3 sulfide. Shooting
conditions on the Setsys Evolution 1750 installation (TG-DSC 1600): vheating = 5 K/mines, vpurge Ar =
25 ml/min., Vcrucible = 100 мкл; B – the phase chart of NdCuS2-EuS system.
Table. The balance equation of phase transformation in CuNdS2-SrS system

Type of phase Coordinates Equation of phase ΔНmelt,
transformation nonvariantny points transformation J/g
structure Т, К
Incongruent melting 50.0 mol. % 1426 SrNdCuS3 sol (0.50 SrS; 0.50 43 ± 4
of of сompounds EuS ±2 NdCuS2) ↔ 0.18 FS SrS (0.95
SrNdCuS3 SrS; 0.05 NdCuS2) + 0.82 liq.
(0.40 SrS; 0.60 NdCuS2)
Scientific research is conducted with financial support of the state represented by the
Ministry of Education and Science of the Russian Federation the agreement No.
14.B37.21.1184.
THERMODYNAMIC PROPERTIES OF 5-(NITROPHENYL) FURAN-

2-CARBALDEHYDE ISOMERS
Dibrivniy V.N., Punyak M. J., Prokop R.T., Rajewskiy J.A.,Obushak N.D.*
National University "Lviv Polytechnic"
e-mail: vdibriv@polynet.lviv.ua
*Lviv Ivan Franko National University
5-(Ortho-, meta- and para - nitrophenyl) furan-2-carbaldehyde isomers (in the table
substances O, M and P, respectively) are crystalline materials under normal conditions. They
are used as intermediates in synthesis of organic biologically active substances.
Samples of the investigated compounds were synthesized by interaction of furfurol with
arenediazony chloride solution obtained by diazotization of the corresponding amine. The
product was filtered and purified by double recrystallization from ethanol –
dimethylformamide mixture. Substances were identified by elemental analysis and PMR
spectroscopy. The compounds purity (more then 99% wt.) was determined by high pressure
liquid chromatography method.
Temperature dependence of the vapor pressure of O-isomer in liquid state, P-isomer in
solid state and M-isomer in both solid and liquid states were determined by Knudsen effusion
method. Accuracy of temperature determination, thermostating temperature maintaining and
effusion duration determinination were ± 0,05 K, ± 0,5 K and ± 1s, respectively. The
coefficients A and B in the linear approximation of the temperature dependence of the
saturated vapor pressure ln p (Pa) = A + B / T, the number of experiments n, enthalpy of
vaporization ΔvN , and sublimation ΔsubH are presented in the table.
Sub- Temperature ΔsubH ΔvH

А - В∙10-2, К n
stance range, К kJ/mole kJ/mole
О (l) 363.1-383.0 37.80±0.89 140.0±3.3 11 - 116.1±2.8
М (s) 383.1-418.2 38.57±0.39 152.7±1.6 17 126.9±1.3 -
М (l) 422.7-432.9 29.88±1.37 116.2±5.8 23 - 96.6±4.9
P (s) 402.8-428.1 38.19±0.19 158.07±0.83 12 131.4±0.7 -
Combustion energy of carbaldehyde isomers were determined with the upgraded

calorimeter B-08 MA, with an isothermal (± 0,03 K) shell. The energy equivalent of the
calorimeter system was determined with accuracy ± 0,06% by combustion of reference
benzoic acid grade K-1 (the main component content is 99.995% mol.).
For crystalline ortho-, meta-, and para-isomers standard combustion enthalpy (kJ / mol)
(∆cH0 298, 15K) are -5143.6 ± 7.6; -5135.3 ± 8.5; -5114.5 ± 7.6, and formation enthalpy (∆fH0
298, 15K) are -185.5 ± 7.6; -193,7 ± 8.5; -214.6 ± 7.6, respectively.
PHASE TRANSITIONS IN SOLVATE OF THE HETEROSPIN COPPER (II)

HEXAFLUOROACETYLACETONATE COMPLEX WITH NITRONYL
NITROXIDE RADICAL
Dobrokhotova Zh.V.а, Tyurin A. V.а, Ryumin M. A.а, Gavrichev K. S.а,
Maryunina K.Yu.b, Ovcharenko V.I.b
a
Kurnakov Institute of General and Inorganic Chemistry,
Russian Academy of Sciences, Moscow
e-mail: tyurin@igic.ras.ru
b
International Tomography Center, Russian Academy of Sciences, Novosibirsk
e-mail: Victor.Ovcharenko@tomo.nsc.ru
Recently keen interest is shown in a new group of breathing crystals, which are
aromatic solvates of a heterospin complex hexafluoroacetylacetonate Cu(II) with nitronyl
nitroxide radical of structure [Cu(hfac)2L] • 0.5Solv, where L – 2 (1-butyl-1H-pirazol-4-silt) -
4,4,5,5-tetramethyl-4,5-digidro-1H-imidazole-3-oxide-1-oxil and Solv – solvate molecules of
aromatic solvents. The main feature of the nature of single crystals of these compounds is the
high plasticity. At the temperature variation the reversible change of structure takes place and
caused the spin transition without the simultaneous destruction of single crystals. Among
studied [Cu(hfac)2L] • 0.5Solv stood out [Cu(hfac)2L] • 0.5 (1,4-(CF3)2-C6H4) for which two
magnetic anomalies on the dependence of the effective magnetic moment (µeff) from
temperature were registered. For the purpose of thermochemical confirmation of existence of
two effects in polycrystalline [Cu(hfac)2L] • 0.5 (1,4-(CF3)2-C6H4) in the range of 5-298 K, we
carried out measurement of its temperature dependence of the heat capacity by a method of an
adiabatic calorimetry.
It was found that the complex undergoes phase transformations in temperature intervals
50-62 K and 116-130 K. Temperatures and integrated values of thermal effects are well
correspond with the earlier obtained data of magnetochemical and X-ray diffraction
measurements. At heating of polycrystalline [Cu(hfac)2L] • 0.5 (1,4-(CF3)2-C6H4) near 50-62
K. The “defrosting” and a structural relaxation of high-spin exchange clusters >N-•O–Cu–O•-
N< trapped at the sample cooling were observed, while at temperatures 116-130 K the
structural phase transition accompanied with the reorientation of solvent molecules and
pushing the paramagnetic centers in the >N-•O–Cu–O•-N< spin triads what switches the
antiferromagnetic exchange to ferromagnetic one and causes the jump of magnet moment.
This work was financially supported by the Ministry of education and science of the
Russian Federation (grant 8437), Russian Foundation for Basic Research (grants № 12-03-
00438, 12-03-00067) and Presidium of the Russian Academy of Sciences and Siberian Branch
of RAS.
ENTHALPIES OF FORMATION OF NITROGEN CONTAINING ORGANIC

COMPOUNDS: A HIGH-LEVEL QUANTUM CHEMICAL STUDY
Dorofeeva O.V., Marochkin I.I., Suntsova M.A., Ryzhova O.N.
Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia
e-mail: dorofeeva@phys.chem.msu.ru
Direct quantum chemical computation of a molecular enthalpy of formation from the
atomization energies requires the high-accuracy energy methods with high-level correlational
calculations and large basis sets. However, such computational levels can be now applied to
only small molecules because of their computational expense. To make accurate predictions
of thermochemical data for larger molecules, a number of composite methods (Gaussian-n,
CBS-n, W-n, ccCA and others) have been developed over the past two decades.
The gas-phase enthalpies of formation of a large number of nitrogen containing organic
compounds have been calculated in this study using the Gaussian-4 (G4) method which is one
of the most successful today in calculating thermochemical properties of large molecules.
Special attention was paid to nitro compounds and azides which are the basis of many
energetic materials. It was found that the G4 method reproduced the experimental enthalpies
of formation of amines, amides, amino acids, and nitrogen heterocycles with high accuracy,
whereas the calculated values for nitro compounds were systematically underestimated by
5-20 kJ/mol. Somewhat better results for nitro compounds were obtained with G3 and ccCA
methods. The analysis of results allows us to suggest that the G4 and similar composite
methods cannot be used to predict the values of nitro compounds with high accuracy.
In order to avoid (or lessen) the errors in calculated enthalpies of formation of nitro
compounds, the method of isodesmic reaction was used. It is well known that the applying the
isodesmic reactions would be successful if the accurate experimental enthalpies of formation
are available for the chosen reference compounds. For that reason, first of all, a set of
reference nitro compounds with internally self-consistent enthalpy of formation values was
determined. The isodesmic reaction calculations give support for the experimental values of
most nitro compounds. However, the experimental data for some compounds
(trinitromethane, 1,1,1-trinitroethane, 1,1,1-trinitropropane, hexanitroethane, N,N-
dinitromethanamine, n-butyldinitramine, 1,1-dinitrocyclopropane, 5-nitrouracil et al.) may be
unreliable. Besides, we recommend a value of ∆ f H 298

(g) = 63 kJ/mol for nitrobenzene that is
4 kJ/mol less than the experimental one.
Experimental enthalpies of formation of organic azides are often determined with large
uncertainty, and so it is difficult to choose the reliable reference compounds. A set of
reference azido compounds (•N3, HN3, CH3N3, C6H5N3, C6H5CH2N3, 1,4-NO2-C6H4-N3,
NCN3, HOCH2CH2N3, CH3C(NO2)2N3, C(NO2)3N3, azidocyclopentane, azidocyclohexane)
with consistent enthalpy of formation values was obtained in this study using isodesmic
reaction calculations. For five of these compounds, the calculated values agree well with the
experimental ones, while the calculated values for remaining species are supposed to be more
accurate than the experimental ones. The ∆ f H 298
(g) values of different organic azides are
calculated based on the above reference compounds. A good agreement with the experimental
values for N3CH2C(O)OC2H5 and (C6H5)3CN3 gives additional support to the approach used
in this study. The enthalpy of formation of perspective energetic compound, 4,4′,6,6′-
tetra(azido)azo-1,3,5-triazine (TAAT), was substantially refined not only for gaseous phase,
but also for solid state.
THE APPLICATION OF THERMOCHEMICAL APPROACH TO WORK FUNCTION

DETERMINATION OF CERIUM AND PRASEODIMIUM TRIHALIDES
Dunaev A.M., Motalov V.B., Ivanov D.A., Sergeev D.N., Kudin L.S.
Ivanovo State University of Chemistry and Technology, Ivanovo
e-mail: amdunaev@ro.ru
Electron work function (φe) is one of the most important characteristics of solids which
defines emissive properties of materials. Available experimental methods to determine φe are
not sufficiently suitable for ionic crystals. The new approach to calculation φe is applied in
this work for lanthanide trihalides widely used as scintillators, metal-halide lamps, high-
performance flash-devices, etc.
The method was based on the evaluation of φe from a thermochemical cycle including
ion and molecule transitions from crystal surface into gas at equilibrium conditions. The main
equation is:
F·φe = – 5/4∆sH°(LnX3) – 1/4D(LnX3) + EA(X) + ∆desH°(LnX4–) + ∆dissH°(LnX4–),
here ∆desH°(LnX4–) is the desorption enthalpy of LnX4–; ∆dissH°(LnX4–) is the
dissociation enthalpy of LnX4– onto molecule–precursor and halogen anion; ∆sH°(LnX3) is
the sublimation enthalpy of LnX3 molecule; D is the atomization energy dissociation
enthalpy of LnX3 molecule; EA(X) is the electron affinity of halogen; F is the Faraday
number.
The Sublimation and desorption enthalpies included into the cycle were experimentally
determined by the high-temperature mass-spectrometry technique. The experimental and
reference data are given in table together with the calculated work functions.
∆sH°(LnX3) D(LnX3) EA(X) ∆dissH°(LnX4–) ∆desH°(LnX4–) φe

LnX3
kJ/mol eV
CeCl3 327±9 1514±6 355±0.3 331±21 355±11 3.6±0.3
CeBr3 305±6 1340±4 331±0.3 307±27 377±10 3.4±0.3
CeI3 304±6 1102±5 302±0.3 248±25 305±3 3.2±0.3
PrBr3 299±10 1288±4 331±0.3 308±27 241±14 2.9±0.3
PrI3 297±7 1044±5 302±0.3 302±25 264±8 2.8±0.3
The obtained values of work function for cerium and praseodymium iodides are in good
agreement with the corresponding ones for bromides and chlorides thereby providing the
established regularity  decreasing of φe with increasing of the halogen mass.
The work was supported by Russian Foundation for Basic Research, project № 12-03-
31753 mol_a.
BIOMASS-DERIVED PLATFORM CHEMICALS: THERMODYNAMIC ANALYSIS

OF THE CONVERSION OF GLUCOSE INTO BULK INTERMEDIATES AND FUELS
Emel’yanenko V.N.1, Verevkin S.P.1, Maskow T.2
1
Universität Rostock; 2UFZ, Helmholtz Zentrum für Umweltforschung
e-mail: vladzimir.yemelyanenko@uni-rostock.de
Environmental problems have stimulated increasing efforts toward synthesizing liquid
biofuels as transportation energy. Compared to the traditional biofuel, ethanol, advanced
biofuels should offer advantages such as higher energy density, lower hygroscopicity, lower
vapor pressure, and compatibility with existing transportation infrastructure. Metabolic
engineering offers an alternative approach in which synthetic pathways are engineered into
user-friendly hosts for the production of these fuel molecules. A microbial hosts using the
enzyme Clostridium acetobutylicum have been engineered as a promising biocatalysts for
butanol biosynthesis. The butanols synthetic pathway of could be designed as follows:
In this work we explored the thermochemistry of pyruvate, 2-ketobutyrate, and 2-

ketovalerate including the vaporization enthalpies and the standard enthalpies of formation in
the condensed state. Different experimental methods were applied (combustion calorimetry,
DSC, and vapor-pressure measurements). For a validation of the experimental data on these
compounds, high-level ab initio calculations of the gaseous enthalpies of these molecules have
been performed using the GAUSSIAN-09 program package. Thermodynamic analysis of the
fermentation process has been performed and the feasibility of the reaction steps has been
assessed. High-precision reaction microcalorimetry calorimetry has been applied to study
fermentation processes and validation of the thermochemical measurements and calculations.
ALLOY SOLUTIONS ENTHALPY OF ALUMINUM SYSTEM WITH ADDITIONS

OF LANTHANUM, CERIUM, PRASEODYMIUM AND NEODYMIUM
Eshov B.B.1, Razozi M.B.2, Pulatov P.1, Rustamov S.Т.3, Badalov A.B.3
1
V.I.Nikitin Institute of Chemistry under AS of the Republic of Tajikistan, Dushanbe
2
Open University, Majlisi, Isphahon, Iran
3
Academician M.S.Osimi Tajik Technical University, Dushanbe
e-mail: badalovab@mail.ru
Initial metals of the following qualifications: Al- A99, La -La – EO OST 48-295-85, Се
- Ce EO ТU 48-295-85, Рr – Pr М-1 ТU 48-4-215-72, Nd - N М-2 ТU 48-40-205-72 are used
for synthesis of investigated objects. Element composition and alloy structure are defined on
scanned electronic microscope SEM AIS2100 and Canon microscope.
Alloys solution enthalpy of systems Αℓ–Ln, where Ln – La, Се, Рr and Nd are
determined by calorimetry solution method with isothermic surface. The most optimal
dissolvent was 0,5 М solution of hydrochloric acid. Dilution rate was 1:1100.
Intermetal (IM) disslotion process is expressed by equation:
3( х + 1)
ΑℓLпх(т) +3(х+1) ΗCℓag+ уΗ2Οж =ΑℓCℓ3.6Η2Οag+ хLnCℓ3.7Η2Οag+ (у-13)Η2Ο+ Η2
2
Solution heat measuring of Αℓ(met), aluminum chlorine crystalline hydrides and
lanthanides is carried out as side reaction. Н+ag ion transformation heat in Н2 is taken, equal to
-1317.75 kJ. Experimental values are produced according to the results of three-five tests.
Αℓ(met) solution heat values is equal to 4601,0±70 J. Enthalpy formation of hydrated aluminum
ions (3) is equal to -529,6 kJ, which is well in compliance with reference data. Alloys solution
heat values (-ΔНdissolution, J*mole-1) of studied systems are provided in the table.
Table. Alloy dissolution heat of the system aluminum – lanthanides
Al-Ln Content Ln, % mass.
0,05 0,1 0,5 1,0 2,0 4,0 6,0
La 9561±600 8598±300 8539±300 8800±300 7978.5±60 7314±300 7320±300
0
Ce 1396±100 1668±100 1792±90 1804±70
Pr 1567±140 1966±200 1401±50 1319±30 7058±500 6679.0±10 7457.7±60

0 0
Nd 1658±90 2003±40 1280±20 1602±70
The sharp increase of dissolution enthalpy value is observed at low additions of

lanthanum (from 0.05 % mass.) to aluminum comparing to pure aluminum and remains at the
same level within experimental error, an in other systems visa versa, the double decrease of
current value is observed. Alloys dissolution enthalpy remains almost at the same level at
lanthanide content more than 2% mass.
RELATIVE THERMODYNAMIC STABILITY OF SYN AND ANTI ISOMERS

OF SUBSTITUTED π-ALLYL PALLADIUM COMPLEXES
Evstigneeva E.M.
e-mail: eme2003@list.ru
Electronic polarization induced by the interaction of a transition metal complex with a
liquid environment is expected to affect the reactivity of catalytic reaction intermediates.
Quantitative evaluation of polarization effects in allyl palladium complexes of general
formula [(1-R-η3-C3H4)PdL1L2 (1) was made by means of combination of DFT calculations
R L
1 R = Me, Ph, H, CH2OH, CH2OMe, C2H,
L1
Pd
Pd СO2H, CF3 , СO2Me, COMe, CHO, COCF3,
L2 CN, CHMe2 ; L1=L2=Cl-, L1=acetone, L2=Cl-,
L2
syn -1 anti-1 L1=acetone, L2=H2O.
R
(B3LYP/6-31+G* both in gas phase and in polarized continuum with ε=78.39) and three-
parameter correlation analysis (eq 1, where εMO is molecular orbital (MO) energy of
equilibrium structure, F and R- are Swain-Lupton field and resonance parameters, σα is a
polarization constant).
ε = Const + ρ − R− + ρ F + ρ σ
МО R F α α
(1)
It was shown that electronic effects of substituents in anionic, neutral and cationic
complexes 1 are responsible for relative thermodynamic stability of both syn and anti isomers
of 1. The ratio between values of ρR-, ρF and ρα depends on MO type, syn or anti substituent
orientation, on environment, but not on the basis set. Destabilizing influence of both
polarizing continuum and positive charge on HOMO-N (N=0÷4) of 1 can be successfully
assessed by means of polarization constants σα. Polarization does not affect LUMO’s energies
in 1 (ρα=0). The remarkable fact is deviation from linearity for 1 with unsaturated substituents
R=Ph, C2H (Fig.). Thus, HOMO and HOMO-3 energies are by 0.2 and 0.1 eV respectively
above the values obtained from correlating equations.
As a conclusion, along
with polar and resonance
effects of substituents, -5.8
polarization effect can make
an influence on relative Ph
anti
thermodynamics of syn and -6.0 Ph syn
anti isomers. Observed
phenomenon seems to be
εHOMO, эeV
-6.2 C2H
common for neutral, cationic
and anionic complexes as
-6.4 CH2OH
well. The results are in good
agreement with the experi-
mental data and are -6.6 CHO
important for proper
understanding of electronic
effect of substituents. -6.8
-0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5
F + 0.27R- + 0.43σα (syn), F + 0.27σα (anti)
THERMAL PROPERTIES OF Sr2Ni0.75Mg0.25MoO6

Filonova E. A., Dmitriev A. S., Tsvetkov D. S., Medvedev D. A.*, Pikalova E. Yu.*
Ural Federal University named after the first President of Russia B. N. Yeltsin, Ekaterinburg
e-mail: helen.filonova@usu.ru
*Institute of High-Temperature Electrochemistry, Ural Branch,
Russian Academy of Sciences, Ekaterinburg
Double perovskites Sr2MMoO6 (M = Mg, Ni) attract the attention of scientists due to
their potential application as anode materials for solid-oxide fuel cells (SOFC). Currently it is
of interest to get a material which would be stable both under oxidizing and reducing
conditions. It has been found out previously that Sr2NiMoO6 decomposes in the atmosphere of
hydrogen at 1180 K. On the contrary, Sr2MgMoO6 possesses significant amount of impurities
in air. That is why it has been decided to synthesize new complex oxide with formula
Sr2Ni0.75Mg0.25MoO6 in order to eliminate these disadvantages and investigate its
thermodynamic stability and thermomechanic properties under the various conditions (versus
temperature and pO2).
The thermal properties of Sr2Ni0.75Mg0.25MoO6 were studied by X-ray diffraction,
dilatometry and thermogravimetric methods. The diffraction analysis was carried out on Inel
Equinox 3000 diffractometer in CuKα-radiation supplied with a high-temperature attachment,
HDK S1 (Edmund Buechler GmbH). The lengthening of the Sr2Ni0.75Mg0.25MoO6 sample
with temperature increase measurements was determined in a high-temperature dilatometer.
The thermogravimety data was obtained on STA 409 PC device that possessed to measure the
sample mass changes depending on temperature.
By means of the high-temperature X-ray diffraction it was stated that nearly at
temperature of 510 K the crystal phase transition from a tetragonal to a cubic phase occurs and
the calculated average coefficient of thermal expansion equals (TEC) to 13.5·10-6 K-1 in
temperature range of 298 ≤ T, K ≤ 873. According to the dilatometric data, TEC values
calculated in two temperature ranges of 300-500 K and 500-1073 K are 12.3∙10-6 and
13.5∙10-6 K-1, respectively. Based on our data, we propose that the thermal expansion
coefficients of Sr2Ni0.75Mg0.25MoO6 at 303–1373 K are close to those values of the most
popular electrolyte materials.
The isothermal expansion of material has been measured at 1073 K at
1·10-18≤ pO2, atm ≤ 0.21. At high and intermediate pO2 values the sample size changes are not
observed and visible extension associated with the reduction of molybdenum is registered
only with a decrease in oxygen partial pressure below 10-15 atm. As long as the ionic radii of
Mo6+ and Mo5+ are close (0.59 and 0.61 Å, respectively) the percentage elongation does not
exceed 0.1%.
The thermogravimetric properties have been investigated in temperature range of
298 ≤ T, K ≤ 1200 in 5% H2/Ar flow. It was found that in contrast to Sr2NiMoO6, the sample
is much more stable under reducing atmosphere, for instance, noticeable mass loss occurs at
temperature of 900 K. XRD data showed that the sample contained negligible amount of
impurity (3% wt. of MgO).
Thus, we propose this material may represent a potential anode material for high-
temperature elements.
This work was supported by Russian foundation for basic research program (project
№ 11-03-00282-а).
ENERGY CHARACTERISTICS OF CRYSTALLINE LANTHANIDES BOROHYDRIDES

Gafurov B.А.1, Mirsaidov I.U.2, Nasruloeva D.Kh.2, Islomova M.S.3.
1
Abu Ali Ibn Sino Tajik State Medical University, Dushanbe
2
Nuclear and Radiation Safety Agency AS Republic of Tajikistan, Dushanbe
3
M.S.Osimi Tajik Technical University, Dushanbe
Physico-chemical properties of coordinated crystalline compounds, in particular
hydrides, are defined not only by individual properties forming their structural particles, but
also by colligative property of interaction and force intensity of short and long-range order in
the whole volume of crystal.
The basic criteria of crystalline compounds stability is lattice energy (Uк) for ionic and
sublimation energy (Еsubl) for covalent compounds.
Uк calculation results of borohydrides of whole lanthanide range according to
Kaputinskiy equation and Born-Gaber cycle are provided in the current work. Thermo-
0
chemical ion radius ВH 4− , equal to r( ВH 4− )=2.3 A and gaseous formation enthalpy of
∆ f H 298
0
( BH 4− ) =-96.2±20 kJ∙mole-1 are used during calculations. Produced by us experimental
and calculated values of lanthanides borohydrides formation enthalpy are used during
calculations according to thermo-chemical cycle of Born-Gaber. Energy balance of complex
borohydrides formation is compiled on the basis of above-mentioned data, which can be
expressed according to Born-Gaber cycle in the following way:
[Ln] + 6(H2) +3[B] ∆ f H 0 [ Ln( BH 4 ) 3 ] [Ln(BH4)3]
SLn+6D(H2) + 3S[B]
Uк [Ln(BH4)]
(Ln) + 12H +3(B)
ILn+3E(H) +3S[BH3]
(Ln3+) + 3(H-) + 3[BH3] ∆ f H [ BH 4− ] Ln3++3(BH-4)
where Ln – lanthanides, designation (…) – gaseous and […] – solid state of substance. From
this cycle we find the value of Uк accrding to the following
equation:
U ê [ Ln( BH 4 ) 3 ] = −∆ f H 0 [ Ln( BH 4 ) 3 ] + S [ Ln] + 6 D( H 2 ) + 3S [ B] + I ( Ln) +
D
+ 3E ( H ) − 3d [ BH 3 ] = −∆ f H 0 [ Ln( BH 4 ) 3 ] + {S [ Ln] + I ( Ln)} + 6{ ( H 2 ) + E ( H )} +
2
+ 3S [ B] − 3d [ BH 3 ] = −∆ f H 0 [ Ln( BH 4 ) 3 ] + ∆ f H 0 ( Ln 3+ ) + 3∆H ( H − ) − 3d [ BH 3 ] =
= −∆ f H 0 [ Ln( BH 4 ) 3 ] + ∆ f H 0 ( Ln 3+ ) + 3∆ f H 0 ( BH 4− )
Calculation results is evident of noticeable share of covalent nature of chemical bond in

lanthanide borodydrides molecules.
PYRUVIC ACID: THE ENTHALPY OF FORMATION

AND THE THERMODYNAMIC FUNCTIONS IN THE STATE OF AN IDEAL GAS
Garist I.V.1, Roganov G.N.1, Emel’yanenko V.N.1, Verevkin S.P.2
1
Mogilev State University of Food Technologies,
Mogilev, Belarus, e-mail: garistina@rambler.ru
2
University of Rostock, Germany
Pyruvic acid (PA) - one of the most widespread keto-acids, containing in atmosphere,
where it gets as a result of photochemical oxidation and direct issue of organic substances
from biogene and anthropogenous sources (as a product of oxidising disintegration of
carbohydrates, from automobile exhausts, as a result of atmospheric oxidation isoprene,
allocated with trees, other). PA plays a fundamental role in biological systems, it is found out
in clouds and rain water, in the remote continental and sea atmosphere and as the organic
substance forming aerosols, influences climate formation.
From combustion calorimetry has been obtained the standard molar enthalpy of
formation of pyruvic acid, Δ f H om (l.) (298.15 К) = -601±0.8 kJ·mol-1.
The thermodynamic functions of PA and of the three stable conformers Tcе (II), Ttе
(III) and Сtе (IV) for substances in a state of ideal gas within temperature 50-1500 K were
determined using known data sets of fundamental frequencies on the basis of experimental IR,
Raman spectra and references ab initio calculations data. Structural parameters of molecules
are known from spectroscopic H H H
H
H
H
H
H
H
H H H
(microwave, FTIR, Cavity Ring-Down) C H
C
H
C C
H
C
H
researches and ab intio calculations. The HO C C O O

C
C
O
O
C
C
O
O
C
C
O
H O
C
C
O
gas-phase equilibrium mixture were H

O
H
O O H
H
O O
(I) (II ) (II I) (IV) (V)

determined on the basis of data of
calculation DFT/B3LYP/aug-cc-pVDZ their relative energies: Tcе:Ttе:Сtе at 298.15 and 1000
K are equal accordingly 98.6:1.3:0.1 and 71.3:19.7:8.8 % mol. Mixing conformers (II-IV) is
considered. Contributions of enol (I) and conformer Ссе (V) in thermodynamic functions PA
were not considered, since their maintenance at 1000 K does not exceed 0.5 % mol.
Calculation results of thermodynamic functions of PA and conformers (II-IV) are
received for eighteen temperatures in the range of 50-1500 K (J⋅mol-1⋅K-1, ideal gas), in the
table they are resulted for 298.15 and 1000 K:
H oT − H o0 H oT − H o0
Т, К C op Som Ф om C op Som Ф om
T T
PA (equilibrium mixture of conformers) Tcе-conformer
298.15 98.03 327.88 63.40 264.47 103.14 337.66 68.33 269.33
1000 186.18 501.96 126.10 375.86 188.03 514.88 129.17 385.71
Ttе-conformer Сtе-conformer
298.15 97.10 337.43 64.94 272.49 97.32 339.52 64.73 274.79
1000 182.10 506.52 123.45 383.07 182.36 509.15 123.69 385.46
THERMODYNAMIC PROPERTIES OF VOF3 AND VOCl3 MOLECULES:

QUANTUM-CHEMICAL CALCULATION
Gorokhov L.N., Osina E.L.
Joint Institute for High Temperatures RAS, Moscow, Russia
e-mail: gorokhov-ln@yandex.ru
The experimental and theoretical information on structural and thermochemical data
needed for evaluation of reliable values for the enthalpy of formation and calculation of
thermodynamic functions of VOF3(g) is extremely scarce; and is far from being complete for
VOCl3g) molecules. Early works on the VOCl3(l) enthalpy of formation, as summarized in the
Reference Book "Termicheskiye Konstanty Veschestv” (TKV) led to the values (kJ mol-1):
ΔfHo(VOCl3, l, 298.15 K) = -735.5 ± 5.4; and ΔfHo(VOCl3, g, 298.15 K) = -696.2 ± 5.4-1, the
latter value being obtained with the use of the enthalpy of evaporation, ΔfHo(VOCl3, l, 298.15
K) = 39.3 ± 0.8. Later, two studies of V2O5 chlorination (Sonin et al., 1971; Sano and Belton,
1980) and two calorimetric measurements (Vasil’ev et al., 1993; Dmitriyeva et al., 2010) of
VOCl3 dissolution have led to good consistency of results for the value of VOCl3(l) enthalpy
of formation. In combination with the TKV enthalpy of vaporization VOCl3(g), 39.3 ± 0.8 kJ
mol-1, we have selected the value ΔfHo(VOCl3, g, 298.15 K) = -662.4 ± 2 kJ mol-1.
The only experimental result that could be used to determine the enthalpy of formation
of VOF3(g) is the appearance energy of the V+ ions in the mass spectrum of vanadium oxide-
trifluoride (Flesch and Svek, 1975). However, the authors of this work found that the
calculated results can be severely distorted due to the formation of fragment ions that are not
only in the ground, but in various excited electronic states as well. In the case of VOCl3(g),
the enthalpy of formation calculated from the appearance energy of the V+ ions was found to
be -817 kJ mol-1, whereas the value selected in our work is -662.4 kJ mol-1. It should be
expected that for the same reasons, VOF3(g) enthalpy of formation would be distorted as well.
To determine more reliable value, we have used the results of quantum-chemical calculations
for VOF3 and VOCl3 molecules and F– and Cl– ions. DFT method with the BPW91 functional
and the 6-311 + G(d,p) basis set was used in the calculations of geometrical structure,
vibrational frequencies, and electronic energy values. The latter values made it possible to
find the enthalpy of the gas-phase reaction:
VOCl3 + 3F– = VOF3 + 3Cl–.
For calculation of the standard enthalpy of this exchange reaction (for the temperature T
= 298.15 K), were used the electronic energy values in combination with the thermal energy
values corresponding to this temperature. The standard enthalpy of this reaction was found to
be equal -480.2 kJ∙mol-1. This value corresponds to the value of enthalpy of formation
(rounded to integers): ΔfHº(VOF3, g, 298.15 K) = -1210 ± 30 kJ∙mol-1. The uncertainty is
estimated taking into account possible inaccuracy of energies in the used version of the
quantum-chemical calculations.
Using calculated molecular constants, the tables of thermodynamic functions of
VOF3(g) and VOCl3(g) were calculated for the temperature range 298.15-6000 K. Excited
electron energy levels contributions to the statistical sums were not taken into account because
these molecules with closed electronic shells have no low-lying excited electronic states. For
the standard temperature 298.15 K the following values were obtained:
VOF3(g) VOCl3(g)
Cp(298.15), J·K-1·mol-1 79.966 ± 2.4 89.973 ± 2.9
So(298.15), J·K-1·mol-1 309.293 ± 2.1 345.349 ± 3.2
H (298.15)-H (0), kJ·mol-1
o o
14.346 ± 0.4 19.789 ± 0.5
THERMODYNAMICS OF CRYSTAL–GAS EQUILIBRIA IN THE ZnO–SnO2 SYSTEM

Gribchenkova N.A., Steblevsky A.V. Alikhanyan A.S.
Kurnakov Institute of General and Inorganic Chemistry,
Russian Academy of Sciences, Moscow, Russia
e-mail: haguk@mail.ru
The vaporization processes in the system ZnO–SnO2 were studied by the Knudsen
effusion method with mass-spectrometric analysis of the vapor phase. Silica cells were used in
effusion experiments. The vapor composition and the vapor species partial pressures were
obtained (table). Incongruent vaporization of Zn2SnO4 was observed and p-x–projection of the
ZnO–SnO2 system phase diagram was constructed (figure). The standard enthalpy of
formation of Zn2SnO4 at the temperature 298 K was found to be -1296.2 kJ·mol-1.
Table. Partial pressures of the vapor species above the ZnO–SnO2 system at 1450 K, Pa.
Vapor
Solid phase
p(Zn) p(SnO) p(O2) p(total) composition,
composition
% SnO2
[ZnO] 13.78 - 4.83 18.61 0
[ZnO+Zn2SnO4],
13.78 0.02 4.83 18.63 0.14
field I
[Zn2SnO4+SnO2],
7.90 0.12 2.78 10.80 1.49
field II
[SnO2] - 0.26 0.28 0.54 100
Note. The partial pressures accuracy in the table is necessary for the equilibrium constants
calculation.
Figure. p-x–Projection of the ZnO–SnO2 system phase diagram (1450 K). Two cases of the
system behavior near pure ZnO are presented in the circles.
THERMODYNAMIC PROPERTIES OF FRIEDEL’S SALT AND POLYTHERMAL

SECTION OF PHASE DIAGRAM OF CaO–Al2O3–CaCl2–CaCO3–H2O SYSTEM
Grishchenko R.O., Emelina A.L., Orlov N.K.
M.V. Lomonosov Moscow State University, Moscow
e-mail: RomanGrishchenko@gmail.com
Friedel's salt (FS) is one of the high-performance reagents for desilication in the Bayer
process. To select the optimal conditions of desilication there is a need in the thermodynamic
properties of this compound. There is information on the standard enthalpy of formation of FS
[1], other properties have not been studied yet. So the purpose of present investigation is to
measure the temperature dependance of isobaric heat capacity and calculate the
thermodynamic properties of FS.
The substance was synthesized from water suspension of 3CaO·Al2O3 and CaCl2 by the
procedure [2]. The composition of the phase obtained was characterized by X-ray diffraction,
infrared spectroscopy, thermogravimetric analysis, simultaneous thermal analysis with mass
spectrometry and chemical analysis. The resulting product is a single-phase and has a
composition [Ca2Al(OH)6]Cl0.90(CO3)0.05·2H2O.
It is known that FS has a polymorphic transition from monoclinic to rhombohedral
phase at about 35°C [3]. In another paper [4] such a transition was at 6°C. The change in
temperature of the polymorphic transformation is caused by the influence of carbonate ion [5].
For the synthesized FS two anomalies close to 10 and 25°C, corresponding to the
polymorphic transition, were recorded by DSC method. According to the results of thermal
cycling of samples with different water content fragment of polythermal section of CaO–
Al2O3–CaCl2–CaCO3–H2O system was built.
The heat capacity of FS was measured by DSC in the temperature range 150‒250 K.
The dependence obtained was approximated with the combination of Einstein functions:
С p (Т ) = 3R ∑ ai С E (θ i T ) ,
i
where a1 = 8.28, θ1 = 244.2, a2 = 10.84, θ2 = 873.6.
Using these parameters and literature data [1] the standard thermodynamic properties of
FS were calculated. Table below shows the values of thermodynamic functions at 298.15 K.
Table. The standard thermodynamic properties of FS
С p , 298 , 
S 298 , ∆ f H 298

, ∆ f G298

,
−1 −1 −1 −1 −1
J∙mole ∙K J∙mole kJ∙mole kJ∙mole
333.8 ± 5 300.0 ± 20 −3835.02±4.2 [1] –3418.9 ± 7
The work is performed at User Facility Center of M.V. Lomonosov Moscow State
University (contract No. 16.552.11.7081 on 11.07.2012) under financial support of RFBR
(grant 13-03-00328).
References
1. Houtepen C.J.M., Stein H.N. // Cem. Concr. Res. 1976. V. 6, p. 651.
2. Dai, Y.C.; Qian, G.G.; Cao, Y.L., et. al. // J. Hazard. Mater. 2009. V. 170, p. 1086.
3. Rapin, J.-P.; Renaudin, G.; Elkaim, E., et. al. // Cem. Concr. Res. 2002. V. 32, p. 513.
4. Kirkpatrick, R.J.; Yu, P.; Hou, X.Q., et. al. // Am. Miner. 1999. V. 84, p. 1186.
5. Mesbah, A., Rapin J.-Ph., et. al. // J. Am. Ceram. Soc. 2011. V. 94, p. 261.
THE HEAT CAPACITY AND THERMODYNAMIC FUNCTIONS OF SAMARIUM

ORTHOPHOSPHATE SmPO4 IN THE RANGE 10−1600 K
Gurevich V.M.*, , Gavrichev K.S.**, Tyurin A.V.**, Ryumin M.A.**, Komissarova L.N.***
*Vernadsky Institute of Geochemistry and Analytical Chemistry,

**Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences
***Lomonosov Moscow State University, Moscow
e-mail: tac@igiс.ras.ru; gurevichvm@mail.ru
1. Low-temperature heat capacity of samarium orthophosphate SmPO4 was
experimentally measured by adiabatic calorimetry in the range 10.67−345.11 К. Based on
these data and high-temperature literature data [1,2] the thermodinamic functions of SmPO4
were calculated in the range 10−1600 К. The values of standart thermodinamic functions at
298.15 are: Сp0(298.15 К)=105.91±0.05 J K−1 mol−1, S0(298.15 К)– S0(10 К)= 114.75 ±0.14 J
K−1 mol−1, H0(298.15 К)−H0(10 К)=18.416 ±0.012 kJ mol−1, Ф0(298.15 К)– Ф0(10 К)=
52.978±0.15 J K−1 mol−1. The free Gibbs energy of formation was estimated: ∆fG0(298.15 К)–
∆fG0(10 К) = −1844.7 ±2.4 kJ mol−1.
2. The temperature dependence of heat capacity of SmPO4 in the range 10–476 К is
described by this equation:
3
Cp0(T)=а0 T(Cv)2 +n[(1/3) ∑ a j Dj (θj / T )+а4E(θE / T )+ a5K(θL / T ,θU / T )], (1)
j =1
where n − is the number of atoms in molecule (n = 6 for SmPO4); D and E − Debye and
Einstein functions; K − Kieffer K-function [3] θ1,θ2 ,θ3,θE ,θL ,θU − characteristics
temperatures; a0, a1, a2, a3 , a4, a5,− linear coefficients;
3
function Cv=n[(1/3) ∑ a j Dj (θj / T )+ а4E(θE / T )+ a5K(θL / T ,θU / T )]. Parameters of the
j =1
equation (1) were calculated by the non-linear LSM: θ1=271 К, θ2= 452 К, θ3=1743, θE =692,
θL=594 , θU=793 К; a0=3.0943×10-7 J−1 mol, a1=a2=a3=0.83333 , a4=a5=0.083333.
3. The temperature dependence of heat capacity of SmPO4 in the range 476 К–1600 К is
described by the equation :
3
Cp0(T)=а0 T(Cv)2 +n[(1/3) ∑ a j Dj (θj / T )+а4E(θE / T )] +С, (2)
j =1
where С − is the constant term. Parameters of the equation (2):θ1=129 К, θ2= 552 К, θ3=1767,
θE =817; a0=7.5091×10-7 J−1 mol, a1=a2=a3=0.83333 , a4=0.166667; С=−0.95 J K−1 mol−1.
This study was financially supported by the Russian Foundation for Basic Research
(project No 12–05–00033)
References
[1] Popa K., Konings R.J.M. //Thermodynamica Acta 445 (2006) 49–52.
[2] S.V.Ushakov, K.B. Helean, A. Navrotsky, and L.A. Boatner. // Journal of Materials
Research. 2001. V. 16. P. 2623–2633.
[3] Kieffer S.W. // Reviews of Geophysics and Space Physics 1979. V. 17. № 1. P. 35−59.
EXPERIMENTAL THERMODYNAMICS IN LITHIUM–TIN SYSTEM
D. Henriquesa, V. Motalovb, L. Benczec, T. Markusa

a
Forschungszentrum Jülich GmbH, Jülich
b
Ivanovo State University of Chemistry & Technology, Ivanovo
e-mail: v.motalov@gmail.com
c
Eötvös Loránd University, Budapest
An accurate knowledge on thermodynamic characteristics of pure substances and their
binary and ternary systems is a necessary prerequisite for modeling of thermochemical
stability of multi-component materials by semi empirical methods, e.g. CALPHAD. This
work is a part of the project “Experimental Thermodynamics and Phase Relations of New
Electrode Materials for Li-Ion-Batteries” and devoted to the investigation of Li-Sn system by
Knudsen Effusion Mass Spectrometry (KEMS) technique.
The Li-Sn alloys (molar fractions xLi = 0.1; 0.2; 0.3; 0.4; and 0.5) were prepared by
mixing and melting stoichiometric amounts of pure Li and Sn in closed tantalum crucibles
sealed in quartz glass ampoules under vacuum. The composition accuracy is estimated by a
relative error of 1%. The vaporization measurements were carried out in a substantially
modified single-focusing CH5 magnetic mass spectrometer (Varian MAT, Bremen) equipped
with a Knudsen cell assembly. The samples were downloaded in cylindrical tungsten cells
lined completely with Y2O3 inside a dry argon glove box and then transported to the
instrument in closed glass containers.
The liquid Li-Sn alloys have been evaporated in the temperature range 576-1040 K.
Only Li+ ion intensity was recorded during vaporization and Sn+ ion could not be detected in
the temperature range studied. The thermodynamic activity of lithium was determined by the
ratio of ion current intensities measured over the alloys and the pure Li metal. The activity of
tin was determined by Gibbs-Duhem integration. Then the results were approximated by
Redlich-Kister sub-regular solution model. Figs. 1 and 2 show respectively the activities of Li
and Sn for the melt at T = 900 K together with the available literature data. Our results were
found to be consistent with those obtained by the methods of electromotive force and
Knudsen effusion mass loss thus improving the reliability of activity data and demonstrating a
potential of the KEMS technique for thermodynamic studies of Li-containing alloys.
Fig. 1. Activity of Li as a function Fig. 2. Activity of Sn as a function

of composition at 900 K. of composition at 900 K.
THE BOND ENERGIES AND THERMOCHEMICAL PROPERTIES OF RADICALS,

DIRADICALS, AND CARBENES OF EXO-TRICYCLO[5.2.1.02,6]DECANE (TCD)
Hudzik J.M., Bozzelli J.W.
Chemistry, Chemical Engineering and Environmental Science,

New Jersey Institute of Technology, Newark, NJ 07102
Exo-tricyclo[5.2.1.02,6]decane (TCD) or exo-tetrahydrodicyclopentadiene is an
interesting strained ring compound and the single component high-energy density
hydrocarbon fuel. Important initial reactions of TCD at high temperatures would cleave the
strained carbon-carbon (C—C) bonds in the ring system creating diradicals constrained by the
remaining ring system. This study determines the thermochemical properties of these
diradicals (TCD-H2 mj-nj where m and n correspond to the cleaved carbons sites) including
their carbon-carbon bond dissociation energy (C—C BDE) corresponding to each cleaved site
from their parent hydrocarbons. Thermochemical properties including enthalpies (ΔH°f 298),
entropies (S(T)), heat capacities (Cp(T)), and C—H and C—C BDEs for the parent (TCD-H2
m-n), radical (TCD-H2 mj-n and m-nj), diradical (TCD-H2 mj-nj), and carbene (TCD-H2 mjj-
n and m-njj) species are determined. Structures, vibrational frequencies, moments of inertia,
and internal rotor potentials to determine optimized structures are calculated at the B3LYP/6-
31G(d,p) level of theory. Standard enthalpies of formation in the gas phase for the TCD-H2
m-n parent, radical, diradical, and carbene species are determined using the B3LYP density
functional theory and the higher level G3MP2B3 and CBS-QB3 composite methods.
Isodesmic work reactions are used for enthalpy analysis of these compounds to effect
cancelation of systematic calculation errors from ring strain. C– C BDEs range from 69.7 –
79.3 kcal mol-1 corresponding to TCD diradical singlet species and 77.3- 86.4 kcal mol-1 for
diradical triplet species. C– H BDEs for the parent TCD-H2 m-n carbon sites range from
93.2- 101.3 kcal mol-1. A similar range of 95.4- 101.5 kcal mol-1 for loss of the second
hydrogen from the radical species to generate the diradical triplet species with much lower
values of 86.1- 96.9 kcal mol-1 for diradical singlet species. Higher C– C BDEs are seen for
the carbenes which range from 80.5- 95.8 kcal mol-1 for the singlet and 85.8-94.2 kcal mol-1
for the triplet compared to the diradicals. Results from the DFT methods for the parents,
radicals, diradicals (triplet), and carbenes are in good agreement with results from the ab initio
composite methods using our sets of work reactions.
STUDY ON DENSITY FUNCTIONAL THEORY METHODS

FOR THE DETERMINATION OF MERCURY-HALOGEN
THERMOCHEMISTRY AND KINETICS
Itsaso Auzmendi-Murua, Alvaro Castillo, Joseph W. Bozzelli *
New Jersey Institute of Technology, NJ, USA
e-mail: Bozzelli@NJIT.edu
Emissions of gaseous mercury from combustion sources are the major source of Hg in
the atmosphere. Thermochemistry and kinetics for reactions of Hgo(g) with halogens are
important in the environment and in understanding Hg and ozone loss in Antarctic and Arctic
early spring ozone hole events. The formation of mercury-halides is also a method for capture
of Hg emissions from combustion processes. In this study we evaluate the geometry,
frequencies and energetic (thermochemistry) of Hg, Cl2, Br2, I2, HgCl, HgBr, HgI, HgCl2,
HgBr2 and HgI2, by the use of several density functional methods (B3LYP, B2PLYP,
ωB97X, M06,M06-2X) and basis sets (B3LYP, SDD, aug-cc-pVTZ-PP). We further study the
kinetics of a Hg insertion reaction into X2 (Hg + X2 → HgX2, X = Cl, Br, I) at the
aforementioned levels of theory. We present a comparison between the methods, and with the
available literature data, and recommend the use of M06-2X/aug-cc-pVTZ-PP.
ENTHALPY OF FORMATION OF THE ION IN THE GAS PHASE

Gruba O.N., Ryabukhin A.G.
South Ural State University, Chelyabinsk, Russia
e-mail: grox73@mail.ru
By definition the ion’s formation enthalpy in the gas phase (own steam, gas) is
composed of the element’s formation enthalpy ∆fH°(E0, g), ionization potential I1,2... and the
molar enthalpy of the electron gas. When charge (electron) moves from one energy level to
another, it arises at the same time with electromagnetic interaction, which value (∆H) is
described by Coulomb equation where the radius equal to the distance between the energy
levels (this distance equal to the ion’s radius in the limit).
Earlier, in [1] the enthalpy’s calculation model of a crystal lattice (∆pH) is described in
details. The model’s adequacy is confirmed by X-ray and thermochemical properties of
substances in numerous examples. According to the proposed model, enthalpy of destruction
(formation) of a crystal lattice is composed of two components: ∆H0 –the enthalpy of zero
level and ∆Hin – the enthalpy of the ion’s electromagnetic interaction
∆ р Н = ∆Н 0 + ∆Н in = 83,581728 ⋅ z 2К ⋅ z 2А ⋅ f1 + 138,9305405 A M (с.n.) z K z A f 2 rp−1 .
As you see, the second addend of the basic model’s equation also contains the inverse of
the ion’s radius rp as the factor. It was decided to test the possibility of model’s using in
calculation of the cation’s formation enthalpy in the gas phase. Elements of IIA subgroup
were taken as objects of research. The calculation’s results, which were received on proposed
model, are given in the table.
∆fH°(Me0,g), [2] ∆fH°(Me2+,g), [2] ∆fH°(Me0,g), [2] ∆fH°(Me2+,g), [2]

Ме Ме
∆fH°(Me0,g), calc. ∆fH°(Me ,g), calc.
2+
∆fH°(Me0,g), calc. ∆fH°(Me2+,g), calc.
143,846±1,674 2344,641±2,092 183,259±8,368 1663,703±8,368
Mg Ва
144,722 2345,567 181,450 1661,894
192,631±1,674 1940,249±1,674 149,012±12,552 1649,7958±12,552
Ca Rа
192,642 1940,260 150,055 1650,838
171,335±7,322 1797,365±7,322
Sr
178,302 1804,332
It was proved that the cation’s formation standard enthalpy in the gas phase can be
calculated from the equation, which was originally developed for the destruction (formation)
enthalpy of the crystal lattice.
Agreement between the calculated and experimental values is good in the confidence
intervals of the available experimental data. The possibility of the thermodynamic
determination of the atom ionization potential is sown using the values of standard formation
enthalpies.
References
1. A.G. Ryabukhin. Efficient ionic radiuses. An enthalpy of a crystal lattice. An enthalpy
of a hydration of ions. The monography. Chelyabinsk, 2001. 115 p. (In Russian).
2. Energy required to break chemical bonds. Ionization potentials and affinity for
electrons. Ref. ed. / Ed. V.N. Kondratiev. M. Nauka, 1974. 351 p. (In Russian).
THERMODYNAMIC PROPERTIES OF FLAVONOIDS –

PERSPECTIVE BIOLOGICALLY ACTIVE COMPOUNDS
Kasenova* Sh.B., Abildaeva* A.Zh., Rakhimova** B.B.,
Kasenov* B. K, Sagintaeva* Zh.I., Adekenov ** S.M.
*Zh. Abishev Chemical and Metallurgical Institute,
Karaganda, Kazakhstan, e-mail: kasenov1946@mail.ru
**JSC “International Research and Production Holding “Phytochemistry”,
Karaganda, Kazakhstan
In pharmacology and pharmaceutics the specific interest is represented by phenolic
compounds, in particular, flavonoids, possessing wide spectrum of biological activity.
The calculation results of thermodynamic constants of flavonoids and their derivatives
calculated by the approximate methods are presented in this paper: ΔН0comb. at 298.15 by
methods of Karash and Frost (averaged value ±5 %); ΔН0melting at 298.15 К by Gambill’s
equation, inaccuracy ± 10 %, ΔfН0(298.15) by Gess ±5-7%.
- ΔfН0(298.15),
№ Compound - ΔН comb.,
0
ΔН melting.,
0
kJ/mole
kJ/mole kJ/mole liquid solid
1 Axillarin 8325 131.3 371.3 502.6
2 Arcapillin 9049 174.6 326.6 501.2
3 Velutin 8528 108.3 168.4 276.6
4 Pectolinarigenin 8528 103.7 168.4 272.1
5 Penduletin 9107 136.8 269.1 405.9
6 Sudachinin 9049 147.4 326.6 474.0
7 Eupalitin 8427 135.9 269.4 405.3
8 Eupatolitin 8325 152.3 371.3 523.6
9 Eupatilin 9107 139.0 269.1 408.1
10 Cirsimaritin 8528 114.0 168.4 282.4
11 Yaceozidin 8427 121.8 269.4 391.2
12 3,5-dihydroxy-6,7,8-trimethoxyflavon 9107 135.6 269.1 404.7
13 5,3′,4'-trihydroxy-6,7,5′– 9049 156.3 326.6 482.9
trimethoxyflavon
14 3′,7,3'- trimethyl ether of quercetin 9107 135.7 269.1 404.8
15 5,7,3'-trihydroxy-6,4′,5'-trimethoxyflavon 9049 157.5 326.6 484.1
16 5,7,4'-trihydroxy-6,3,5'-trimethoxyflavon 9049 140.4 326.6 467.1
17 3,3'-dimethyl ether of quercetin 8427 121.0 269.4 390.4
18 3,5' – dimethyl ether of miricetin 8325 147.8 371.3 519.1
19 7,4'- dimethyl ether of apigenin 8630 84.6 66.4 151.0
HEAT CAPACITY IN THE RANGE OF 10-330 K AND RELAXATION TRANSITIONS

OF CHITINE AND CHITOSAN FROM THE CRAB SHELL
Kashtanov E.A., Kokurina N.Yu., Uryash V.F.
Research Institute of Chemistry, Nizhny Novgorod State University
e-mail: ltch@ichem.unn.ru
Heat capacity or chitin from the shell of the king crab (Paralithodes camtchaticus) and
chitosan made from it as well as their hydrolyzed specimens were measured in the range of
10—330 K using vacuum adiabatic calorimeters. The temperatures of relaxation transitions
and decomposition of the above specimens were studied with the method of differential
thermal analysis (DTA) in the temperature range of 80-550 K. Their thermodynamic
characteristics (enthalpy, entropy, and the Gibbs function) were calculated in the range from
Т→0 K to 320 K. The analyzed materials were as follows: “crystalline” crab chitin (CCT)
(TU 64-14-170-89) (the molecular mass of 1.4∗106, the deacetylation degree of 2-4%) and
“crystalline” chitosan (CCTS) (TU 9289-067-00472124-97) (the molecular mass of 8.3∗105,
the deacetylation degree of 85%) manufactured by ZAO “Bioprogress” (Shelokovo, Moscow
Oblast) and hydrolyzed chitin (HCT) (the molecular mass of 1.0∗106, the deacetylation degree
of 2-4%) and chitosan (HCTS) (the molecular mass of 6.0∗105, the deacetylation degree of
84%) fabricated from them at the “Bioengineering” Center of the Russian Academy of
Sciences. The crabs were fished out at the Okhotsk Sea during one fishing season at the stage
of intermolt. The specimens were subjected to demineralization and deprotonation. Since air-
dry CT and CTS specimens contained 4-10 mass% of adsorbed water which, as far as we
know, evaporated from the obtained polysaccharides at 400-407 K, they were dried prior to
calorimentric experiments in 0.6 Pa vacuum at the above temperature for several hours till
constant mass.
The mole heat capacity of chitins is higher than that of chitosans in the entire analyzed
temperature range that corresponds to a higher molar mass of the recurring links of CT as
compared to CTS. The comparison of heat capacities of CCT and HCT shows that heat
capacity of CCT is lower than that of HCT. This points to a more ordered CCT structure as
compared to HCH. The C°p =f(T) curves of HCT and HCTS in the temperature range of 230-
250 K demonstrate anomalies of the endothermal nature (γ-transition). However, this
transition is absent in CCT and CCTS. This is likely to point to the fact that the CCT and
CCTS structure becomes less ordered upon hydrolysis. In addition, one more relaxation period
is observed on the C°p =f(T) curve of HCTS in the range of 315-325 K (β-transition) which is
induced by libration of pyranose rings around a glucoside bond. These transitions were also
detected using the DTA method as well as two devitrification temperature ranges that points
to the inhomogeneous structure of the studies polysaccharides which consists of highly
ordered and amorphous microregions. Chitin decomposition is accompanied by absorption of
energy in the form of heat; that of chitosan, by energy release.
GAS PHASE COMPOSITION OVER ALUMINUM, GALLIUM, INDIUM OXOPIVALATES.

THERMODYNAMIC PROPERTIES OF GALLIUM OXOPIVALATES
Kayumova D.B., Kamkin N.N.*,Yaryshev N.G.*, Sirotkin D.A.,
Malkerova I.P., Alikhanyan A.S.
Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow
*Moscow State Pedagogical University
e-mail: alikhan@igic.ras.ru
Aluminum, Gallium and Indium oxopivalates with the general chemical formula
MxOy(piv)z (M = Al, Ga, In) were synthesized by solid phase interaction of silver pivalate and
gallium, indium and aluminum hydride at vacuum with residual pressure 5.0 Pa and
temperature range 100-220оС. The study of vaporization thermodynamics was performed by
the Knudsen effusion technique with mass-spectrometric analysis of the vapour phase.
Condensed oxopivalates were considered as the substances with the composition
nM(piv)3·mM2О3 of two-component system М(piv)3 – M2O3. The gaseous phase over
synthesized compounds was shown to consist of polymeric molecules M2O(piv)4, M3O(piv)7,
M3O2(piv)5, M4O(piv)10, M4O2(piv)8, M4O3(piv)6, M5O3(piv)9, M5O4(piv)7, M6O5(piv)8. In
this work synthesized gallium oxopivalate with the general formula Ga2,1O(piv)4,34 was
supposed to be two-component system Ga(piv)3 – Ga2O3 with starting composition 81,3 mol%
Ga(piv)3. The experimental results of the sample vaporization were used to calculate the
standard enthalpy of formation some gallium oxopivalates.
Enthalpy of formation of gallium oxopivalates (kJ/mol)

-ΔfHo298
Compound -ΔfHo298 (standard)
(nGa(piv)3, mGa2O3)
Ga3O(piv)7(g) 4142 ± 35 -27 ± 33
7Ga(piv)3·Ga2O3 (s) 12984 ± 88 478 ± 181
4Ga(piv)3·Ga2O3 (s) 7892 ± 87 280 ± 152
7Ga(piv)3·2Ga2O3 (s) 14085 ± 162 490 ± 226
The values of the standard enthalpy of formation of condensed gallium oxopivalates

have shown their high thermodynamics stability and high probability of formation in various
industrial processes with using pivalate complexes. These thermodynamic properties can
significantly inhibit the formation of oxide films and coatings with fixed physical-chemical
characteristics by using of CVD, molecular beam, magnetron evaporation methods.
This work was supported by the Russian Foundation for Basic Research (grant 12-03-
31669) and Presidium of the Russian Academy of Sciences (Program P8-1).
THERMODYNAMIC PROPERTIES OF THERMOTROPIC

MESOGENS. CALCULATION METHODS
Kazmina T.M., Lozeiko T.V., Solovov R.D., Pestov S.M.
e-mail: kazm.tm@gmail.com
Liquid crystals (LC) are widely used as components of materials for electronics [1, 2].
At present more than 100,000 compounds forming mesophase are synthesized [3]. Calamitic
LC are the most interesting substances for a practical usage. However, for the majority of
mesogens only temperatures of phase transitions and a type of mesophase are known. To
enlarge areas of industrial application, it is necessary to have a reliable information on
thermodynamic properties of LC. It gives an opportunity to optimize a selection of
components for LC materials and to determine their miscibility [4].
For properties estimation, a scheme based on molecular structure is proposed.
Applicability of the group-contribution methods has been first tested on p-substituted "model
substances", (i.e. compounds having a structure typical for calamitic mesogens, for which a
set of physical properties had been well studied). Methods, that gave the minimum difference
between the estimated and experimental data, have been tested on calamitic mesogens.
Corresponding states methods were checked on LC. Critical properties and boiling
temperature were estimated basing on Lydersen and Meissner methods [5]. A scheme for the
estimation of thermodynamic properties, i.e. heat capacity, temperatures and enthalpies of
phase transitions of calamitic LC was proposed. A possibility to spread the scheme for the
estimation of heat capacity for banana and discotic LC was demonstrated.
To decrease the time of electrooptic effects, LC materials were doped by non-mesogenic
additives having low viscosity. Scheme for estimation of vapour pressure of mesogens was
developed. It gives a possibility to determine the most volative components in LC mixtures.
Different correlation dependencies have been tested on a huge volume of experimental
data that were tested by the expert evaluation [6]. Precision of estimation methods is enough
for engineering calculations.
References
1. Tomilin M.G., Pestov S.M. // Opt. Zh. 2012. V. 79. № 9. P. 66-80.
2. Tomilin M.G., Pestov S.M. Properties of liquid crystalline materials. SPb.: Polytechnika,
2005. 296 p. (in Russ.)
3. Pestov S., Vill V. Liquid Crystals. / In: Springer Handbook of condensed matter and
materials data. /ed.: W. Martienssen. Berlin: Springer, 2005. P. 941.
4. Molochko V.A., Pestov S.M. Phase equilibria and thermodynamics of systems containing
liquid crystals. Moscow: Print. Center MITHT, 2003. 242 p. (in Russ.)
5. Lyman W.J., Reehl W.F., Rosenblatt D.H. Handbook of chemical property estimation
methods. Washington: Am. Chem. Soc., 1990. 960 p.
6. Pestov S. Physical properties of liquid crystals. / Landolt-Boernstein. N.S. VIII/5A. -
Berlin: Springer, 2003, 492 p.
CHEMICAL THERMODYNAMIC OF CERTAIN TITANIUM-

AND TUNGSTEN-CONTAINING OXIDES
Knyazev A.V., Chernorukov N.G., Knyazeva S.S.
Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod, Russia
e-mail: knyazevav@gmail.com
Ternary and binary oxides of titanium and tungsten may crystallize into different
structural types: hollandite, spinel, pyrochlore, brannerite and other. These compounds can be
used as ionic conductors, catalysts, sorbents, pigments and matrices for radioactive wastes.
The objects of our study within the hollandite-type structure are compounds of the general
formula MI2AIII2Ti6O16 (AIII– Al, Cr, Fe, Ga). The framework of these compounds is built of
(AIII/Ti)O6 octahedra that share edges in a zigzag fashion to form blocks linked via octahedral
apices. The ideal spinel structure has cubic symmetry (space group Fd3m) and crystal
chemistry formula MA2O4. In the defect pyrochlore (BV/W)O6 octahedra share corners to form
a three-dimensional framework possessing tunnels running down the c-axis in which M
cations are located. We carried out a full-profile X-ray analysis of 15 compounds. The
coordinates and isotropic thermal parameters of the atoms were determined. The temperature
dependences of heat capacities at constant pressure for 7 compounds in a temperature interval
from 7 to 350 K were studied in an adiabatic vacuum calorimeter. The obtained data allowed
to describe possible phase transitions and to calculate absolute entropies of formation of the
compounds. We should point out that heat capacities of the part compounds, in particular,
LiVWO6, NaVWO6, KSbWO6, CsTaWO6 monotonously grow with rising temperature
without any visible anomalies. On the contrary, the physical transitions are observed in
K2Fe2Ti6O16, Li4/3Ti5/3O4 and RbNbWO6. The description of transitions was made by means
of McCallaf - Vestrum classification of physical transitions. Isothermal (I) transitions in
Li4/3Ti5/3O4 and RbNbWO6 are seen as “peaks” on the curve of heat capacity; the area of
“peaks” is numerically equal to the enthalpy of phase transition. The sole compound which
shows the third kind of physical transitions, that is G-type (glass-like) one, is dipotassium
diiron(III) hexatitanium oxide (K2Fe2Ti6O16). The nature of this anomaly is, probably, related
to the presence of cation–cation interactions in the structure of this compound which we have
confirmed by using Voronoi - Dirihle calculations of polyhedra with program complex
TOPOS. Using differential scanning calorimetry in combination with the method of high-
temperature X-ray diffraction all compounds were studied for the first time. For example,
endothermic effect at 1345 K on the DTA curve of Li4/3Ti5/3O4 is connected with
decomposition of compound to crystalline Li2Ti3O7 (mineral ramsdellite with space group
Pbnm) and liquid lithium oxide. Rubidium niobium tungsten oxide decomposes at 1465 K.
Thermal decomposition produces crystalline Rb0.27NbO3 and, probably, liquid Rb0.73WO3.
Differential scanning calorimetry data, reaction calorimetry data and thermodynamic
modeling allow to put together phase diagrams. For system LiVWO6 - NaVWO6 modeling
includes the following steps: 1. calculating solidus and liquidus temperatures based on
crystal-liquid equilibrium; 2. calculating the critical temperature on a solid-solution
segregation curve (TM) using Becker's equation. The enthalpy of formation of Li4/3Ti5/3O4 was
experimentally determined by reaction calorimetry.
PHASE TRANSITIONS OF DENDRITIC AZOMETHINE IRON COMPLEXES

Kolker A.M., Chervonova U.V., Gruzdev M.S.
Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo
e-mail: amk@isc-ras.ru
The purpose of this work is to obtain a two series of dendritic iron(III) complexes based
on Schiff base with composition [2L∙Fe∙X] (L – azomethine (I - 3,5-di(3,4,5-
tri(tetradecyloxy)benzoiloxy)benzoiloxy-4-salicyliden-N’-ethyl-N-ethylenediamine; II - 3,5-
di(3,5-bis(3,4,5-tri(tetradecyloxy)benzoiloxy)benzoiloxy)benzoiloxy-4-salicyliden-N’-ethyl-
N-ethylenediamine), X – counter-ion NO3-, Cl-, PF6-, BF4-, ClO4-) and to study phase behavior
of this complexes. Structural model of the compounds investigated are given on Scheme.
+
R C N N CH3 NO3- I.1
H H H29C14O
PF6- I.2
O O
Fe Cl- I.3
O H29C14O
BF4- I.4 O
H I.5 O H29C14O
H 3C N N C R ClO4-
H R=
O H29C14O
+ O
R H29C14O
O O
H29C14O
O C N N CH3 NO3- II.1
H H
R PF6- II.2
O Cl-
Fe II.3
O BF4- II.4
H R
ClO4- II.5
H 3C N N C O
H
O
R
In order to verify the purity and structure of the compounds obtained UV/Vis spectra,
infrared spectra, 1H NMR and mass spectra were registrated and chromatographic and X-ray
diffraction experiments were performed. Based on elemental analysis and MALDI-ToF MS it
was established that complexes are bisligand compounds with octahedral packing of iron(III)-
ion. Based on the data of chromatographic analysis it is possible to conclude about purity and
individuality of compounds, as well as their ability to form associate. Phase behavior of
complexes was studied by means of the differential scanning calorimetry and polarized optical
microscopy. It was found that obtained coordination compounds exhibit solid-phase transition
as well as mesomorphic properties subject to counter-ion. Mesomorphic properties are
characteristic for complexes who conter-ions are able to form associate by means of hydrogen
bond. It is the complexes of first group with PF6-, BF4-, СlO4- ions and second group with
NO3-, Cl-, ClO4- ions.
The work was carried out with financial support of grant of RFBR № 12-03-31006
mol_a and Program of Presidium RAS №24.
THE STUDY OF THERMODYNAMIC OF SORPTION OF BIOLOGICALLY ACTIVE

ADAMANTANE'S DERIVATIVES BY THE METHOD OF HIGH PERFORMANCE
LIQUID HROMTAOGRAPHY ON HYPERCROSSLINKED POLYSTYRENE
Konstantinov A.V., Shafigulin R.V., Ermokhin V.A., Bulanova A.V., Purygin P.P.
Samara State University, Samara
e-mail: konav88@mail.ru
In recent years, increasing attention of researchers draw frame hydrocarbons -
adamantanes. First of all, it is connected with the developing of biological activity due to the
pronounced lipophilic nature of frame-carbon fragment of adamantane, which determines the
permeability or adsorption of agents on cell membranes.
Study of the thermodynamics of sorption from liquid multicomponent solutions is actual
direction of modern physical chemistry, as these studies will not only develop the
thermodynamics of solutions, but also to develop practical methods for the extraction and
concentration of substances of different chemical nature.
Most suitable for this study of physical-chemical method is high-performance liquid
chromatography (HPLC), where the mobile phase (eluent) can be a mixture of organic and
inorganic liquids.
This paper presents a study of the thermodynamics of adsorption of adamantane's
derivatives on hypercrosslinked polystyrene by reverse-phase high-performance liquid
chromatography.
The experiment was carried out on the liquid chromatography system Varian ProStar
with UV detector. Detection was performed at a wavelength of 210 nm, the flow rate of eluent
was 0.5 ml/min, at the temperature 293 K, 313 K, 323 K, 333 K. The mobile phase consisted
of a mixture of water and acetonitrile in different volume ratios.
The plots of logarithm of the retention factor of 1000/T were constructed , and it was
calculated the heat effect of the transition of the sorbate from volume's solution in the surface
layer (Q).
Change of standard differential Gibbs' energy of adsorption (ΔGº) was calculated. For
all compounds ΔGº<0, which indicates a shift of equilibrium "sorption-desorption" toward
sorption.
To assess the impact of structural changes on the retention it was calculated the δ(ΔG)i,st
- the difference between the free energy of adsorption of an infinitely dilute solution of the
substance i in relation to the adsorption of some substance comparison - the standard material
for this series of compounds.
For studying of influence of physical and chemical properties of the sorbate on retention
it would be considered a model-based retention correlations "chromatographic retention -
physico-chemical property of the sorbate". Correlations of the retention factors, which
calculated by the equations linking the retention factor with the physical and chemical
properties of the sorbate molecules of the same sample group studied adamantanes, have high
predictive ability of the retention factor values from water-acetonitrile solutions at
hypercrosslinked polystyrene.
This work was supported by the state task Ministry of Education and Science of the
Russian Federation № 3.3209.2011.
THERMOANALYTICAL INVESTIGATION
OF SULFUR-CONTAINING AMMONIUM SALTS
Kosova D.A., Kozyulina A.V., Emelina A.L.
e-mail: dakosova@gmail.com
Sulfur-containing salts are of interest from the point of view of their use in agricultural
technology as herbicides and nitrogen fertilizer additives. Thermodynamic properties of
ammonium salts, in particular, phase transitions of these compounds are necessary for the
prediction of chemical and phase equilibria in the systems including these substances.
Two salts - ammonium sulfate and sulfamate - were the object of investigations in this
paper. The available data about the phase transitions of (NH4)2SO4 and NH4NH2SO3 are
fragmentary and contradictory. In this context, the goal of this paper was to study of these
compounds by differential scanning calorimetry method (DSC) in a wide range of temperatures
and pressures.
It was shown that any anomalies at the temperature dependence of ammonium sulfamate’s
heat capacity from -150 ° C (123 K) to the melting point of 130.9 ˚ C (404.4 K) [1,2,3] were
absent. It was refined tentative data of Konkoly Thege [2, 3] for the melting heat of NH4NH2SO3.
The phase transition of ammonium sulfate at -50 ° C (223 K) was studied. The source of
the discrepancy in the value of corresponding heat effect obtained by different authors [4,5] was
found. For the first time a high-temperature phase transition of ammonium sulphate was
registered and its parameters were determined by high-pressure calorimetry method. Previously,
the existence of this transition was predicted on the basis of the theory of groups [6, 7] and by
analogy in the temperature dependence of the physical properties of (NH4)2SO4 and isostructural
compounds K2SO4, K2SeO4.
The authors acknowledge partial support from M.V.Lomonosov Moscow State University
Program of Development and URALCHEM OJSC. The work is performed at User Facilities
Center of M.V. Lomonosov Moscow State University (contract number 16.552.11.7081 at 11 July
2012).
References
1. Gordon W. E., Martin E. Industrial and engineering chemistry. 1932. V. 31. P. 1237 –
1238.
2. I. Konkoly Thege. Thermochimica Acta. 1983. V. 60. P. 149 – 159.
3. I. Konkoly Thege. Journal of Thermal Analysis. 1983. V. 27. P. 275 – 286.
4. Shomate C .H. J.Am.Chem. Soc. 1945. V. 67. P. 1096 – 1098.
5. Hoshino S. etc. Physical Review. 1958. V. 112. P. 405 – 412.
6. A. Sawada etc. Journal of the Physical Society of Japan. 1976. V. 41. P. 174 – 180.
7. S. Jerzak. Ferroelectrics. 1997. V. 200. P. 197 – 205.
INVESTIGATION OF PHASE TRANSITION

IN CERTAIN LAYERED PEROVSKITES
Krasheninnikova O.V., Knyazev A.V., Komshina M.E.
Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod, Russia
e-mail: kraska1991@inbox.ru
Bismuth-containing ferroelectric with a layered structure of the mineral of perovskite,
first described by Aurivillius, recently started to receive increasing attention from researchers.
General formula for these compounds can be written as Аm-1Bi2BmO3m+3, where m typically
ranges from 1 to 5. A usually stands for one-, two-, and trivalent cations or combinations with
CNA> 6. B most commonly stands for transition elements with octahedral coordination (CNB
= 6). The structures of these stoichiometric compounds are built from packets and blocks. The
packet consists of n layers of anion octahedra and with n → ∞, is similar to the cubic
perovskite. The block can be regarded as a fragment of the structure of cubic BiF3. Bismuth-
containing ferroelectric with a layered structure (BLSF) are characterized by a low dielectric
conductivity, high Curie temperatures, low temperature coefficients of resonant frequency and
highly anisotropic electromechanical coupling coefficients.
The "ideal" crystal structure of Aurivillius phases, due to its layered nature, has a
tetragonal syngony with space group I4/mmm. However, many compounds of this family have
a lower symmetry of the unit cell due to the rotational distortion of the structure. Nevertheless,
the majority structures when heated undergo phase transitions generally resulting in an
increase in the symmetry of the unit cell and the drift of Aurivillius phase to their "ideal"
structure. In our work, we have set the goal of obtaining low-temperature modifications of
compounds in order to study the behavior of the structure under heat, mechanisms of phase
transitions and to determine the Curie temperature. Using solid-state reactions we have
obtained Aurivillius phases containing packages of one to five layers of octahedra, namely
Bi2MoO6 (m = 1, orthorhombic syngony, space group Pca21), Bi3NbTiO9 (m = 2,
orthorhombic syngony, space group A21am), Bi4Ti3O12 (m = 3, orthorhombic syngony, space
group B2cb), BaBi4Ti4O15 (m = 4, tetragonal syngony, space group I4/mmm), Ba2Bi4Ti5O18
(m = 5, tetragonal syngony, space group I4/mmm). Using differential scanning calorimetry
determined the Curie temperature and the melting temperature of the obtained compounds.
The Curie temperature (TC) is the temperature of phase transition of type II associated with an
abrupt change in the symmetry properties of the substance. It should be noted that most of the
Aurivillius phases are stable up to the melting point. The only exception are those in which
the package consists of only one octahedron. Lower stiffness of the structure is making
possible the restructuring, which leads to the formation of framework structures of layered
Aurivillius phases. On the example of Bi2MoO6 we have demonstrated irreversible
restructuring into zeolite-like structure, which results in reducing of the coordinative
nonsaturation of bismuth atom and increase of its coordination number from 4 to 8 and 9. We
found a downward trend in the Curie temperatures and melting compounds through the
increase of the number of octahedra in the packet of Aurivillius phase. Using high-
temperature X-ray diffraction we have determined the temperature dependencies of the unit
cell parameters and thermal expansion coefficients for all of the synthesized compounds. In
studying of the compound Bi4Ti3O12 it has been determined that in fact the increase of
temperature triggers the alignment of parameters a and b, and then an abrupt increase in
symmetry.
THERMODYNAMICS OF PHASE TRANSITIONS OF LANTANIDOMESOGENS

EXHIBITING SMECTIC C MESOMORPHISM
1
Krupin A.S., 1Shamsutdinova R.D., 1Molostova E.Yu, 1,2Knyazev A.A., 1,2GalyametdinovYu.G.
1
Kazan National Research Technological University, Kazan
2
Kazan Physical-Technical Institute, Kazan Scientific Center,
Russian Academy of Sciences, Kazan
e-mail: krupin_91@mail.ru
Thermotropic liquid crystals (LCs) have been widely used as a liquid anisotropic
medium in different devices that can display and processing information. Introduction of
lanthanide ion to the liquid crystal molecules allows to combine orientation behavior of liquid
crystalline mesophases with high magnetic anisotropy and fluorescent properties of a series of
lanthanide ions and to approach the creation of multifunctional materials with unusual
magnetic and optical properties.
This work presents tris [1-(4-(4-propylcyclohexyl)phenyl)decane-1,3-dione]-[1,10-
phenanthroline]europium (Fig. 1), exhibiting a smectic C mesomorphism in the temperature
range from 55 up to 135oC.
1,5
C3H7 Охлаждение
C7H15 1,0
Тепловой поток, мВ
0,5
O O 3
0,0
Eu
N N -0,5 I
Cr Sc
-1,0 Нагрев
-1,5
40 60 80 100 120 140
Температура, C
Fig. 1. Structure of the europium (III) Fig. 2. DSC thermogram of the europium
complex (III) complex during heating and cooling
Thermodynamics of phase transitions were studied by polarization polythermal

microscopy and differential scanning calorimetry. Synthesized complex vitrified at cooling
from mesophase preserving molecular packing defined in the mesophase. This is evidenced by
the absence of peaks in the DSC curve during the cooling (Fig. 2) and storage at room
temperature the texture of the smectic C mesophase observed in the polarizing microscope.
Synthesized complex has effective luminescence with a maximum pick at a wavelength
612 nm.
Thus, the possibility of the creation of supramolecular-organized luminescent materials
with specific packing of the molecules in a wide range of temperatures, including room
temperature was shown.
The work was carried out with the support of the Russian Foundation for Basic
Research (RFBR) grant №12-03-31424 мол_а.
THERMODYNAMIC PROPERTIES OF SYNTHETIC CARBONATE CANCRINITE

Kurdakova S.V., Grishchenko R.О., Druzhinina А.I.
e-mail: s.kurdakova@gmail.com
Cancrinite are minerals of subclass of framework aluminosilicates. These compounds
have structure and composition, which are close to hydroaluminosilicates formed as waste
product during desilication in the Bayer process (DSP - desilication product). It is known a lot
of works on determination the structure of natural and synthetic cancrinites, while data on the
thermodynamic properties is scattered and often contradictory. Thus the purpose of this work
was to synthesize and to determine the thermodynamic properties of cancrinite.
Powdered sample was synthesized in titanium autoclave with a teflon insert in the
hydrothermal conditions. Product identification was performed by X-ray powder diffraction
and infrared spectroscopy. The Na/Al/Si ratio was determined according to the analysis by
scanning electron microscopy with energy-dispersive analyzer. Thermogravimetric analysis
with infrared spectroscopy of evolved gases allowed determining the content of carbonate
groups and water in the sample. According to the above results the cancrinite has a
composition Na8.28[Al5.93Si6.07O24](CO3)0.9(OH)0.51·3.85H2О (number of hydroxyl groups was
calculated according to electroneutrality).
The heat capacity of cancrinite was first measured in the range 6 - 259 K by the method
of low-temperature adiabatic calorimetry. The data were approximated by the combination of
three Einstein’s functions:
C P (T ) = 3R ∑ ai
(θi / T )2 e θ / T i
,
i (e θi / T
)
−1
2
where аi and θi – variable parameters. Their numerical values with spare significant figures
are given in Table 1.
Table 1. The parameters of Einstein’s functions

a1 = 29.214 ± 0.46 а2 = 21.650 ± 0.36 а3 = 7.382 ± 0.46
θ1= 898.121 ± 19.5 (K) θ2 = 308.479 ± 7.4 (K) θ3 = 114.442 ± 3.5 (K)
Based on the data obtained the standard thermodynamic functions of cancrinite in the
temperature range 5 - 300 K were calculated. The values of the functions at 298.15 K are
presented in Table 2.
Table 2. Thermodynamic functions of synthetic cancrinite at 298.15 K

Cp,298.15, S298.15, H298.15–
−1 − −1 −
J∙mole ∙K J∙mole ∙K H0,
1 1
kJ∙mole−1
1035.6 ± 2 1057 ± 20 287.2 ± 2
The work is performed at User Facility Center of M.V. Lomonosov Moscow State
University under financial support of RFBR (grant 13-03-00328).
MODEL-STATISTICAL REPRESENTATION OF THERMODYNAMIC PROPERTIES

OF GLASS AND MELT
Kut’in A.M.
G.G. Devyatykh Institute of Chemistry of High-Purity Substances RAS, Nizhny Novgorod
e-mail: kutyin@ihps.nnov.ru
In the conceptual model that defines the thermodynamic properties of various condensed
states of individual substances by characteristics of elementary excitations we show that the
glassy state in its parametric basis inherits the liquid state.
Contribution of m collective degrees of freedom to the structural (formulas) unit
substance in thermic properties of condensed matter is defined by parastatistics functions
with argument in the form of the reduced energy g* in activation of elementary excitations.
1+ b  1+ b 
G (T) – (H (0) - T S (0)) = − m⋅RT⋅ln , S (T) - S (0) = m⋅R⋅ ln − g*'⋅n 
1 + bp  1 + b p 
H (T) - H (0) =−mRT g*'⋅ n , Cp (T) = mR⋅[(g*') (b(1+b)−(p+1) bp⋅(1+bp)) − (g*'+ g*") n ],
2 2
b = 1/(exp(g*) − 1), bp = 1/(exp((p+1)g*) − 1), n = b − (p+1)bp.

Taking into account the anharmonicity of the vibrational contribution to the
thermodynamic functions of optical, quasilocal modes, represented by the number of Einstein
me of degrees of freedom, is determined by the following expressions (p → ∞ and g* = θ i /T):
Ge(T) = − me R и ln(1+be), He(T) = me R·и be,
Se(T) = (He(T) − Ge(T))/T, CPe (T) = me R (θe /T)2be(1+be),
Where be = 1/(exp(θe(1/T – α*)) −1), θe is the Einstein temperature, parameter α* is
interconnected with the anharmonicity constant.
Glassy state d = d0 / (1 - (T / Tg) t ) at T ≤ Tg; Liquid state
g*= d ln (1 + gl*/ d) d = ∞ at T > Tg. gl*=h*/ T – s*
Δgl/lCP = mRTgA{(A-2h*/Tg)[b(1+b) - (p+1)2bp(1+ bp)] + [3+4s*/g*-t(4g*/(3d0)+1)] n }
Δgl/lH(0) = mRTgA n Δgl/lS(0) = Δgl/lH(0)/ Tg, where A = g*2t/(2d0)
Liquid enthalpy (h*) and entropy (s*) parameters in gl* are supplemented for glass with
parameter of internal dimension d which ”critical” temperature dependence, automatically
providing transition g* for liquid in gl* for glass, describes the change in the properties of
glass and liquid at glass transition. The last of the above expressions, in particular, determine
the "jump" of heat capacity at glass transition as well as enthalpy and entropy redundancy of
glass.
Thermal equation of state for liquid and glass is represented by the dependence of
molar volume V = V0 + ΔVl/g +ΣΔVe upon temperature and pressure. In their turn, the
contributions to the change in molar volume of the collective (ΔVl/g) and Einstein (ΣΔVe)
degrees of freedom is determined by the derivatives of pressure from the corresponding Gibbs
energies (ΔV = (∂G/∂P)T).
For inclined to vitrification representatives of organic and inorganic compounds we
represent the results of successful quantitative approximation of calorimetric and volumetric
data set of condensed states with capabilities for calculating the thermodynamic functions,
their extrapolation and compensation for insufficient information.
AN ESTIMATION OF SEVERAL PROPERTIES OF CYCLIC

AND ACYCLIC CARBONATES
Kuz’min A.E.
Topchiev Institute of Petrochemical Synthesis RAS, Moscow
e-mail: kuzmin@ips.ac.ru
Organic carbonates are a category of substances having constantly growing interest to its
methods of synthesis (oxidative carboxylation of alkenes, alcohol hydroformilation, possible
carboxylation of glycerol to glycerol carbonate [1]) and application opportunities (components
of electrolytes, varnishes, resin solvents, monomers, reagents for synthesis of glycols,
plasticizers etc, among them [2] a value of dimethyl carbonate as a fuel additive have been
shown), and the information on their thermochemical, critical and other properties is
extremely important. However, known experimental data for these properties are few, usually
ambiguous and are represented very irregularly for different substances in the category: so,
values ∆Н°(g)298 and ∆Н°(l)298 are known for many carbonates (both cyclic and acyclic), but it
is few values of S°298 for both states; for propylene carbonate there are values ∆Н°(g)298,
∆Н°(l)298, сp(g)(T), сp(l)(T) and S°(g)298, for glycerol carbonate – only ∆Н(vap)298 and ∆сp298. Then,
it is very interesting problem to realize on the basis of existing data a systematic estimation of
the still unknown properties of well-known organic carbonates; the situation becomes
complicated because nearly no one group additive method have an carbonate group SO-O2
increments, and it seems that last attempts to fill the gap during calculations of chemical
equilibria with participation of liquid carbonates [3] are methodically disputable.
Calculations carried out in following directions:
1) discrepancies for known ∆Н°(g)298 values and correctness of known Benson СО–О2
group increment (-125 kJ/mol) were analyzed;
2) contributions for СО–О2 and dioxolane ring group values for ∆Н(vap)298 and ∆Н°(vap)
were calculated both directly (by Kolska-Ruzicka, Constantinou-Gani, Joback-Reid methods)
and via Watson's temperature dependences and Fish-Lielmezs (with definition of СО–О2
contributions for critical temperatures and normal boiling temperatures by Wilson-Jasperson,
Constantinou-Gani, Joback-Reid methods). Mismatches between the calculated values were
analyzed;
3) heat capacity temperature rows for ideal-gas and liquid states (with the further
transition to S°(g)298 and S°(l)298 calculations) and its СО–О2 group contributions were
estimated by Benson (сp(g)) and Ruzicka-Domalski (сp(l)) methods; additional check of сp(l)
values also carried out by results of comparison of the dimethyl carbonate equation of state
from [4] with more common Lee-Kesler equation of state for the substance (elimination of
CO-O2 group corrections).
References
1. Ezhova N.N., Korosteleva I.G., Kolesnichenko N.V., Kuz’min А.Е., Khadzhiev S.N.,
Vasil’eva M.A., Doronina Z.D./ Petr. Chem., 2012, v. 52, p. 91
2. Katrib Y., Deiber G., Mirabel P., Calve S. L., George C., Mellouki A., Bras G. L./ J.
Atmos. Chem. 2002, v. 43, p. 151.
3. Jiabo Li, Tao Wang/ J. Chem. Thermodynamics, 2011, v. 43, p. 731
4. Yong Zhou, Jiangtao Wu, Lemmon E. W. / J. Phys. Chem. Ref. Data, 2011, v. 40, p.
043106
INFLUENCE OF MIXED SOLVENT METHANOL–ACETONITRILE

ON SOLVATION PIPERIDINES
Кuz’mina I.А., Sharnin V.А., Sitnikova К.А., Volkova М.А.
Institute of Thermodynamics and Kinetics of Chemical Processes, Ivanovo, Russia
е-mail: oxt703@isuct.ru
The reactivity of the reagents, energy and reaction rate depend not only on nature, but
also on the solvate state of members of chemical reactions [1]. To characterize the state of
solvate molecule or ion in solution the thermodynamic parameters of solvation (Gibbs energy
(ΔG), enthalpy (ΔH), entropy (ΔS)) are used. They allow to judge the strength of the
interaction, the presence or absence of association between the particles, and identify and
describe the influence of the environment on the processes in solutions.
In the present work the effect of the mixed solvent of methanol-acetonitrile (χMeOH = 0,0
÷ 1,0 mol. fraction) on the thermochemistry solvation of secondary aliphatic amine piperidine
(Ppd) is investigated. For this purpose standard enthalpies of solution of piperidine
(∆solHo(Ppd)) in the whole range of compositions of methanol-acetonitrile mixtures are
defined by the calorimetric method at T = 298.15 K. The data obtained allow to count
enthalpies of transfer of the amine in its mixture of acetonitrile and methanol:
∆trHо(Ppd)AN→ MeOH = ∆solНo(Ppd)(MeOH-AN) - ∆solHo(Ppd)(AN),
where ∆solНo(Ppd)(MeOH-AN) and ∆solHo(Ppd)(AN) which are the standard enthalpies of solution
of piperidine in a mixed solvent of MeOH-AN of certain composition and in acetonitrile,
respectively.
In the composition of the mixed solvent from 0.0 to 0.2 mol. fraction of methanol, a
sharp increase in the exothermicity of solvation piperidine can be observed. A further increase
in the content of methanol in the binary mixture does not lead to significant changes in the
solvation state of the amine.
Piperidine is a strong base. The increase of exothermicity of Ppd transfer by changing
the solvent MeOH→AN mainly is due to increased solvation of the atom of piperidine imino
nitrogen as a result of the increase in acidity of the mixed solvent (ANAN = 19,3; ANMeOH =
41,3 [2]). Changes in the solvation state of the hydrocarbon radical and proton imino Ppd by
changing the composition of the mixed solvent are likely to be insignificant (DNAN = 14,1
kJ/mol; DNMeOH = 19,01 kJ/mol [2]), and they have no significant influence on the general
solvation energy of the molecule.
The study was supported by the Ministry of Education and Science of Russian
Federation № 14.V37.21.0801 agreement.
References
[1] Krestov G.A., Afanasyev V.N., Agafonov A.V. Complexation in non-aqueous solutions
(The Problems the Chemistry of Solution). M.: Science. 1989. 256.
[2] Y.A. Fialkov. Solvent as a means to control a chemical process. L.: Chemistry, 1990. 237.
SOLVATION OF PYRIDINE IN BINARY SOLVENT

METHANOL–ACETONITRILE
Kuz’mina I.A., Sharnin V.A., Volkova M.A., Sitnikova K.A.
Ivanovo State University of Chemical and Technology,
Institute of Thermodynamics and Kinetics of Chemical Processes, Ivanovo
e-mail: oxt703@isuct.ru
Generalization of thermodynamic data of complexation d-metal ions with amine and
carboxylate ligands types in aqueous-organic solvents made it possible to establish a number
of important correlations in the change of the thermodynamic functions of solvation reactions
and reagents [1,2]. As a result a set of equations [3], was offered to forecast the change in
stability of coordination compounds of these classes by changing the state of the ligand
solvate and the heat effects of reactions of their formation by replacing water on the organic
solvent. Data for mixtures of non-aqueous solvents is limited by few works. In this regard, the
effect of the mixed solvent of methanol-acetonitrile (χAN = 0.0 ÷ 1.0 mole fraction) for the
solvation enthalpy characteristic of pyridine (Py) was investigated in this work.
Standart enthalpy values of pyridine solution in all amount of methanol-acetonitrile
composition were defined by calorimetric method at T = 298.15 K. Using investigateded data
amine transfering from methanol to its composition with acetonitrile enthalpies were
calculated: ∆trHо(py)MeOH→AN = ∆solНo(MeOH-AN) – ∆solHo(MeOH) where ∆solНo(MeOH-AN) and
∆solHo(MeOH) – which are standart enthalpies of pyridines solution in mixed solvent MeOH-AN
of definite composition in methanol respectively.
Replacement of methanol to acetonitrile leads to the reduction of pyridines solvation
exothermicity. General effect of changing ∆trHо(py) from solvent composition substitution is 6
kJ/mol.
In fact, exothermically amine transfer reduction with grow of a-protonic components
content in binary composition is due to worsening of reaction centers (nitrogen atoms) Py as a
result of mixed solvent acid characteristics decreasing (ANMeOH = 41.3, ANAN = 19.3 [4]).
Changes in solvate condition of benzene ring CH-groups after changing the mixed solvent are
likely to be insignificant (DNMeOH = 19,01 kJ/mol; DNAN = 14,1 kJ/mol [4]) and do not have
considerable influence on general solvatation energy profile of the molecule.
The study was supported by the Ministry of Education and Science of Russian
Federation, project 14.B37.21.0801.
References
[1] V.A. Shormanov, V.A. Sharnin. Achievements and problems of the theory of solvation:
structural and thermodynamic aspects. M.: Science, 1998. Pp. 172-205. (rus)
[2] V.A. Sharnin// General Chemistry, 1999. No 69. Pp. 1421-1429. (rus)
[3] V.A. Sharnin// Coordination Chemistry, 1996. No 22. Pp. 418-421. (rus)
[4] Y. Fialkov. Solvent as a means of controling a chemical process. L.: Chemistry, 1990. 237
p. (rus)
THE EFFECT OF COMPOSITION OF CHITOSAN BLOCK-COPOLYMER

WITH METHYL ACRYLATE ON ITS THERMOCHEMICAL CHARACTERISTICS
Larina V.N., Kashtanov E.A., Uryash V.F., Kokurina N.Yu.,
Smirnova L.A., Mochalova A.E., Kush D.S.
Research Institute of Chemistry, Nizhny Novgorod State University
e-mail: ltch@ichem.unn.ru
For the fundamental scientific base for designing hybrid biostructured composites based
on copolymers of polysaccharides and acryl monomers to be developed, it is necessary to
reveal the dependence of their thermodynamic characteristics and physical-chemical
properties in the copolymer composition. This problem was solved by determining standard
enthalpy of combustion (∆сНо) and formation (∆fНо) of chitin (CT), chitosan (CTS),
polymethyl acrylate (PMA), and block-copolymers of CTS and methyl acrylate (MA) with the
help of a modified V-08MA calorimeter with a static calorimateric bomb. The CTS/MA ratio
in the copolymer was 1:3 and 1:2.5 (conditional moles). The temperatures of relaxation
transitions and thermal destruction of hybrid polymer composites based on CTS and PMA
were studied using the method of differential thermal analysis in the temperature range of 80-
650 K. The Practical Grade CT from crab shells (Aldrich Chemical Company, Inc.) was
analyzed. Prior to the analysis, CT was additionally cleaned, The degree of its deacetylation
was 2-4 %, and its molecular mass was 1.4●106 D. Coplymerization was performed using CTS
manufactured by “Shanghai AZ import & export Co., Ltd” (China) which was obtained from
the chitin extracted from the crab shell. Its molecular mass was 1●105 D, and its deacetylation
degree was 78%. Before using, MA was dried with CаН2 and distilled at the setup with a
complete condensation head; the fractions with tboil = 353.35 K and ρ298=0.950 g/cm3 was
collected. The calculations were performed for the following combustion reactions:
С8H13O5N (s) + 8.75 О2 (g) → 8 CO2 (g) + 6.5 Н2О (l) + 0.5 N2 (g)
C6H11O4N (s) + 6.75 O2 (g) → 6 СO2 (g) + 5.5 Н2О (l) + 0.5 N2 (g)
C4H6O2 (s) + 4.5 O2 (g) → 4 СO2 (g) + 3 Н2О (l)
C4.5H7.25O2.5N0.25(s) + 5.0625 O2 (g) → 4.5 СO2(g) + 3.625 Н2О(l) + 0.125 N2(g)
C4.6H7.43O2.57N0.29 (s) + 5.1725 O2(g) → 4.6 СO2(g) + 3.715 Н2О(l) + 0.145 N2(g).
The value of ∆сНо(s, 298.15) estimated for the CT manufactured by Aldrich was
−4030.95±4.94 kJ/mol. Then the estimate was obtained for ∆fНо(s, 298.15) = −975.04±4.94
kJ/mol. The standard combustion enthalpy for the China-made CTS is ‒3155.6±13.4 kJ/mol,
and the standard enthalpy of its formation is ‒777.6±13.4 kJ/mol. The value of ∆сНо(т,
298.15) for PMA turned out to be ‒2006.2±2.7 kJ/mol, and its ∆fНо(s, 298.15) = ‒425.3±2.7
kJ/mol. Thermochemical characteristics of the CTS/MA (1:3) block-copolymer (∆сНо(s,
298.15) = ‒2310.3±4.7 kJ/mol and ∆fНо(s, 298.15) = ‒496.7±4.7 kJ/mol) and the CTS/MA
(1:2.5) block-copolymer (∆сНо(s, 298.15) = ‒2299.2±2.0 kJ/mol and ∆fНо(s, 298.15) =
‒561.4±2.0 kJ/mol) point to their additive dependence on the copolymer composition.
HEAT CAPACITY AND THERMODYNAMIC PROPERTIES OF ALKALI METAL

URANYL TUNGSTATES AND URANYL MOLYBDATES
AI2UBVI2O10 (AI – Li, Na, K, Rb, Cs; BVI – W, Mo)
Lelet M.I., Suleimanov E.V.
Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod
e-mail: maxlelet@gmail.com
Nuclear technologies in the Russian science and economics traditionally have high level
of development. They are aimed not only at energy issues, but also at the creation of a wide
range of new technologies in the remote from energy industry areas: medicine, agriculture,
environment, security, space, materials, and others, for which the nuclear industry is a
technological donor. The development and commercialization of these technologies in foreign
markets is one of the main priorities of innovative development of the Russian nuclear
industry.
In this connection one of the most relevant scientific challenges facing researchers in the
field of nuclear technology is the search for new materials with desired properties, which
stipulate the relevance of the study of complex systems based on different metal oxides. The
systems AI2O – UO3 – W(Mo)O3 (AI - Li, Na, K, Rb, Cs) are one of mentioned above. The
study of alkali metal uranyl tungstates and uranyl molybdates attracted the attention of many
scientists working in the nuclear industry. These compounds are convenient objects for the
organization of the fundamental model research and can be formed at various stages of
nuclear waste and materials treatment with high probability. At the same time these
compounds can be one of the forms of technogenic uranium binding in the biosphere.
Moreover, some of them are distributed in the nature in the form of commercially significant
uranium minerals and exhibit useful electrical and optical properties.
Unfortunately, most of the researches in this area were devoted to obtaining single
crystals of uranyl tungstates and uranyl molybdates for further clarification of the crystal
structures. Their properties have not been investigated. Although knowledge of
thermodynamic functions, physical and chemical properties of these compounds is necessary
in order to describe quantitatively various processes in which these phases can participate.
In the order to provide such study, two families of known uranyl tungstates and uranyl
molybdates with the general formula AI2UBVI2O10 (where AI = Li, Na, K, Rb, Cs and BVI = W,
Mo) have been obtained by high temperature solid state reactions. A thermochemical
investigation of these compounds was undertaken. The temperature relation of the heat
capacity of uranyl tungstates and uranyl molybdates in the range of 7 to 320 K was determined
by low-temperature vacuum adiabatic calorimetry. Final values of the heat capacity of these
compounds calculated by numerical integration were applied to calculate the standard
thermodynamic functions: the heat capacity Ср°(Т), the enthalpy H°(Т)–H°(0), the entropy
S°(T)–S°(0) and the Gibbs function G°(Т)–H°(0) in the range from 0 to T→320K. The Gibbs
energies of formation of obtained compounds have been calculated. The study concluded that
the composition of alkali metal uranyl tungstates and uranyl molybdates have a strong
influence on their thermodynamic properties.
THERMODYNAMIC PROPERTIES OF CARBOSILANE DENDRIMERS

OF THE SIXTH GENERATION G-6(Si-O-Si, EtOx)256 AND G-6(Si-O-Si, 3EtOx)256
Letyanina I.A.a, Smirnova N.N.a, Markin A.V.a, Muzafarov A.M.b
a
Lobachevsky State University of Nizhni Novgorod, National Research University,
Nizhni Novgorod, e-mail: irina-letyanina@mail.ru
b
Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy
of Sciences, Moscow
Dendrimers are a new organization form of polymer matter, where the properties of a
macromolecule and a particle are combined. Dendrimers attract considerable interest of
researchers due to huge possibilities of construction of dendritic molecules with different
architecture, structure and composition of outer and inner spheres on the one hand, and valid
expectations of wide perspectives of dendrimers’ practical applications in material science,
electronics, medicine and other fields on the other hand.
о
In the present research the temperature dependences of heat capacity C p = f(T) of
carbosilane dendrimers of the sixth generation G-6(Si-O-Si, EtOx)256 and G-6(Si-O-Si,
3EtOx)256 were measured for the first time with the methods of adiabatic vacuum calorimetry
over the range from 6 to 350 K and differential scanning calorimetry over the temperature
range from 330 to 580 K.
The compounds devitrified over the above temperature range, at T = (174±1) K in case
of G-6(Si-O-Si, EtOx)256, and at T = (182±1) K in case of G-6(Si-O-Si, 3EtOx)256. Also, an
anomaly on the curve of the temperature dependence of heat capacity of G-6(Si-O-Si,
EtOx)256 over the interval from 50 to 80 K was detected. This anomaly was plotted as positive
deviation from normal (interpolated) trend of curve. It reproduced every time on cooling and
о
subsequent C p measurement over this range. This anomaly was hypothetically conditioned
with vibration excitation of shielded groups of repeating fragments (for example, methyl ones)
in macromolecules on their heating and vibration freezing on their cooling.
High-temperature relaxation transition was found on the curve of temperature
dependence of the heat capacity of G-6(Si-O-Si, EtOx)256 in the range of 370-500 K. Such
transition was also observed for carbosilane dendrimers of high generations studied earlier.
Other thermal behavior was revealed for G-6(Si-O-Si, 3EtOx)256 within the interval from 350
to 430 K, where considerable exo-effect was found, which was not reproduced on cooling and
subsequent heating of the dendrimer.
The experimental data were used to calculate the standard thermodynamic functions:
о
heat capacity C p (T), enthalpy H°(T) - H°(0), entropy S°(T), residual (zero) entropy S°(0), and
Gibbs function G°(T) - H°(0) in the range from T → 0 K to 580 K for different physical states
of dendrimers, and standard entropies of formation of the compounds under study were
estimated at T = 298.15 K.
The low-temperature (20 K ≤ T ≤ 50 K) heat capacity data were analyzed using the
Debye’s heat capacity theory of solids and the multifractal model of heat capacity treatment.
The values were analyzed subject to composition and structure data and were compared
with corresponding values for other carbosilane dendrimers studied earlier.
The work was financially supported by the Russian Foundation for Basic Research
(Project No. 11-03-00592) and Ministry of Science and Education (Contract No.
14.В37.21.0799).
STATISTICAL THERMODYNAMICS OF POLAR LIQUIDS − THE MODEL

OF HINDERED ROTATION OF MOLECULES
Litinskii G.B.,Tarahno E.V.
National University of Civil Defense of Ukraine, Kharkov, Ukraine
e-mail: litinskii@yandex.ru
There are two approaches to describe the properties of polar fluids: one of them is based
on quasi-chemical models such as the theory of association equilibria (AE), and the other, on the
«strict» equations of the theory of liquids − the integral equation method and thermodynamic
perturbation theory (TPT).
In quasi-chemical models, most of the results are analytical; however, this is achieved
by an a priori choice of the structure of the associates representing the polar fluid. Here the
underlying model is a chain cluster.
The structure and mean size of the associates is determined by a set of chemical
equilibrium constants that are, as a rule, unknown, and the associates themselves are
considered to be rigid (kinetically independent) because only their translational degrees of
freedom are taken into account. These approximations correspond to a strongly-interacting
rarefied system (fluid) and not a “normal” polar liquid, in which the internal (rotational and
vibrational) degrees of freedom of clusters cannot be neglected.
As regards the “strict” methods, their main weakness is low accuracy and computational
complexity: even for the simplest dipolar hard sphere (DHS) fluid can give only numerical
results. The only exception is the thermodynamic perturbation theory (TPT), in which an
accurate and simple empirical formula (the Pade approximant) has been derived, but it proves
to be inapplicable at sufficiently low temperatures and densities.
In this communication we presents a brief review of the basic results of application of
the model of hindered rotation of molecules (HRM) for the description of thermodynamic
and dielectric properties of polar liquids.
In the framework of this model the main structural element of the polar liquid is an
infinite statistical (percolation) chain of particles, connected with each other by dipolar forces
and the conformational dynamics of this chain imitates the vibrational and rotational dynamics
of polar molecules in liquid. Such approach, in witch instead of rotations of individual
particles considers the dynamics of a macroscopic object (DHS chain) is quite similar to the
Einstein (or Debye) theory of solids, in which the vibrational dynamics of bound harmonic
oscillators proves to be equivalent to the dynamics of non-interacting normal vibrations −
macroscopic objects (waves) formed by these particles.
It is clear that a quasi-one-dimensional representation of a three-dimensional liquid in
HRM model allows one to facilitate considerably the calculation of different statistical mean
values and leads to simple analytical formulae for thermodynamic and dielectric functions of
model liquids of dipolar, quadrupolar and dipole-quadrupolar hard spheres, which are in a
good agreement with Monte-Carlo simulation data..
We discuss also the generalization of HRM model for rarefied systems and its
connection with TPT and Widom-Rowlinson penetrable sphere model. This connection can be
obtained by the many-body interpretation of TPT-series for the internal energy of a DHS fluid,
which provides an opportunity for justification of AE models from the "first principles".
THERMOCHEMICAL PROPERTIES OF GASEOUS In2MoO4, In2WO4 AND In2W2O7

Lopatin S. I., A.I. Panin, S. M. Shugurov
Department of Chemistry, St. Petersburg State University, St. Petersburg
e-mail: sergeylopatin2009@yandex.ru
Oxides and multicomponent systems on their base are still considered as most important
materials which are used in glass manufacturing, nuclear power engineering, metallurgy,
refractories industry, nuclear-waste disposal, etc. The demand for developing high
temperature technologies processes has prompted intensive research into thermodynamic
properties of individual oxides and multicomponent systems on their basis, stable at high
temperatures, and also research into gaseous compounds formed under these conditions. In
this connection there arises the barest necessity to study thermal stability of gaseous associates
which can be formed in the course of high-temperature processes as well as their structure and
energy characteristics. In the present paper gaseous indium molybdates and tungstates formed
on interaction of In2O with molybdenum and tungstate oxides are studied. In properties oxide
of indium (I) is comparable with alkali element oxides and it seems reasonable to expect that
molybdates and tungstates of indium (I) are thermally stable.
The Knudsen effusion technique with mass spectrometric analysis of the vapor
composition was employed. The molybdenum and tungsten double two-temperature effusion
cells heated by electron bombardment were used. The temperature was measured with an
accuracy of ±5 K using an optical pyrometer EOP-66 of high precision. The appearance
energies (AEs) of ions were obtained by the vanishing current method with Au as an energy
standard, which was found to be accurate within 0.3 eV. The partial vapor pressures of the
gaseous species were determined by differential mass spectrometry with Au as the internal
standard.
When we evaporated In2O3 from the molybdenum or tungsten cell, the sample reacted
with the material of the cell and the In+, In2+, In2O+, XO2+, XO3+, In2XO3+, In2XO4+, and
In2W2O7+ ions (X = Mo, W) were detected in the mass spectra in the temperature range from
1600 to 2000 K. The partial vapor pressures of the gaseous species were determined by the
method of ion current comparison using Au as external pressure standard. To determine the
standard enthalpies of formation for indium molybdate and tungstates, we derived the
equilibrium constants Kp and enthalpies for gaseous reactions (1-4) using eqn (5).
In2О + MoО3 = In2MoО4 (1)
In2О + WО3 = In2WО4 (2)
In2О + 2 WО3 = In2W2О7 (3)
In2WО4 + WО3 = In2W2О7 (4)
∆ r H 0 (0) = − RT ln K p (T ) + T∆Φ 0 (T ) (5)
The free-energy functions and heat capacities of gaseous oxides In2O, MoO3, and WO3
necessary for the calculation of the enthalpies of reactions were taken from the reference
book. The free-energy functions and heat capacities of gaseous indium salts were calculated
by the statistical thermodynamic method in the rigid rotor-harmonic oscillator approximation
on the base of molecular parameters and vibrational frequencies obtained by quantum
chemistry computation. Using the enthalpies of reactions (1-4) recalculated to temperature
298 K, together with the reference values of gaseous oxides In2O, MoO3, and WO3 formation
enthalpies, we determined standard formation enthalpies for gaseous In2MoO4, In2WO4 and
In2W2O7, which are -855±33, -773±30, and -1565±30 kJ⋅mol-1 respectively.
THE ENTHALPY OF FORMATION OF DODECA(TRIFLUOROMETHYL)FULLERENE

С60(CF3)12
Lukyanova V.A., Papina T.S.
e-mail: lukyanova@phys.chem.msu.ru
Trifluoromethyl derivatives of fullerene show rather high electron-accepting ability and
stability against oxidation and thermal decomposition. Therefore they are promising
precursors for synthesis of new materials.
The sample of isomer S6 of C60(CF3)12 was obtained in preparative amount. It contained,
according to the elemental analysis data (INEOS RAN), 55.7±0.2 mass. % of carbon and
43.8±0.3 mass. % of fluorine; theoretical values are 55.84 and 44.16 correspondingly.
The energy of combustion of C60(CF3)12 was measured in a calorimeter with an
isothermic jacket and rotating bomb fettled with platinum. The temperature rise was measured
by a copper resistance thermometer using a bridge circuit; the sensitivity of measurement was
ca. 5·10-5 K. The energy equivalent of the calorimeter was determined by burning benzoic
acid.
Since C60(CF3)12 is difficult to burn, a great deal of attention was given to finding
optimal conditions of burning. The initial pressure of oxygen in the bomb was 4.05 MPa. The
sample was pressed on a hydraulic press into a pellet, the pieces of which (ca. 0.03 g) were
weighed and sealed into a polyester-film ampoule. The ampoule was placed into a platinum
crucible and closed round with three pellets of benzoic acid. Benzoic acid and film served as
auxiliary substances and were responsible for about 95% of the whole heat measured in the
experiment. At these conditions the sample was burnt up giving rise only insignificant
amounts of soot in crucible and CF4. Before each ran, 10 ml of water was introduced into the
bomb to dissolve HF (the product of combustion of C60(CF3)12) and NO2 ( formed of nitrogen
occurring in oxygen as an impurity). The products of combustion were analyzed quantitatively
for CO2(g), HF(sol-n) and HNO3 (sol-n). Corrections for formation of CF4 were calculated
basing on the deficiency of CO2 and HF as compared to their theoretic amounts.
The value of the standard mass energy of combustion was obtained as a result of five
calorimetric runs: ∆cu0(C60(CF3)12,cr) = (-18548±94) J/g. The standard molar energy of
combustion, ∆cU0(C60(CF3)12, cr), is equal to (-28726±146) kJ/mol. It corresponds to the
reaction:
C60(CF3)12(cr) + 63O2 (g) + 18H2O(l) + aq = 72 CO2(g) + 36HF (sol-n HF⋅20 H2O)
In accordance with the equation of the reaction, the standard enthalpies of combustion
and formation in crystalline and gaseous states are equal: ∆cH0C60(CF3)12,cr) = (-28704±146),
∆fH0(C60(CF3)12,cr) = (-6072±148) and ∆fH0(C60(CF3)12, g) = (-5923±148) kJ/mol.
In the calculation were used literature data on the enthalpies of formation (kJ/mol):
CO2(g) (-393.51±0.13), H2O(l) (-285.830±0.040) and F-(aq) (-335.35±0.65), as well as
the enthalpy of sublimation of C60(CF3)12, ∆sH0 (298K) = 149±4.
The obtained value of ∆fH0 C60(CF3)12(g) was used for calculation of the dissociation
enthalpy of C-CF3 bond, equal to (233±14) kJ/mol.
Authors acknowledge the postgraduate N.A. Romanova and Ph.D. A.G. Buyanovskaya
for the synthesis and analysis of the sample C60(CF3)12.
THERMODYNAMIC INVESTIGATIOM OF SOME TUNGSTEN

PYROCHLORES AND BRANNERITES
Mączka M.a, Knyazev A.V.b, Bulanov E.N.b
a
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
Wroclaw, Poland, e-mail: M.Maczka@int.pan.wroc.pl
b
Nizhny Novgorod State University, Nizhny Novgorod, Russia
e-mail: knyazevav@gmail.com
One of the most promising classes of inorganic materials are complex oxides of
tungsten. These compounds are used in the creation of new functional materials with valuable
physico-chemical, electro, optical, catalytic, and some other properties. The most interesting
class of complex tungsten oxides are compounds with the general formula MIBVWO6, where
MI - atom monovalent elements, BV - elements of the fifth group. According to our research,
the studied compounds can crystallize in the cubic and monoclinic system with space group
Fd3m and C2/m, respectively. In this case, 23 of the 25 compounds crystallize in the defect
pyrochlore structure type, and two of them (LiVWO6 and NaVWO6) crystallize in the
brannerite structural type. In order to obtain structural information, we carried out a full-
profile X-ray analysis of 8 compounds. The coordinates and isotropic thermal parameters of
the atoms were carried out. A thermodynamic study of five representatives from a number of
pyrochlores (KSbWO6, RbNbWO6, CsTaWO6) and brannerites (LiVWO6 and NaVWO6) was
also done. We studied the specific heat capacity and thermodynamic functions in the
temperature range of 7 - 630K. The standard thermodynamic functions (heat capacity Cp°(T),
the enthalpy Hº(T) - Hº(0), the entropy Sº(T) - Sº(0) and the Gibbs function Gº(T) - Gº(0))
were calculated in the temperature range 0 - 630K. In the case of niobium-rubidium-tungsten
oxide a transition from the paraelectric to the ferroelectric state was observed. It is observed in
the form of two consecutive endothermic effects on the heat capacity curve in the temperature
range 355 - 365K. In other cases, the heat capacity increases monotonically showing no
visible abnormalities. In order to analyze data on chemical thermodynamics of triple tungsten-
containing oxides and its correlation with the structural data we calculated the entropy of
synthetic reactions of the oxides for studied compounds. There is a tendency to reduce the
entropy of the reaction with the increasing of packaging density of atoms in the structure. In
addition, the fractal dimension and characteristic temperatures of studied complex oxides of
tungsten, which are in good agreement with our structural data, were calculated. Fractal
dimension for frame pyrochlores is 3, and for brannerites with quasilayered structure is 2.4
and 2.5. Using differential scanning calorimetry in combination with the method of high-
temperature X-ray diffraction 11 compounds, including all the compounds with brannerite
structure and oxides of the pyrochlore structure type, in which the atom MI has different
crystallographic positions, were studied for the first time. It was found that all the studied
compounds are characterized by high thermal stability and undergo decomposition according
to the following mechanisms: incongruent and congruent melting and thermal decomposition
of the solid phase. For the three compounds thermal decomposition products were identified.
In compounds with the structure of the mineral pyrochlore phase transitions were observed in
the temperature range 320-1310K, whereas in complex oxides with the brannerite structure
polymorphism is absent. For the binary system LiVWO6 - NaVWO6 a thermodynamic
modeling was carried out. As a result we made the phase diagram of the system. The resulting
melting diagram corresponds to the formation of regular solid solutions in the crystalline state
and ideally solid solutions in a liquid state. Temperatures of decomposition of solid solutions
(the Becker curve) were also calculated.
THERMODYNAMIC INVESTIGATION OF ZINC AND TIN PIVALATES Me(Piv)2

Malkerova I.P., Alikhanyan A.S., Sirotkin D.A., Kamkin N.N.*, Povalisheva D.V.*
N.S. Kurnakov Institute of General and Inorganic Chemistry
of Russian Academy of Sciences, Moscow
e-mail: IMalkerova@gmail.com
*
Moscow Pedagogical State University, Moscow
Investigation of zinc and tin volatile coordination compounds, in particular
carboxylates, is an actual problem, because these metal complexes are used as new precursors
for MO CVD technique of thin films and metal coverings. The data about sublimation and
thermodynamic characteristics are necessary for this purpose.
In present work we report the results of the study of zinc and tin pivalate complexes
Zn(Piv)2, Sn(Piv)2, where Piv=(CH)3CCOO·, vaporization. We used effusion Knudsen
method with mass-spectral analysis of gas-phase composition in temperature range 430-550 K
and 360-550 K, accordingly. Analysis the mass-spectra and results of full isothermal
evaporation experiments have shown, that Zn, Sn pivalates sublimate congruently without
chemical decomposition in the selected temperature range. The gas phase of Zn pivalate
consists mainly of dimeric molecules Zn2(Piv)4, saturated vapor above pivalate complex Sn
containes of monomeric molecules Sn(Piv)2.
On the basis of these data the saturated vapor pressures of gas-phase components and
the standard enthalpies of sublimation were calculated: ΔSHO[Zn2(Piv)4,k.,Т] = 178,5 ±14,5
kJ/mol, ΔSHO[Sn(Piv)2,k.,T] = 198,1 ± 13,2 kJ/mol. The upper limit ΔfHO(T) value of
enthalpy of formation Sn(Piv)2(g.) was estimated.
This work was supported by the Presidium of the Russian Academy of Sciences
(program P8-1), the Russian Foundation for Basic Research (project nos. 12-03-31669).
THERMODYNAMIC STUDY OF COCRYSTAL SUBLIMATION PROCESSES

Manin A.N.1, Voronin A.P.2, Perlovich G.L.1
1
G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences,
Ivanovo, Russia
2
Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
e-mail: alexnmanin@gmail.com
The development of highly effective new drug compounds produced in Russia is the
main objective of relevant research institutions of the Russian Federation for the domestic
drug market formation. 40% of all development compounds have a poor solubility and
membrane permeability. That is why; one of the important tasks in pharmaceutical industry is
to design pharmaceutical solid materials with improved physicochemical properties. Recently,
creation of co-crystals has gained increased interest within the pharmaceutical industry
foremost as a route for modification of physicochemical properties of active pharmaceutical
ingredients (APIs) such as solubility, physical and mechanical properties, hydration stability
and other, without changing the pharmaceutical activity, but also as means of patenting a
protected API without outraging the originator’s patent.
Study of the physicochemical and structural properties of the cocrystal is interesting
both from a scientific and practical point of view. Cocrystals are widely known, but
insufficiently studied. There are a number of methods for cocrystal screening has been
reported [1]. The cocrystal preparation techniques are well studied too [2]. But experimental
thermodynamic study of co-crystal crystal lattice has been not studied yet. Knowledge of
cryst1al lattice energy of co-crystals could help researchers in the investigations of the co-
crystal formulation main principles.
The aim of our study is to study sublimation process of a new cocrystal of salicylamide
with 4-acetamidobenzoic acid and to estimate the cocrystal sublimation thermodynamic
parameters.
The temperature dependencies of cocrystal vapor pressure have been obtained by
transpiration method. The mechanism of cocrystal sublimation has been described. The
thermodynamic parameters of cocrystal sublimation process have been calculated and have
been compared with the thermodynamic parameters sublimation of the cocrystal individual
components. The values of cocrystal vapor pressure are similar with salicylamide vapor
pressure values. But magnitude of cocrystal lattice energy is close to 4-acetamidobenzoic acid.
The entropy contribution to Gibbs energy for cocrystal is significantly higher than that for the
individual components in the pure state.
This work was supported by Project BioSol (2010-1.1-234-069), the federal program
for supporting science and innovation (N 02.740.11.0857) and grant of President of the
Russian Federation (MK-2309.2013.3).
References
1. A. Newman. Org. Process Res. Dev. 2013, 17, 457-471
2. A. Jayasankar, L. S. Reddy et al. Cryst. Growth Des. 2009, 9 (2), 889–897
THERMODYNAMICS OF FULLERENE NANOSTRUCTURES

Markin A.V., Smirnova N.N.
Nizhni Novgorod
e-mail: markin@calorimetry-center.ru
The discovery of the method for producing С60 fullerenes in macroquantities has laid the
new field of research. The C60 and C70 fullerenes are more interesting for fundamental science
and practice. Now evidently, that based on fullerenes the building of new materials having
potential valuable properties. The fullerenes considers as new type π-acceptors having the
substantial differences: large size, molecular non planar, unique electron structure, high
symmetry and polarizability. These facts defines the reactionary of fullerenes.
In the present work the heat capacity in the temperature range from 6 to (350-600) K for
functional derivatives of C60 and C70 fullerenes were determined by precision adiabatic
vacuum calorimetry and differential scanning calorimetry. The phase, physical and in some
case chemical transformations were detected for compounds rank under study. The
thermodynamic characteristics of these transformations were determined and analyzed with
literature results about composition and structure of objects.
Thus, covalent bounded fullerene contained polymers was investigated. The influence of
C60 and C70 fullerenes on thermodynamic characteristics and parameters of devitrification and
glassy state was revealed. The dependence of temperature of destruction onset for polymers
from fullerene content was established.
The heat capacity, characteristics of phase transitions and standard thermodynamic
properties of C60 and C70 fullerides with organoelement fragments were studied for the
temperature range from 6 to 350 K. The standard thermodynamic properties of the fulleride
complex, studied earlier the neutral (C60)2 dimer and C60 fullerite were compared and
discussed. On the based of our thermodynamic data, information about the structure and the
composition of these and the respective data for the neutral dimer (C60)2 the some conclusion
about the bound nature between fullerene fragments in the complex was made. Thus, the
stability of dimeric dianions (С60-)2 depends significantly on the nature of substitute. Also, for
indicated fullerides it was established that the isotherms (T = 100 K) dependences of the heat
capacities and derived thermodynamic functions (enthalpy, entropy and Gibbs energy) vs.
their molar weights are linear. The dependences will allow prediction of the thermodynamic
properties of different fullerides of this rank.
The standard thermodynamic properties of crystalline polymeric nanostructures of C60
fullerene and amorphous graphite-liked and diamond-liked nanostructures were studied. The
dependences of thermodynamics properties vs composition and structure of compounds were
analyzed. The rank of relative thermodynamic stability of crystalline phases of C60 at T =
298.15 K and standard pressure was determined. Thus, standard thermodynamic properties of
indicated nanostructures, C60 and C70 fullerites, graphite and diamond were compared.
The work was financially supported by the Ministry of Science and Education (Contract
N 14.В37.21.0799).
ENTHALPIES OF REACTIONS WITH POTASSIUM DIHYDROPHOSPHITE

Matskevich N.I., Vyazovkin I.V. , Bryzgalova A.N.
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy
of Sciences, Novosibirsk
e-mail: nata.matskevich@yandex.ru
Inorganic solid acids like MHxAOy (M = K, Cs, Na, etc.; A = S, Se, P, etc.) exhibiting a
high proton conductivity can be potentially used as electrolytes in fuel cells [1-2]. The typical
transition temperatures of MHxAOy are between 50 and 150 °C. The superprotonic state
relates to the phase transition when the proton conductivity increases by several orders of
magnitude reaching values up to 10-2 and 10-3 S/cm. The alkali-metal hydrogen sulphates and
selenates decompose in hydrogen containing atmospheres. It was assumed [2] that alkali-
metal acid phosphites MH(PO3H) have a good stability in hydrogen atmosphere. It is
necessary to have thermodynamic data to study the stability. There are no thermodynamic data
for KH(PO3H) in literature. This paper is devoted to the thermodynamic investigation of
KH(PO3H) and its reactions.
KH(PO3H) powders were prepared by slow evaporation of an aqueous solution obtained
by mixing H3PO3 and KOH in molar ratio 1:1. The powders were dried in an oven at ~105 °C
for 20 h, ground in an agate mortar and stored in desiccators due to hygroscopicity of the pure
salt. X-ray data were obtained using a diffractometer (STADI-P, Stoe, Germany, Cu
Kα1) at room temperature. The samples were shown to be a phase-pure phase. KH(PO3H)
had a monoclinic structure (space group P 21/a).
Solution calorimetry was carried out in an automatic calorimeter with an isothermal
jacket. The construction of the solution calorimeter and the experimental procedure are
described elsewhere [3].
2.0 M HCl (aq) (reagent grade) was chosen after trying some different concentrations
since it readily dissolves KOH, H3PO3 and KH(PO3H). The thermochemical cycle designed in
such a way that it was possible to compare the solution enthalpy of KH(PO3H) and the
solution enthalpy of KOH + H3PO3 mixture. The samples were stored in dry argon before
use.
The standard dissolution enthalpies of potassium hydroxide, phosphoric acid, and
potassium dihydrophoshite were used to calculate the enthalpy of the following reaction:
KOH(s) + H3PO3(s) = KH(PO3H) (s) + H2O(l).
The following literature data were used to calculate the standard formation enthalpy of
KH(PO3H) (s): ∆fHo(KOH, s, 298.15 K), ∆fHo(H2O , l, 298.15 K), ∆fHo(H3PO3, s, 298.15 K).
We obtained the following value of standard formation enthalpy for KH(PO3H) (s):
∆fHo(KH(PO3H), s, 298.15 K) = –1216.81 ± 0.92 kJ/mol.
References
1. S.M. Haile, D.A. Boysen, C.R.I. Chshold, R.B. Merle, Nature 410 (2001) 910-913.
2. W. Zhou, A.S. Bondarenko, B.A. Boukamp, H.J.M. Bouwmeester, Solid State Ionics 179
(2008) 380–384.
3. N.I. Matskevich, Th. Wolf, Yu.I. Pochivalov, Inorg. Chem. 47 (2008) 2581-2584.
This work is supported by Program of Fundamental Investigation of Siberian Branch of

the Russian Academy of Sciences.
QUANTUM-CHEMICAL CALCULATION OF STANDARD THERMODYNAMIC

PARAMETERS OF MACROCYCLIC CHELANTS AND METALCHELATES
FORMED AT «SELF-ASSEMBLY» IN GELATIN-IMMOBILIZED MATRIX SYSTEMS
AND CORRELATION BETWEEN THEM AND DEGREE OF PLANARITY
Mikhailov O.V., Chachkov D.V.
Kazan National Research Technological University, Kazan
e-mail: olegmkhlv@gmail.com
Results of DFT OPBE/TZVP quantum-chemical calculation of standard entropies Sf,2980
and Gibbs’ energies ∆Gf,2980 of formation and parameters of molecular structures (namely, the
degree of deviation from planarity DP) of a series asymmetric (545)-, (555)-, (565)- and
(666)macrotricyclic complexes, among their number
O O HN S S NH2
NH
M HN S S NH2 M
H 3C CH3 N
N N M S HN N
N
S N N
H3C CH3
H3C CH2
NH
S S
S HN
M
NH HN
HN S
and, also, of a series of symmetric (5454)-, (5555)-, (5656)- and (5456)macrotetracyclic

complexes, for example
NH
NH
H3C N N
CH3 N N
M S S O N N O
H 3C CH3 S N N S M
N
M
N M S HN NH S S HN NH S
S N N S
NH O
arising as a result of «self-assembly» processes (template synthesis) in the [3d-element ion

M(II)– (N,S)-ligand– mono- or dicarbonyl compound] triple systems into biopolymer matrix,
and, also, of the same parameters of chelants that are in the inner coordination sphere of these
metalchelates, have been generalized and systematized in the given review report. The
comparison of standard thermodynamic characteristics of the given complexes and
corresponding chelants with above-indicated DP parameters for these compounds [which is the
aggregate (sum of bond angles at the metal atom in the chelate unit – 360°), (sum of non-valence
angles between donor atoms – 360°), (the sum of internal bond angles in each of the 5-
membered chelate cycles – 540o) and (sum of internal bond angles in each of the 6-membered
chelate cycles – 720o)] has been conducted. The certain correlation between Sf,2980 and DP of
complexes considered here, has been found.
Russian Foundation of Basic Researches (RFBR) is acknowledgement for financial
support of the given research (grant No. 09-03-97001).
DEFINITION OF ENERGIES OF THE DISSOCIATION OF BONDS

IN 3-ALKYL-4-NITROFURAZANS
Miroshnichenko E.A., Kon’kova Т.С., Matyushin J.N., Vorob’ev A.B., Inozemtcev J.O.
Semenov Institute of Chemical Physics of the Russian Academy of Sciences, Moscow
e-mail: eamir02@mail.ru
Bonds C - NO2 and enthalpies of formation of radicals in cyclic compounds on the basis
of experimental values of differences of enthalpies of an atomization nitro-and corresponding
alkylderivations the design procedure of energies of a dissociation of bonds is developed for
cyclic and linear compounds. By this technique unknown values of energies of reorganization
of fragments of molecules in radicals are mutually excluded, and received values reflect
change of energies of a dissociation of bonds in cyclic structures concerning linear
compounds. On the basis of it energy of a dissociation of bond С - NO2 in a 3-methyl-4-
nitrofurazan (I) both a 3- butyl-4-nitrofurazan (II) is defined and enthalpies of formation of
radicals 3- methyl- (III) and 3- butylfurasan-4-yl (IV).
In table 1 give thermochemical characteristics 4-replaced-3-alkylfurazans are resulted.
Energies of combustion are defined on a bombing calorimeter, and an evaporation enthalpy on
microcalorimeter Calvet [1].
Table 1. Thermochemical properties I and II
Compound –∆BU, J∙g-1 –∆сHо, kJ·mol-1 ∆fHо, kJ ·mol-1 ∆fHоg, kJ·mol-1
C3H3O3N3(l) 13661.2 ± 5.0 1755.6 ± 0.84 146.44 ± 0.84 198.3 ± 1.7
C6H9N3O3 (l) 21779.4 ± 15.1 3720.0 ± 2.5 75.7 ± 2.5 135.6 ± 5.2
In table 1: ∆BU - energy of combustion of substances in the conditions of a bomb; ∆сHо

- combustion enthalpies in a standard condition; ∆fHо - formation enthalpies in a standard
condition; ∆fHоg - enthalpies of formation of compounds in a gas phase.
For calculation of energy of a dissociation of bond C-NO2 in I, as basic data we use
values of energies of a dissociation of bonds in mononitroalkanes [1] and values of
differences of enthalpies of an atomization nitro-and corresponding alkyl derivations, Р(R),
for cyclic and linear compounds.
Р(R) = ΔatH (R1NO2) - ∆atH (R1R) (1),
where R - atom of hydrogen or hydrocarbon group; R1 - a radical at which the nitrogroup is
replaced on R; ΔatH (R1NO2) and ∆atH (R1R) - enthalpies of an atomization of nitrocompound
and its hydrocarbon analogue. After subtraction from values Р(R)cyc for the cycles,
corresponding values for alkanes, Р(R) alk, and transformations, we receive
D (С-NO2)cyc = D (С-NO2) alk + [Р (R) cyc - Р (R) alk] + D (С-R) cyc - D (С-R) alk (2)
We compare differences of enthalpies of an atomization of nitroalkanes and alkanes [1]
and I with 3, 4-dimethylfurazane [2]. Value D (С-R)cyc - D (С-R)alk is equal to a difference of
energies of joining CH3 to heterocyclic and to alkanes (20 kJ ·mol-1). Using energies of a
dissociation of bonds C-NO2, known for mono-nitro [1], we define value of energy of a
dissociation of this bond in I equal to 176.1 kJ ·mol-1. Enthalpies of formation of radicals III
and IV have made 341.4 and 278.7 kJ ·mol-1, accordingly. At calculation of energies of a
dissociation of bonds differential method of value of enthalpies of formation of radicals do not
depend on values of enthalpies of formation of cyclic nitro compounds.
Reference
1. Matjushin J.N. etc.// Izv. Russian Academy of Sciences. Ser. Chem. 1971. №1. P.
181-183. 2. Miroshnichenko E.A., etc.// Izv. Russian Academy of Sciences. Ser. Chem. 2011.
№1. P. 36-41.
THERMODYNAMIC PROPERTIES OF VANADYL ACETYLACETONATE

Nenashev R.N. *, Tyurin A.V.**, Tatevosyan S.S.*, Zlomanov V.P.*
* Department of Chemistry, Moscow State University
e-mail: zlomanov@inorg.chem.msu.ru
**Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow
Vanadyl acetylacetonate VO(C5H7O2)2 is one of the frequently used precursor for the
synthesis of vanadium dioxide films due to their ability to evaporate at relatively low
temperatures. VO2 films are used in the recording, storing optical information elements for
visualizers, detectors, laser technology and other devices. Selection of the optimal conditions
of synthesis and control of the film structure requires knowledge of the thermodynamic
properties of vanadyl acetylacetonate, which are currently unknown. This article presents the
results of the heat capacity and thermodynamic functions of VO(C5H7O2)2 determination in
the range 5 - 345 K.
Sample of VO(C5H7O2)2 was synthesized from vanadyl sulfate and acetylacetone[1]. It
is a blue-green crystalline powder. The phase composition of sample was proved by XRD.
Heat capacity СР was measured by the adiabatic method [2] in the laboratory of IGIC
RAS. In the calorimeter was placed 0.4521 g of sample. The entire temperature range
includes 119 measurement points. There are no abnormality of the heat capacity in the entire
temperature range. СoP(298.15 K) = 316.33 J mol-1K-1. Thermodynamic functions are
calculated:
So(298.15 K) = 383.42 J mol-1K-1,
Н (298.15 K) - Нo(0 K) = 55520 J mol-1.
o
References:
1. Moeller T. Inorganic Synthesis. – McGraw-Hill Book Company, inc, 1957. V. 5. P.
113–115.
2. K.S. Gavrichev, N.N. Smirnova, M.A. Ryumin, A.V. Tyurin, V.M. Gurevich, L.N.
Komissarova. Heat capacity and thermodynamic functions of Na2MoO4 in the temperature
range 0-300 K // Thermochimica Acta. 2007. V. 463. P. 41–43.
THERMODYNAMICS OF RARE EARTH ORTHONIOBATES

Nikiforova G.E.1, Gurevich V.M.2, Tyurin A.V.1, Gavrichev K.S.1, Kholodyuk E.A.1
1
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Moscow
2
Vernadsky Institute of Geochemistry and Analytical Chemistry,
e-mail: gen@igic.ras.ru
Orthophosphates of rare earth elements possess the set of unique functional properties
and have the high thermal and chemical stability. And reiable thermodynamic data in the wide
themperature range are necessary for their application in various fields of science and
technology.
Thermodynamic properties of LnNbO4 were studied by relaxation and adiabatic
calorimetry in the temperature range 2 - 300 K and by drop calorimetry in the range 350 -
1800 K. The agreement of low- and high-temperature data was carried out by method
developed in our laboratory.
For some of rare-earth ortoniobates there were detected the heat capacity anomalies in
the low-temperature range. These are due to cooperative transition from paramagnetic to
antiferromagnetic phase.
In the high-temperature range (800-1150 K) rare earth orthoniobates are characterized a
reversible phase transformation from a monoclinic fergusonite-type structure to a tetragonal
scheelite-type structure. This transformation is accompanied by a transition from the
antiferroelectric state to the dielictric. The phase transition temperature depends on the rare-
earth ion. This transition was found to correspond to a jump in the heat capacity curve. The
temperature range of structure phase transition was refined for several LnNbO4.
Smoothed thermodynamic properties of rare-earth orthoniobates (heat capacity, entropy,
enthalpy change and derived Gibbs energy) were calculated in the range from 10 K up to
phase transition temperature.
This investigation was supported by the Russian Academy of Sciences Research
Program (Project No.8).
CRITICAL PROPERTIES OF STRAIGHT-CHAIN (C3 TO C12) ALKANEDIOLS

Nikitin E.D., Popov A.P., Bogatishcheva N.S.
Institute of Thermophysics, Ural Branch of RAS, Ekaterinburg
e-mail: e-nikitin@mail.ru
Alkanediols with straight-chain molecules HO(CH2)nOH are an important family of
organic compounds. They are of industrial importance as well. For instance, the first member
of this homologous series, 1,2-ethanediol (ethylene glycol) is widely used as an antifreeze, as
a raw material in the production of polyester fiber, as a desiccant, and so forth. Other diols are
employed in cosmetics (solvents, moisturizers, anti-microbial agents). The critical properties
of alkanediols are difficult to measure because they have high critical temperatures and begin
to decompose at temperatures below their critical ones. In this study, the critical temperatures
and pressures of alkanediols with n = 3, 4, 5, 6, 8, 10, 12 have been measured using the pulse-
heating method recognized as a “standard state method (GSSSD)” [1]. The method consists in
measuring the pressure dependence of the temperature of the attainable superheat
(spontaneous boiling-up) of a liquid with the help of a thin wire probe placed into the liquid
and heated by electric current pulses. When the pressure approaches the critical pressure, the
temperature of the attainable superheat approaches the critical temperature. The residence
times in the pulse-heating method are from (0.03 to 1) ms. The short residence times provide
little degradation of the substances in the course of the experiments so the pulse-heating
method is applicable to thermally unstable compounds [2].
Samples of alkanediols were purchased from Alfa Aesar and Sigma-Aldrich. Before and
after measuring the critical properties, the purities of the samples were determined using a
proton magnetic spectrometer BRUKER AVANCE DRX 400. The purities of the samples
changed slightly in the course of measuring and were not less than 98.4 per cent. The
uncertainties of the critical pressure pc and the critical temperature Tc of alkanediols are
estimated by us at 0.04 pc and 0.015 Tc, where Tc is the absolute temperature.
The internal consistency of the data obtained was checked by plotting (M/pc)0.5 and
ln(aTc/pc - b) against n, where M is the molar mass, a and b are constants [3]. In both cases the
experimental points drop with good accuracy on straight lines. There are experimental critical
properties of some alkanediols (n = 2, 3, 4, 6) in the literature. The critical constants obtained
by us for these compounds are in good agreement with the literature values. The experimental
critical properties are compared with the values estimated by the group-contribution methods
of Lydersen, Marrero and Gani, and Wilson and Jasperson. It has been found that all the
group-contribution methods used considerably underestimate the critical temperatures of
alkanediols. These methods underestimate the critical pressures for n = 2, 3, 4, but
overestimate them for n ≥ 5 .
The study was performed in the framework of Program N 2 of the Presidium of the
Russian Academy of Sciences under the support of the Ural Branch of RAS (Project 12-P-2-
1008).
References
1. Nikitin E.D., Pavlov P.A. Method GSSSD ME 163-2010. The Russian Scientific and
Technical Centre for Information on Standardization, Metrology and Conformity
Assessment. FSUO “STANDARTINFORM”, Deposit document No. 865a-2010 kq.
Moscow, 2010.
2. Nikitin E.D., Pavlov P.A., Skripov P.V. J. Chem. Thermodyn.,1993, 25, 869-880.
3. Poling B.E., Prausnitz J.M., O’Connell J.P. The Properties of Gases and Liquids, 5th ed.;
McGraw-Hill: New York, 2000.
ENTHALPY OF FORMATION OF SAPONITE

FROM ARKHANGELSK DIAMOND PROVINCE
Ogorodova L.P., Kiseleva I.A., Melchakova L.V., Vigasina M.F.
Lomonosov Moscow State University, Geological faculty, Moscow
e-mail: logor@geol.msu.ru
Saponite is clay mineral from the trioctahedral smectites group. General crystal-
chemical formula of saponite is M+y-x[(Mg,Fe+2)3-x(Al,Fe3+)x]+x[(Si4-yAly)-yO10](OH)2×nH2O,
where M - interlayer exchangeable cations. Practical interest in the study of saponite is
determined by deficiency of high magnesium clays used as sorbents, refractory and building
materials. The study of diamond deposits in the Arkhangelsk region showed that minerals of
kimberlite rocks are subjected to intense saponitization to depth of 300-400 meters.
Technological tests revealed the feasibility to consider these fields as complex useful
components of which are not only diamond, but also the high magnesium saponite clays. The
use of saponite clays for wastewater treatment around the mining facility and Arkhangelsk
pulp and paper mills will significantly improve the environmental situation in the region. In
this regard, the study of physico-chemical properties including thermodynamic characteristics
of this mineral is of particular importance. The experimental data on the thermodynamic
parameters of saponite is currently lacking in the literature; there are only calculated or
estimated data. Saponite from Arkhangelsk diamond province (Russia) was investigated using
high temperature (1000oC) heat-flux Tian-Calvet microcalorimeter ("Setaram", France). The
sample studied has composition Na0.2K0.1(Mg2.5Fe2+0.2Fe3+0.1Al0.1)[Si3.7Al0.3O10](OH)2.2H2O.
The enthalpy of formation was determined by melt solution calorimetry using a
thermochemical cycle, taking into account the dissolution of the mineral and its constituent
components - oxides and hydroxides. The content of adsorbed and interlayer water in smectite
depends on the humidity of the environment, therefore the determination of the standard
enthalpy of formation was carried out for dehydrated hydroxyl-containing form of saponite.
Dehydration of natural mineral was carried out by calcination for 1 hour at a temperature T =
823 K (550oC), which corresponded to the total removal of molecular water according to the
thermal analysis and infrared spectroscopy data. It has been confirmed also by weighing the
samples before and after heating. The resulting value of ΔfHo(298.15 К), equal -5772.9 ± 5.3
kJ / mol, can be recommended as the standard enthalpy of formation from simple substances
for magnesium-ferrous saponite with composition
Na0.2K0.1(Mg2.5Fe2+0.2Fe3+0.1Al0.1)[Si3.7Al0.3O10](OH)2. The enthalpy of formation of saponites
of theoretical compositions Na0.3(Mg2.5Fe2+0.2Fe3+0.1)[Si3.7Al0.3O10](OH)2 (-5733 kJ/mol) and
Са0.15(Mg2.5Fe2+0.2Fe3+0.1)[Si3.7Al0.3O10](OH)2 (- 5760 kJ/mol) were evaluated based on the
experimental results. First obtained thermodynamic data for saponite of different composition
can be used for the quantitative modeling of the physico-chemical processes, as well as to
estimate the conditions of formation of saponite deposits.
This work was supported by RFBR (grant № 12-05-00211).

THERMODYNAMIC PROPERTIES AND ENTHALPY

OF FORMATION OF TiOF2 MOLECULES
Osina E.L.a, Gorokhov L.N.a, Osin S.B.b
a
Joint Institute for High Temperatures of RAS, Moscow, Russia
b
Lomonosov Moscow State University, Department of Chemistry, Moscow, Russia
e-mail: j-osina@yandex.ru
Formation of transition metal gaseous oxihalide molecules can be result of interaction of
some aggressive reagents with refractory transition metal based materials and coatings. In
particular, hazardous action of fluorine can be anticipated by interaction of fluorine or fluorine
containing species with the titanium-based refractory materials. On this reason, obtaining the
data needed for thermodynamic modeling of such interactions seems to be expedient. In the
present work we report the results of quantum-chemical calculations on the structure and the
enthalpy of formation of titanium oxide-difluoride TiOF2 molecule.
The optimized structure and vibrational frequencies for TiOF2 were obtained with the
DFT methods, using the B3LYP and BPW91 functionals with 6-311+G(d, p) and cc-pvTZ
basis sets. According to the calculations, TiOF2 molecule in the X1A′ ground electronic state
has a pyramidal structure of Cs symmetry. Following distances (Å) and angles (degrees) were
obtained: r(Ti-O) = 1.616, r(Ti-F) = 1.808 ; ∠O-Ti-F=114.4, ∠F-Ti-F = 125.6°. Calculations
were also carried out for a planar structure of C2v symmetry. This structure was found to be a
transition state for inversion of the pyramidal structure through out-of-plane anharmonic
motion of Ti atom. This circumstance points to the necessity of using more sophisticated
models rather than usual "rigid rotator-harmonic oscillator" while calculating the
thermodynamic functions.
The thermodynamic functions for TiOF2 were calculated with the molecular constants
found taking into account anharmonicity of Ti atom out-of-plane motion. To obtain the
potential for this motion, a relaxed scan was performed for the energy dependence of Ti atom
position against F-O-F plane. The potential so obtained was used to calculate the anharmonic
oscillator energy levels. Corresponding partition functions were found by the direct
summation method. Comparison with the result of using "rigid rotator-harmonic oscillator"
approximation show a significant, ≈ 4 JK-1mol-1 difference, in the Φ°(1000 K) values.
There are no experimental or calculational data on the TiOF2(g) enthalpy of formation.
An estimated value is presented in the Reference Book JANAF Thermochemical Tables:
ΔfH°(TiOF2, g, 0 K) = -920.5 kJ·mol-1, together with the value ΔfH°(TiOF, g, 0 K) = -431.0
kJ·mol-1 To obtain more reliable and definite data, quantum-chemical DFT calculations were
carried out for Al(g), AlO(g), AlF(g), TiO2(g), TiOF(g), and TiOF2(g) using BPW91
functional with 6-311+G(d, p), cc-pvTZ, and cc-pvQZ basis sets. Obtained full electronic
energy values combined with ZPE (zero-point energy) values made it possible to calculate
enthalpies for the gaseous reactions (1) and (2):
TiO2 + AlF = TiOF + AlO (1), ΔrH°(0) = 192.0 kJ·mol-1;
TiOF + AlF = TiOF2 + Al (2), ΔrH°(0) = 44.3 kJ·mol-1.
The values ΔrH°(0) for reactions (1) and (2) were combined with the enthalpies of
formation for Al(g), AlO(g), AlF(g), and TiO2(g) from the Reference Book “Thermodynamic
Properties of Pure Substances” to give the enthalpies of formation values:
ΔfH°(TiOF, g, 0 K) = -460.5 kJ·mol-1; ΔfH°(TiOF2, g, 0 K) = -999.0 kJ·mol-1.
Obtained results seem to be more reliable than estimated values given in the Reference Book
“JANAF Thermochemical Tables”. We (optimistically) estimate the uncertainties of our
values as ± (15 – 20) kJ·mol-1.
THERMOCHEMICAL STUDY OF NANOCLUSTER

POLYOXOMOLYBDAT–SOLVENT INTERACTION
Ostroushko A.A., Moricheva N.A., Safronov A.P., Tonkushina M.O.
Ural Federal University, Ekaterinburg
e-mail: alexandre.ostroushko@usu.ru
Nanocluster polyoxomolybdates [1] (POM), in particular with keplerat (buckiball) type
structure represent a great interest from the point of view of their frame and possibility of
usage as selective sorbents, catalysts, sensory materials, agents for address delivery of
medicinal substances [2] etc. These compounds are capable to occlude both on an external
surface and in an internal cavity of various organic molecules [3]. Sorption can be carried out
from a vaporous phase and from solutions. Substances are held more strongly in an internal
cavity. For determination of interaction nature between polyoxomolybdates and organic
compounds (alcohols, hydrocarbons) the solvatation heats by means of thermochemical
method were measured in the present work. The following POM composition Mo132 was
studied:
(NH4)42[MoVI72MoV60O372(CH3COO)30(H2O)72].300H2O.10CH3COONH4.
Dissolution of initial Mo132 in water had endothermic character and the dissolution heat
had rather small value that was shown by us earlier [4]. Mo132 interaction with water after
preliminary dehydration at 100oC opposite gained exothermic character, the value of the
solvatation heat calculated on a thermodynamic cycle was about 60 J/g. Process of
dehydration carried out with preservation of initial onion-wireframe structure of POM.
Dehydrated POM was actively solvated with ethanol, the solvatation enthalpy is not less
than 30 J/g in this case. For alcohols with higher molecular masses (isopropanol, tert-butanol,
n-butanol) exothermic interaction with Mo132 wasn’t observed and the thermal endo-effect
had low values about 10, 6 and 0 J/g, appropriately. The quantity of ethyl alcohol occluded to
polyoxometalat was more [3] in comparison with heavier compounds and decreased among
alcohols by the increase of their molecular weight and the temperature of boiling. On the basis
of the data obtained in the present work concerning the solvatation heats it is possible to
assume that in the course of absorption of molecules on polyoxometalats the essential role is
played by the hemosorbtion processes. These processes are best manifested in the interaction
between POM and water or ethanol, for heavier alcohols processes of molecules absorption
can be related to physical sorption. Influence of a hemosorbtion on increase in quantity of
absorbed substance, apparently, is shown by replacing of POM acetate groups to chloroacetate
[5] possessing the additional electronegative substituent.
The endothermic solvatation heats of Mo132 with n-hexan and tetrachlormethane were
also determined approximately as 10 and 5 J/g consequently.
This work was financially supported by the Russian Foundation for Basic Research.
References
1. Miller A., Gouzerh P. // Chem. Soc. Rev. 2012. V.41. P.7431-7463.
2. Ostroushko A.A., Danilova I.G., Gette I.F. et al. // J. of Biomaterials and
Nanobiotechnology. 2011. V.2. P.557-560.
3. Ostroushko A.A., Tonkushina M.O., Martynova N.A. // Rus. J. Phys. Chem. A. 2010. V.84.
No.6. P.1022–1027.
4. Ostroushko A.A., Tonkushina M.O., Safronov A.P. Rus. J. Inorg. Chem. 2010. V.55, No.5.
P.808–813.
5. Ostroushko A.A., Tonkushina M.O., Safronov A.P. et al. Rus. J. Inorg. Chem. 2010. V.55.
No.8. P.1260–1265.
TEMPERATURE DEPENDENCE OF VAPORIZATION ENTHALPIES OF BIPHENYLS

Pashchenko L.L. a , Miroshnichenko E.A. b
a
Chemistry Department, Lomonosov Moscow State University, Moscow, Russia
e-mail: paschenko@phys.chem.msu.ru
b
Semenov Institute of Chemical Physics RAS, Moscow, Russia
e-mail: eamir02@mail.ru
Biphenyls find ever increasing applications in technology and medicine as liquid
crystals, semiconducting nonamaterials and drugs. The thermochemistry of aromatic
hydrocarbon derivatives is of general interest; however, thermodynamic data on biphenyl
derivatives are scarce. The present study is closing gaps in the experimental thermochemical
data of these substances.
Enthalpies of vaporization, ∆vapHo, were determined for three biphenyls, a namely 1, 1’-
biphenyl (B), 4-nitrobiphenyl (4-nitroB) and 3-isopropylbiphenyl (3-IPB) in the 298 to 380 K
range. Measurements were performed on a Calvet isothermal heat conducting
microcalorimeter according to the standard procedure [1] with an estimated accuracy of ≤ 1.0
per cent. The average values were adjusted to 298.15 K. The uncertainty of the mean value of
vaporization enthalpy of the biphenyls derivatives under study was calculated as ±t⋅s, where s
is a standard deviation of the mean value, and t is a Student's coefficient at the 0.05
significance level.
Using obtained experimental data ∆vapHo, the standard formation enthalpies in the liquid
and gaseous states at 298 K for (3-IPB) was calculated. Treatment of the data for all biphenyl
derivatives under study was carried out by the least square method to get the analytical
dependence of vaporization enthalpy on temperature, ∆vapHo/kJ·mol-1 = α + β (T /K). The
standard molar enthalpy of vaporization for (3-IPB) ∆vapHo =76.6 ± 0.5 kJ·mol-1 is in
agreement, respectively, with the determination of vaporization enthalpy, ∆ vapHo = 76.4 ± 0.8
kJ·mol-1, was calculated from the temperature dependence of vapor pressure [2]. The standard
molar enthalpy of sublimation for B measured in the present work by direct calorimetric
method is equal to ∆subHo = 81.5 ± 0.8 kJ·mol-1. The value obtained in [3] by not available
method was found to be ∆subHo = 81.52 kJ·mol-1. The second-order group additive method has
been applied to calculate the contributions of nitro- and isopropyl groups to the vaporization
enthalpies of derivatives of biphenyl: 26.9 ± 0.4 and 14.16 ± 0.61(kJ·mol-1), respectively, and
of derivatives of benzene: 21.1 ± 0.9 and 15.19 ± 0.40 (kJ·mol-1) and aimed at either
prediction of properties of novel substances.
Table. Enthalpies of vaporization, 298.15 К, kJ·mol-1
B 4- nitroB 3-IPB
sublimation sublimation evaporation
81.5 ± 0.8 108.4 ± 0.9 76.6 ± 0.5
81.52 [3] 76.4 ± 0.8 [2]
References
1. Lebedev Yu.A., Miroshnichenko E.A. Thermochemistry of vaporization of organic
substances. Nauka: Moscow. 1981.
2. Nazmutdinov A.G. et al. // Fluid Phase Equilibria. 2012, V.335, P. 88 – 98.
3. Chirico R.D. // J. Chem. Thermodyn. 1989, V. 21, P.1307 -31.
VAPOR PRESSURE AND ENTHALPY OF VAPORIZATION

OF SOME OF THE SILICON CHLORIDES
Pavlovski Yu.P., Kochubey V.V., Gerasymchuk S.I.
Lviv Polytechnic National University, Lviv, Ukraine
e-mail: yurppa@gmail.com
The thermodynamic characteristics of the process of evaporation of Si2Cl6 and Si3Cl8 are
presented in this work. For each substance have been studied two fractions, taken at
successive stages of fractional distillation. The analysis showed that the experimental data
obtained for both fractions of each of the substances are statistically indistinguishable. This
allowed us to combine them into a single statistical sample and consider that studied silicon
chlorides are sufficiently individualized.
Vapor pressure of silicon chlorides was determined in the Świętosławski type
ebulliometer, which we have modified by model [1]. Temperature accuracy was ± 0.1 K, and
the pressure ± 0.7*102 Pa. Verifying of the accuracy and efficiency of the method has been
done by measuring of temperature dependence of vapor pressures of water, carbon
tetrachloride and decane. Vapor pressure of Si2Cl6 measured in the range 307-418 K, and
Si3Cl8 in 349-494 K.
The experimental data of ebulliometry research were approximated by a linear equation:
lnp (kPa) = A – B/T (1)
In addition, for the same fractions of silicon chlorides, that investigated by ebulliometry,
on the differential microcalorimeter MID-200 by ampoule method [2] was measured the
enthalpy of vaporization at 298 K. The calibration of the calorimeter cells was performed by
evaporation of samples of decane, dodecane and tetradecane with reliably established values
of the enthalpies of vaporization but with different vapor pressure.
The coefficients of equation (1), the enthalpy of vaporization (average in the
investigated temperature range), calculated from the temperature dependence of the vapor
pressure and the enthalpy of vaporization, defined by the calorimetric method, are shown in
the Table. The error of the average values was determined for a significance level of 0.95 by
t-test.
Table. The temperature dependence of the pressure of saturated vapor and enthalpy
of vaporization of investigated silicon chlorides
Ebulliometry data ΔvapH (p-T) ΔvapH298 (cal.)
Substance
f k A (1) B*10-2, K (1) kJ /mol
Si2Cl6 (g) 2 42 16,208 ± 0,013 48,48 ± 0,05 40,31 ± 0,04 41,49 ± 0,14
Si3Cl8 (g) 2 35 16,687 ± 0,067 59,91 ± 0,28 49,81 ± 0,23 52,19 ± 0,18
Note: f and k are the number of series and total number of data points, respectively.
References
[1] Kogan V.B., Fridman V.M., Kafarov V.V. Equilibria between liquid and vapour. Pt. 1. M.:
Nauka, 1966. 648 p. (In Russian).
[2] Lebedev Yu.A., Miroshnichenko E.A. Thermochemistry of vaporization of organic
substances. M.: Nauka, 1981. 216 p. (In Russia).
THERMOCHEMICAL STUDY OF THE 3- ISOPROPYLBIPHENYL

Pimenova S.M.,а Nesterov I.A.,b Sikachov А. Yu. а
a
Chemistry Department, Lomonosov Moscow State University, Moscow
b
Samara State Technical University, Samara
e-mail: smpimenova@yandex.ru
Recently the alkylbiphenyls have applied widely in different fields of science,
technology and medicine. To create the data banс on the biphenyl derivatives thermochemical
properties is important scientific and practical task to develop the industry, to predict
thermochemical properties of the unstudied compounds and the correlation between the
molecules structure and the properties. However, at present the thermochemical data of
alkylbiphenyls are limited. The standard energies of combustion of 4, 4'- tert-butyl- and -di-
4,4'-tert-butyl-biphenyls, 4-methyl- and 4, 4'-dimethyl-biphenyls and 4, 4'-dinitrobiphenyl
ether had been measured by us early. The present study is concerned with the determination of
standard enthalpies of combustion and formation of 3- iso-propyl-biphenyl (3-IPB).
The study sample was obtained and purified at Samara State Technical University. The
purity (99,99 mass%) was determined by GLC, M=196,28754 g⋅mol-1, ρ = 1,02 g ⋅cm -3; Tfus=
= 566,28 K; (∂u/∂p)T = - 0,2 J·g-1·МPa-1 at 298,15 K.
The standard energy of combustion, ∆сНm (l), of 3-IPB was determined by means of a
static bomb isoperibolic macrocalorimeter. The temperature rise was measured with a copper
resistance thermometer and a bridge circuit (the sensetivity ∼ 4·10-5 K). The energy equivalent
of calorimeter was determined by combustion of thermochemical standard benzoic acid.
Before combustion, the liquid sample (the mass ∼0,25g) was placed into terylene film
ampoule and hermetically sealed. It was weighed with "Mettler" balance to within 1·10-5 g,
placed into a platinum crucible and burnt in calorimetric bomb. The bomb was charged with
oxygen purified from the fuel impurities to a pressure of 3,0 МПа. After each run, the
combustion products were analyzed for carbon dioxide by the Rossini method and tested for
CO using the indicator tubes to within ~1⋅10-6g. The high purity of 3-IPB and the
completeness of its combustion were confirmed by result of gas analyses (99,99±0,03
mass%).
As result of six experiments the standard energy of combustion ∆сН°m (l) =-8209,8±2,5
кJ·mol-1. The standard enthalpies of formation of liquid and gaseous 3-IPB was calculated by
experimental values obtained in this work and literary data: ∆fH°m(3-IPB, l) = 20,5±2,5
кJ·mol-1 и ∆fH°m(3-IPB, g) = 97,2±2,5 кJ·mol-1. The standard enthalpy of vaporization was
determined at Institute of Chemical Physics RAS.
The enthalpy increments of С3Н7 groups for substitution of one hydrogen atom in a
position 3 in biphenyl and benzene were calculaited on the base of found values of ∆fH°m(3-
IPB, g) and literary data for ∆fH°m(biphenyl, g), ∆fH°m(isopropilbenzene, g) and
∆fH°m(benzene, g). These increments seems to be equal to 81,0±3,3 и 78,8±1,2 кJ·mol-1
correspodingly and support the group additivity rule.
THERMAL STABILITY AND THERMODYNAMICS OF SODIUM FLUOROSILICATE

Polyachenok O.G., Branovitskaya N.V., Fomina T.G., Polyachenok L.D.
Mogilev State University of Food Technologies, Mogilev
e-mail: polyachenok@mogilev.by
Sodium fluorosilicate Na2SiF6, the by-product of the fertilizer production from apatite, is a
perspective precursor for the solar-grade silicon production. Its thermal decomposition produces
gaseous SiF4, and the main idea of the fluoro-hydride method is to convert SiF4 to SiH4 [1, 2].
Further thermal destruction of SiH4 gives the polycrystalline silicon of high purity. A
thermodynamic substantiation of some occurring processes of this method was proposed in [3].
This interesting technology of silicon production from fluoro-containing raw materials
makes special demands for the quality of sodium fluorosilicate. The fact is that this substance,
obtained from aqueous solutions, usually contains not less than 0.5–1 mass % of the silicic acid,
which is not necessarily detected by the usually used alkalimetric titration with phenolphthalein
as indicator. On heating sodium fluorosilicate to produce SiF4 this silicic acid may form volatile
silicon oxyfluorides, polluting silicon with oxygen. Pure fluorosilicates are also needed for the
investigation of their physico-chemical properties, and most of all for the determination of their
thermodynamic characteristics.
The values of ΔfH°298 Na2SiF6 found in the reference sources [4, 5] are based on the
measurements of the solution heat effects of SiF4 in water and aqueous solutions of HF and NaF
on the understanding that the reaction
SiF4 g + 2 NaF aq → Na2SiF6 s, (1)
is the only one in this system. However, a fast chemical reaction of SiF4 hydrolysis with the
formation of silicic acid may occur at least partially when SiF4 is dissolved in the aqueous
solution of NaF:
3 SiF4 g + 2 H2O l → 2 H2SiF6 aq + SiO2 hydr, (2)
with the following slow formation of the next products. This reaction may be the source of
considerable systematic errors in the determined value of Na2SiF6 standard enthalpy of formation
because the heat of the hydrolysis reaction (2) is much smaller than for the reaction (1) [6].
Calculations show that in case of the reaction (2) 10–20 % contribution to the total process of
SiF4 solution, the value of ΔfH0298 Na2SiF6, equal to – 2912.9 kJ∙mole–1 [4], should be more
negative by 7–15 kJ∙mole–1. Practically the same value (8.5 kJ∙mole–1) of such systematic error
may be found as the result of the data comparison for the experimental [7, 8] and calculated [4]
decomposition vapour pressure:
Na2SiF6 s ↔ 2 NaF s + SiF4 g. (3)
In order to verify the stated above assumptions and to obtain more precise standard
thermodynamic characteristics of Na2SiF6 it is necessary to reinvestigate the equilibrium (3) using
a static method at temperatures below 833 К (phase transition) with use of specially obtained
fluorosilicate specimens practically free from silicic acid.
References
[1] Turovsky B.M., Milvidsky M.G. // Tsvetnie Metalli (in Russian) 1981. – N 9. – P.1–7.
[2] Patent 2077483 RF, MKI C 01 B 33/04. /Fadeev A.L. et al. Bulletin N 11, 20.04.97.
[3] Polyachenok O.G. et al. //Proc. Natl. Acad. Sci. Bel., Chem. Ser. 2001.–N 2.– P.101–105.
[4] Glushko V.P. (Ed.), Thermal Constants of Substances, in 10 Issues, Moscow, 1965–1982.
[5] Wagman D.D. et al. // J. Phys. Chem. Ref. Data. 1982. –11. – P. 2–392.
[6] Vorobyev A.F. et al. //J. Inorg. Chem. (in Russian). 1960 – 5 (7). – P. 1402–1408.
[7] Hantke G. // Z. Angew. Chem. – 1926. –39. – N 31–39. – 1065–1070.
[8] Chiotti P. // J. Less-Common Metals. 1981. – 80. – P. 97 – 104.
ANTIPIRINIUM PERCHLORATES: SYNTHESIS, STRUCTURE,

POLYMORPHIC MODIFICATIONS, QUANTUM-CHEMICAL CALCULATIONS
Rukk N.S., Shamsiev R.S., Albov D.V., Mudretsova S.N.,
Zamalyutin V.V., Skryabina A.Yu., Gramma V.A.
Lomonosov Moscow University of Fine Chemical Technologies, Moscow
e-mail: roukkn@inbox.ru, zamalyutin@mail.ru
The present work is devoted to consideration of the protonation ability for the bioactive
ligand – antipyrine (2,3-dimethyl-1-phenyl-3-pyrazolin-5-one, AP), to elucidation of the
crystal packing specific features for the protonated antipyrine perchlorate compounds
([APH]ClO4·H2O (I, II) and [AP2H]ClO4 (III, IV)), and to revealing the protonation ability –
complex formation ability relationship for a number of organic ligands. Compounds I and III
were prepared in the absence of lanthanide-ions, while II and IV – in the course of the
attempted syntheses of [Tm(AP)6](ClO4)3 and [Yb(AP)6](ClO4)3. The present contribution is
devoted as well to the theoretical calculations on the basis of the scalar-relativistic Density
Functional Theory (DFT) (PBE exchange-correlation functional [1], TZDP basis set).
Quantum-chemical calculations were performed with the Priroda package [2], the geometry
optimization being performed without restrictions on the molecular symmetry. In all the cases
harmonic frequency calculations have been carried out to confirm that the geometries obtained
correspond to energetic minima. The Polarized Continuum solvent Model (PCM) was used in
the Gaussian 09 calculations with water as the solvent. For comparison calculations were
performed using PCM-UFF [3] and PCM-SMD [4] models taking into account both
electrostatic and non-electrostatic interactions.
The prepared compounds were characterized by single crystal X-ray diffraction, IR
vibration spectroscopy, thermal analysis and DFT calculations. Specific features of crystal
packing for antipyrinium perchlorates ([APH]ClO4·H2O (I, II) and [AP2H]ClO4 (III, IV))
were discussed in the light of the lanthanide-ions ability (for example, those of thulium and
ytterbium) to pre-organize structural units before the compound crystallization. The existence
of π – π interaction as non-covalent interaction between π-systems including those of benzene-
and (or) pyrazolone rings has been illustrated for [(АР)2H]СlO4 (III, IV). The theoretical
calculations demonstrate that a number of organic ligands can be aligned in a row according
to their ability to be protonated and to be incorporated into the complex.
References
1. Perdew J. P., Burke K., Ernzerhof M. Generalized Gradient Approximation Made
Simple // Phys.Rev. Lett. 1996. V. 77. P. 3865 – 3868.
2. Laikov D.N. Fast Evaluation of Density Functional Exchange-Correlation Terms Using
the Expansion of the Electron Density in Auxiliary Basis Set // Chem. Phys. Lett. 1997.
V.281. P. 151 – 156.
3. Rappe A.K., Casewit C.J., Colwell K.S., Goddard W.A. III, Skiff W.M. UFF, a Full
Periodic Table Force Field for Molecular Mechanics and Molecular Dynamics
Simulations // J. Am. Chem. Soc. 1992. V. 114. P. 10024 – 10035.
4. Marenich A.V., Cramer C.J., Truhlar D.G. Performance of SM6, SM8, and SMD on the
SAMPL1 Test Set for the Prediction of Small-Molecule Solvation Free Energies // J.
Phys. Chem. 2009. V. 113. P. 4538 – 4543.
THERMODYNAMIC DESCRIPTION OF ZINC AND CADMIUM HALOGENIDE

COMPLEXES WITH ANTIPYRINE
Rukk N.S, Shamsiev R.S, Zamalyutin V.V, Gramma V.A., Skryabina A.Yu.
e-mail: roukkn@inbox.ru, aliona_skr@mail.ru
The present work is devoted to antipyrine derivatives of zinc and cadmium halogenides
[M(AP)2X2] (AP = antipyrine, C11H12N2O; M = Zn, Cd, X = Cl, Br, I). These compounds are
of interest from the viewpoint of investigations on the relationship between the compounds
structure and properties. The aim of the present contribution consists in the synthesis,
identification, and single crystal structure determination for the mentioned complexes. All the
compounds are also characterized theoretically (DFT method, PBE exchange-correlation
functional, scalar - relativistic approximation with the L11 all-electron basis set, Priroda
package [1-3]). Geometry optimization was performed without any restrictions on the
molecular symmetry on the basis of the atomic coordinates determined by the single crystal
XRD. The steady-state character of the optimized structures was confirmed by the absence of
imaginary frequencies in the vibrational spectra.
It has been shown that the compounds prepared are the molecular complexes,
halogenide ions being incorporated into the inner coordination sphere. The structure of
di(iodo)bis(antipyrine)zinc [Zn(AP)2I2] is different from that of [Zn(AP)2Cl2], early studied in
[4], due to participation of larger in size iodide ions. Complex formation is confirmed by
thermal analysis and IR spectra studies. It has been demonstrated that the spectral
characteristics obtained from quantum - chemical calculations are close to the experimental
values. The relationships “ΔG298 for complex formation – the atomic number of the
complexing metal atom” and “ΔG298 for complex formation – type of halogenide” have been
obtained and discussed. The regularities derived have been explained on the basis of the
Pearson’s HSAB (Hard & Soft Acids & Bases) theory. The respective mercury complexes are
very unstable due to competition with formation of very poor soluble mercury halogenides.
The results obtained for the IIB group metal complexes with antipyrine are compared with
those of lanthanides that form compounds with outer coordination sphere.
References
1. Perdew J. P., Burke K., Ernzerhof M. Generalized Gradient Approximation Made
Simple // Phys.Rev. Lett.1996. V. 77. P. 3865 – 3868.
2. Laikov D.N. Fast Evaluation of Density Functional Exchange-Correlation Terms
Using the Expansion of the Electron Density in Auxiliary Basis Set // Chem. Phys.
Lett. 1997. V.281. P. 151-156.
3. Laikov D.N. A new class of atomic basic functions for accurate electronic structure
calculations of molecules// Chem. Phys. Lett. 2005. V.416. No.1-3. P. 116-120.
4. Cingi M. B., Guastini C., Musatti A., Nardelli M. The Crystal and Molecular Structure
of Dichlorobis(antipyrine)zinc, Zn(C11H12ON2)2Cl2, Acta Crysallogr. Sect. B. 1972. V.
B28. P. 667- 672.
THERMODYNAMIC DESCRIPTION OF LANTHANIDE COMPLEX FORMATION

WITH SOME ORGANIC LIGANDS
Rukk N.S, Shamsiev R.S, Zamalyutin V.V, Skryabina A.Yu., Gramma V.A.
e-mail: roukkn@inbox.ru, aliona_skr@mail.ru
The present work is devoted to antipyrine derivatives of lanthanide iodides and
perchlorates characterized by the presence of large cations [Ln(AP)6]3+ (AP = antipyrine,
C11H12N2O; Ln = Sc, Y, La-Nd, Sm-Lu). This type of compounds is of interest due to their
biological activity in some cases exceeding the biological activity of the ligand. To the best of
our knowledge no any information concerning the quantum-chemical calculation possible
application to improve the absorption bands assignment in the IR - spectra of these
compounds, to determine the lanthanide – the ligand donor atom bond length and energy, as
well as to calculate ΔG298 for the complex cations formation has been found.
In this regard, quantum-chemical calculations were performed in the framework of the
scalar-relativistic Density Functional Theory (DFT) (PBE exchange-correlation functional [1])
with the Priroda package [2]. Scalar - relativistic approximation with the L11 all-electron
basis set [3] was used due to the presence of heavy elements for which the influence of
relativistic effects on the structural and spectral characteristics is pronounced. Spin-
unrestricted DFT method was applied for calculations of the open-shell complexes (all Ln,
except La and Lu). Geometry optimization was performed without any restrictions on the
molecular symmetry on the basis of the atomic coordinates determined by the single crystal
XRD. The steady-state character of the optimized structures was confirmed by the absence of
imaginary frequencies in the vibrational spectra.
It was shown that the obtained from quantum - chemical calculations spectral
characteristics are close to the experimental wave numbers for both series of isostructural
compounds. It was found that dependences of the lanthanide – the ligand donor atom length
and energy, as well as the values of ΔG298 for complex cations formation on the atomic
number of the complexing atom are non-monotonous ones due to the tetrad effect. The results
obtained are compared with the protonation energies of a number of organic ligands (PBE
exchange-correlation functional, TZDP basis), the latter ones serving as the criterion of the
ligands ability to be incorporated into complex compounds. The ligands series, on the basis of
their ability to be introduced into the inner coordination sphere of the lanthanide-containing
complexes, was derived and discussed.
References
1. Perdew J.P., Burke K., Ernzerhof M. Generalized Gradient Approximation Made
Simple // Phys.Rev. Lett.1996. V. 77. P. 3865 – 3868.
2. Laikov D.N. Fast Evaluation of Density Functional Exchange-Correlation Terms Using
the Expansion of the Electron Density in Auxiliary Basis Set // Chem. Phys. Lett. 1997.
V.281. P. 151-156.
3. Laikov D.N. A new class of atomic basic functions for accurate electronic structure
calculations of molecules// Chem. Phys. Lett. 2005. V.416. No.1-3. P. 116-120.
ENTHALPYES OF FORMATIONS OF THE SULFUR CONTAIN RADICALS

Rusakova N.P., Chernova E.M., Orlov Y.D., Turovtsev V.V.
e-mail: d002186@tversu.ru
Properties of substances containing polyvalent sulfur (R-SIIH (thiols), R-СН=SIVH2) and
their radicals (R•) represent significant interest in kinetics, energetics and studying
transformation mechanism. Enthalpy of formation under standard conditions (ΔfH0) is one of
the its key characteristics. However according to the literary data [1-4], the number of
molecules and corresponding radicals containing sulfur and characterized by ΔfH0 are much
less than total quantity of existing and using sulfur organic compounds.
Definition of ΔfH0(R•) is made with a) the thermochemical equation (1) and b) by using
the literary data on dissociation energy (D) of S-H bonds and values ΔfH0 of corresponding
molecules RH.
D(R-H) = ΔfH0(R•) + ΔfH0(H) - ΔfH0(RH) (1)
The data base on the enthalpies of formation of not branched organic radicals containing
sulfur is analyzed and expanded. Comparison of ΔfH0 not cyclic thiol radicals with the literary
data on ΔfH0 of molecules [1-4] was performed. For the first time ΔfH0 for R -СН=SIVH2 were
determined. In the framework of the additive - group approach and «structure - property
(enthalpy of formation)» correlations the analysis of the data were made and new parameter
specifications were obtained. The values of computed parameters ΔfH0 were in a good
agreement with experimental data.
The study of «structure - property (enthalpy of formations)» relationship was carried out
within the framework of the first approximation of an additive - group method. Feature of the
additive - group method realization with respect to compounds containing sulfur (the groups -
SH and =SH2) was considered.
The values of ΔfH0 for significant number of radicals not studied earlier were found, and
study of the relationship "structure - property (enthalpy of formations)" with new
parametrization have been carried out.
References
[1] Orlov Y.D., Lebedev Y.A., Sajfullin I.S. Thermochemistry of organic free
radicals. M.: Mir. 2001,-304 p.
[2] NIST Scientific and Technical Databases version 2008.
(http://webbook.nist.gov/chemistry/form-ser.htm)
[3] J.-R. Luo, Comprehensive handbook of chemical bond energies. CRC Press,
Boca Raton: L., N.-Y., 2007.
[4] V.E.Tumanov, E.T.Denisov // Estimation of energy dissociation bonds S-H
and С-Н in compounds containing sulfur // Petrochemistry. - 2003. - Т. 43, N 6. - P. 406-411.
PHASE RELATIONS AND PHYSICOCHEMICAL PROPERTIES OF SOLID SOLUTIONS

FORMED IN LaMnO3–BaMnO3–BaFeO2.5–LaFeO3 SYSTEM
Russkikh O.V., Dmitriev A.S., Sarycheva N.S., Filonova E.A.
Ural Federal University named after the first President of Russia B.N. Yeltsin,
Ekaterinburg, e-mail: olga.v.russkikh@mail.ru
The basic method which allows to achieve desired properties of complex oxide material
is doping with donor and acceptor elements. In present work influence of properties and
concentration of dopant on crystal structure and physicochemical properties of lanthanum
manganite LaMnO3 were studied. Doping was performed in A-site (by substitution for La3+
by Ba2+) and in B-site (by substitution for Mn3+ by Fe3+) at the same time.
The samples of La1-xBaxMn1-yFeyO3 were synthesized by standard ceramic route in three
24h-steps in temperature range of 1123 ≤ T, K ≤1373 followed by quenching to room
temperature. The phase purity was investigated by means of X-ray diffraction on a DRON-3
UM diffractometer using Cu Кα-radiation. XRD data were refined by the Rietveld method
using FullProf software. As a result, phase composition data allowed to propose a fragment of
phase diagram for LaMnO3-BaMnO3-BaFeO3-LaFeO3 system at 1373 K in air.
For thermal properties investigation, the samples of La1-xBaxMn1-yFeyO3 were pressed
into bars and annealed at 1773 K within 24h. Relative expansion measurements were carried
out by means of a high-temperature dilatometer NETZSCH DIL 402C in temperature range of
293 ≤ T, K ≤1373 and heating/cooling speed of 2 K/min. Thermal expansion coefficients of
La1-xBaxMn1-yFeyO3 phases calculated from dilatometric data in temperature range of
303 ≤ T, K ≤1373 are close to TEC of YSZ which allows to recommend those compounds as
promising cathode materials for high-temperature fuel cells.
Particle size measurements for single-phase powders of La1-xBaxMn1-yFeyO3 were
performed by means of a laser diffraction particle size analyzer SALD-7101 Shimadzu. The
samples were carefully ground in an agate mortar in ethanol. The resulting powder was put
into sample preparation device where it was dispersed by means of stirring and ultrasonic.
Then the suspension was delivered automatically into measuring cell. Calculation results of
particle size distribution are presented.
Measurements of ASR polarization resistance was carried out by means of impedance
spectroscopy on a Elins-Z500-PX impedancemeter in frequency range of 10 Hz to 0.5 MHz
and in temperature range of 973 ≤ T, K ≤1373 using symmetrical cells. Zr0.9Y0.1O2 and
Ce0.8Sm0.2O2 were used as electrolytes. The obtained impedance curves were analyzed by the
graph-analytic method using ZView software. As a result, it was found that polarization
resistance of La0.8Ba0.2Mn1-xFexO3 cathodes depends on used electrolyte material to a large
extent.
This work was supported by Russian foundation for basic research program (project
№ 12-03-31875).
REGULARITIES IN INTERMETALLIDES MELTING TEMPERATURE CHANGE

OF ANTIMONIDE–LANTHANIDE SYSTEM
Rustamov S.Т.1, Khakerov I.Z.2, Abdusalyamova M.N.3, Tsyuan Tszinchzhi1, Badalov A.B.1
1
M.S.Osimi Tajik Technical University, Dushanbe
2
Tajik Technological Institute, Dushanbe
3
V.I. Nikitin Institute of Chemistry AS Republic of Tajikistan, Dushanbe
Alloys thermal characteristics regularities determinations which are necessary for
production of materials with given properties have an applied value. Intermetallides (IM) of
the following compositions: Sb2Ln, SbLn, Sb3Ln4, Sb3Ln5 and SbLn2 are formed in
antimonide-lanthanide (Sb-Ln) system.
Reference data on IM melting temperature (Тm) of the system Ln-Sb are differ from
each other or are absent. We calculated missing and made more precise values of Tm of all IM
of current system with the help of semi-empirical method. Calculation is made according to
correlation equation
Tm[(LnxSby)] = Tm (LaxSby) + αNf + βS +γ’L(Ce-Eu)γ’’L(Tb-Yb))
where Nf – number of 4f-electrons, S – and L–values of spin – and motion orbital angular
momentum of basic condition of lanthanide’s ions and coefficients defines
contribution of each from constituents on the value of IM Тm.
Regularities in IM Tm change of Ln-Sb system depending on composition (fig.a) and
lanthanide’s nature (b) are established. IM Tm in Ln-Sb system is growing up with increase of
antimony concentration (fig.а) and reaches maximum for LnSb equimolar composition.
Further increase of antimony content in the system will lead to sharp decrease of IM Tm for
LnSb2 composition. IM Tm of Ln-Sb system dependence on lanthanide’s nature has more
complicated character (fig.b). Curve clearly is divided into two lanthanides sub-groups. IM Tm
value is increasing in cerium subgroup with increase of lanthanide’s serial number and
reaches maximum value in the middle of subgroup with sharp decrease for EuxSby
system.Gradual decrease of Tm with minimal value in the middle of subgroup is observed in
yttrium subgroup starting from GdxSby system.
Fig (a) (b)
Fig. IM Tm of NdxSby system dependence on composition of (a)

and Ln-Sb from lanthanide’s nature (b).
THERMODYNAMIC CHARACTERISTICS OF THERMAL DECOMPOSITION

PROCESS OF ALKALINE METALS HYDROFLUORIDES.
Ruzmatova G.K., Sharipov D.Sh.,Nasriddinov S.K., Khakimova D.K., Badalov A.B.
Academician M.S.Osimi Tajik Technical University, Dushanbe
Alkaline metals hydrofluorides of МHnFn+1 compositions (where М – Li, Na, К) are
produced by interaction of their carbonates with hydrofluoric acid solutions. It is determined
that hydrofluorides are formed in concentrated (> 35% mass) hydrofluoric acid solutions and
while increasing concentration, the number of HF adjoint molecules is increasing as well.
Studied processes enthalpies are determined by calorimetry solution method.
Hydrofluorides formation enthalpies are calculated on their basis. Hydrofluorides chemical
composition is determined by thermogravimetry, chemical analysis methods and quantitative
tensimetry tests.
Thermal decomposition process of dehydrated hydroflurides in equilibrium conditions is
studied by tensimetry method. Conditions and tests results are provided in Table 1.
Table 1. Thermodynamic characteristics of alkaline metals hydrofluorides decomposition

process
lgРatm = В - •103 Thermodynamic properties of
Compound ∆Т,К decomposition process
А В H0298, S0298, G0298,
kJoule/mole Joule/mole kJoule/mol
e
LiHF2 2730±101 7,08±0,15 296-384 52,2±2,1 135,4±2,6 11,85±2,1
NaHF2 4340±105 6,45±0,55 330-370 80,05±2,5 123,46±2,9 30,07±2,7
NaH2F3 5480±111 16,35±0,91 300-350 104,25±2,7 257,85±3,5 34,68±3,3
KHF2 5220±120 6,27±0,72 430-500 110,53±3,1 119,33±7,5 64,82±2,1
KH2F3 4380±125 5,57±0,63 350-403 83,84±5,7 106,73±5,7 52,34±3,2
KH4F5 4310±115 14,48±0,71 300-350 88,81±9,7 228,72±9,7 3,26±1,2
Enthalpy reactions of alkaline metals hydrofluoride formation are determined by
calorimetry solution methods. Thermodynamic characteristics’ standard values of alkaline
metals hydrofluorides are calculated on their basis (table 2.).
Table 2. Value of standard thermodynamic properties of lithium, sodium and potassium
hydrofluorides
fH0298,kiloJoule ·mole-1 S0298, Joule·mole-1· К-1
Compound Experiment Literature
Tensimetry Calorimetry Tensimetry Literature
LiHF2 885,7±8,7 935,5±5,0 921,3 74,1±8,0 71,0
938,1
NaHF2 822,57±8,5 827,89±6,7 906,0 128,42±7,0 90,91
NaH2F3 1117,68±7,3 1126,96±9,3 - 258,67±6,5 -
КHF2 782,52±4,5 833,52±9,5 893,1 120,4±5,0 109,49
КH2F3 1014,48±11,0 1128,62±11,0 - 187,33±0 -
КH4F5 1557,38±13,0 1736,41±15,0 - 247,93±1,0 -
STUDY OF RE ORTHOPHOSPHATES IN THE HIGH TEMPERATURE REGION

Ryumin M.А.1, Khoroshilov А.V.1, Nikiforova G.Ye.1, Gurevich V.М.2, Gavrichev K.S.1
1
Kurnakov Institute of General and Inorganic Chemistry
of the Russian Academy of Sciences, Moscow
2
Vernadsky Institute of Geochemistry and Analytical Chemistry
e-mail: Ryumin@igic.ras.ru
RE orthophosphates draw attention of researchers owing to the high thermal stability,
chemical inertness and very small solubility in water. Thermal and thermodynamic properties
of orthophosphates are studied insufficiently: the enthalpies of formation were determined for
all RE orthophosphates, whereas a low-temperature heat capacities and high-temperature
enthalpies were studied mainly for cerium subgroup REPO4. Experimental data on high-
temperature studies of RE orthophosphates by the DSC methods and a drop-calorimetry are
presented.
Orthophosphates were prepared by a solid-state method; the hydrated precursors were
annealed at 900ºС. One-staging of samples was confirmed by the X-ray diffraction method.
Orthophosphates with monoclinic (monazite-type) (Ln = La-Tb) and tetragonal (xenotime-
type) structures (Ln = Dy-Lu, Y) were synthesized.
The enthalpy increment in the range of 300-1700 K was measured in the SETARAM
DSC 2000K. The thermal behavior studies and high-temperature heat capacity measurements
(300-1500 K) were carried out by NETZSCH STA 449 F1 Jupiter.
Temperature dependences of a high-temperature enthalpy and heat capacity in the
temperature region 300-1700K were determined. The thermal effects connected with the
phase transformations in RE orthophosphates including the unknown earlier very high
temperatures for terbium and dysprosium orthophosphates were revealed. Entropy, change of
enthalpy and derived Gibbs's energy were calculated by the equation with use of Debye,
Einstein and Kiffer models. Thermodynamic functions of RE orthophosphates in the region
from 2 to 1600 K were estimated using the earlier obtained data for low-temperature range.
This investigation was supported by Presidium of the Russian Academy of Sciences
Research program № 8.
EMPIRICAL AND AB INITIO CALCULATIONS OF THERMOCHEMICAL

PARAMETERS OF STANDARD AND NON-STANDARD L-AMINO ACIDS
Sagadeev E.V., Gimadeev A.A., Chachkov D.V.*, Barabanov V.P.
Kazan State Technological University, Kazan, e-mail: sagadeev@list.ru
∗Interdepartmental Supercomputer Center, Kazan Branch, Russian Academy of Sciences
To date, there are over one hundred and seventy amino acids of various structures [1].
Of these, twenty standard amino acids are involved in protein biosynthesis. The remaining
non-standard (non-protein) amino acids exist in biological organisms in the free form. They
are involved in various biochemical processes [1]. A study of the thermochemistry of these
compounds is of special interest. In particular, an understanding and follow-up modeling of
protein biosynthesis necessitate an elucidation of values of energy parameters for the amino
acids. However, despite an importance of the compounds of this class, we can conclude on the
basis of a literature data that thermochemistry of the amino acids in comparison with other
classes of organic nitrogen compounds is poorly studied.
For a computation of standard thermochemical characteristics of L-amino acids we used
increment method [2] that earlier gave good results at the examination of thermochemical
characteristics of organic compounds. Using this approach we have calculated the formation
enthalpies in the gas phase and in the crystalline state of more than fifty of standard and non-
standard L-amino acids [2-6]. Enthalpy of sublimation of amino acids were calculated from
the difference in the formation enthalpies of compounds in the gas phase and in the crystalline
state.
Next, we performed the ab initio calculations of gas-phase formation enthalpies of
amino acids. The B3LYP/6-31G(d) method was chosen as a first approximation to find
rapidly the optimal molecular conformations of the compounds. Then for the most
energetically favorable conformations of amino acids we performed the calculation of their
ΔH0f values by the B3PW91/cc-pVQZ and B3PW91/cc-pVTZ methods.
All quantum-chemical calculations were carried out with the Gaussian 98 software in
the Interdepartmental Supercomputer Center of Russian Academy of Sciences (Kazan Branch)
(http://wt.knc.ru).
References
[1] Greenstein J.P., Winitz M. Chemistry of the amino acids. New York, London. John
Wiley & Sons, 1961.
[2] E.V. Sagadeev, A.A. Gimadeev, D.V. Chachkov, V.P. Barabanov. Russian Journal of
General Chemistry. 79 (2009) 453.
[4] E.V. Sagadeev, A.A. Gimadeev, V.P. Barabanov. Russian Journal of Physical
Chemistry A, Focus on Chemistry. 84 (2010) 209.
THERMODYNAMIC PROPERTIES, PARTICULARITIES OF STRUCTURE

AND THERMAL STABILITY OF LAYERED PEROVSKITE-TYPE TITANATES
Sankovich A.M., Blokhin A.V., Kohut S.V., Zvereva I.A.
Saint Petersburg State University, Department of Chemical Thermodynamics
and Kinetics, Saint Petersburg
e-mail: annasankovich@yandex.ru
Layered perovskite-type oxides represent promising materials due to a wide range of
their physical and chemical properties (electrical, magnetic, catalytic) depending on
composition and structure. Moreover cation-ordered oxides are attractive as precursors in soft
chemistry roots for synthesis of new layered compounds.
In report we present results of the study on thermal stability and heat capacity of
titanates NaNdTiO4, Na2Nd2Ti3O10, and NaGdTiO4 with general formula (NaLn)(n+1)/2TinO3n+1
that belong to the Ruddlesden-Popper phases and built by the intergrowth of alternating
perovskite-type blocks and Rock-salt type slabs.
Thermal stability of layered oxides NaNdTiO4, Na2Nd2Ti3O10, and NaGdTiO4 is
investigated by isothermal annealing-quenching method followed by X-ray powder diffraction
analysis and methods of thermal analysis with constant speed of heating (DSC and TG) in the
temperature ranges of 1050–1350 K, 1350–1650 K, and 1150–1300 K, respectively.
The structure-chemical mechanisms of oxides decomposition and temperature intervals
of phase transformations are determined. The comparison of oxides stability is carried out in
terms of crystal chemistry. The essential contribution in the phase transformations are brought
by the effect accompanying change of the coordination environment of Nd+3 (C.N. = 9, 12, 6)
and Ti+4 (C.N. = 6, 5) cations and considerable distortions of their coordination polyhedra.
The difference in the length of Na–O bond connecting P and RS layers also results in the
greater stability of Na2Nd2Ti3O10 layered structure in comparison with the NaNdTiO4. In turn
single-layer oxide NaGdTiO4 is less stable than NaNdTiO4. The tetragonal structure of single-
layer oxides is distorted to orthorhombic when replacing Nd by Gd owing to a mismatch of P
and RS layers of tetragonal symmetry.
The present work combines the results of heat capacity measurements obtained from
different calorimetric methods such as adiabatic calorimetry and differential scanning
calorimetry (DSC).
The heat capacities (Cp) of NaNdTiO4 and Na2Nd2Ti3O10 in the low-temperature range
(5–370 K) are measured in a TAU-10 adiabatic vacuum calorimeter (Moscow, Termis). The
relative uncertainty using the calorimeter did not exceed ±4∙10-3Cp in the range of 20–370 K,
±1∙10-2Cp in the range of 10–20 K, and ±2∙10-2Cp at the temperature less than 10 K. Standard
molar heat capacities, enthalpies, entropies, and derived Gibbs energies for NaNdTiO4 and
Na2Nd2Ti3O10 compounds are calculated.
The high-temperature Cp measurements for NaNdTiO4, Na2Nd2Ti3O10, and NaGdTiO4
are performed in a DSC 204 F1 Phoenix calorimeter (Germany, Netzsch) in the range of 300–
920 K.
An anomaly is noticed on a curve of temperature dependence of Na2Nd2Ti3O10 heat
capacity. The increase of Cp at temperature decrease is observed at temperatures below 7.4 K.
Such behavior is most likely to be caused by the phase transition of second type due to the
ordering of magnetic moments of Nd3+ paramagnetic ions.
This work was supported by Russian Foundation for Basic Research (N 12-03-00761)
and Saint Petersburg State University research grant (reg. 12.0.105.2010).
STRUCTURAL-ADDITIVE APPROACH FOR ESTIMATION

OF PHYSICAL PROPERTIES OF LIQUID CRYSTALS
Seminozhenko D.G., Safronova T.O., Pestov S.M.
e-mail: dariya-seminozhenko@yandex.ru
Liquid crystals found a wide application in electro-optical devices including display
technologies. At present more than 100,000 mesogenic compounds are synthesized [1].
However, for the majority of them (∼98 %) only temperatures and enthalpies of phase
transitions are known. To enlarge the practical application areas, it is necessary to have the
more complete set of data on physical and thermodynamic properties of individual mesogens
and their mixtures [2].
We made measurements of density of mesogenic aromatic esters and their mixtures in
mesophase and in isotropic state. For correlation analysis of density of crystals in homologues
series we used data of X-ray analysis [3].
For physical properties estimation, a scheme based on the minimum experimental
information (molecular structure) was developed. Applicability of the group-contribution
methods has been first tested on p-substituted "model substances", (i.e. compounds having a
structure typical for calamitic mesogens, for which a set of physical properties had been well
studied). Methods, that gave the minimum difference between the estimated and experimental
data, have been tested on liquid crystalline substances. Scheme for the estimation of density,
refractive index and sound velocity in mesophase and in isotropic state was proposed.
At estimation of density and sound velocity, a good coincidence was obtained by Yen-
Woods and Rao equations [4] usage. Different correlation dependencies were checked on a
large volume of experimental data [5]. Precision of estimation methods is enough for
engineering calculations.
References
1. Pestov S., Vill V. Liquid Crystals. / In: Springer Handbook of condensed matter and
materials data. /ed.: W. Martienssen. Berlin: Springer, 2005. P. 941.
2. Tomilin M.G., Pestov S.M. Properties of liquid crystalline materials. SPb.: Polytechnika,
2005. 296 p. (in Russ.)
3. Pestov S.M., Molochko V.A., Klimova E.V. // Liquid crystals and their practical usage.
2005. №. 3-4., P. 100.
4. Reid R., Prausniz J., Sherwood T. Properties of gases and liquids. 3 ed. L.: Khimiya, 1982.
592 p. (in Russ.).
5. Pestov S. Physical properties of liquid crystals. / Landolt-Boernstein. N.S. VIII/5A.
electron. edition. Berlin: Springer, 2003. 2780 p.
KNUDSEN EFFUSION MASS-SPECTROMETRIC

STUDIES OF Sm, Eu, Yb IODIDES
Sergeev D.N., Ivanov D.A., Butman M.F., Kudin L.S., Dunaev A.M.
e-mail: butman@isuct.ru
Samarium, europium and ytterbium halides are distinguished from the other lanthanide
halides by specific physicochemical properties. The possibility of disproportionation and
decomposition reactions due to heating has been shown in the previous studies. It requires a
more detailed study of this processes. In our previous research the new approaches for the
determination of a vapor composition and thermodynamic characteristics of the Sm, Eu, Yb
bromides species have been proposed. In this work these approaches were used for detailed
studying of LnIn (Ln = Sm, Eu, Yb; n = 2, 3) sublimation.
The research is performed on the magnetic sector-type mass spectrometer MI 1201
(∠90°, 200 mm curvature radius) modified for high temperature studies. A special ion source
allowed to carry out measurements in the electron ionization (EI) and thermionic emission
(TE) regimes in order to study both neutral and charged vapor components. Molecular and
ionic vaporization of the Sm, Eu, and Yb iodides was investigated in the temperature range of
800 – 1300 K.
In the EI mass spectra of LnI2 the ions Ln+, LnI+, LnI2+, Ln2I3+ were identified and
ionization efficiency curves (IEC) were obtained. An example of the IEC for the ytterbium
diiodide compared with the dibromide is presented.
Figure. Ionization efficiency curves upon vaporization of YbI2 and YbBr2
In the TE mass spectra of LnI2 the ions I-, LnI3-, Ln2I5- were detected. Analysis of these
data indicates to the thermal stability of Sm, Eu, Yb diiodides for disproportionation as
opposed to dibromides. The experimental study of Sm and Yb triiodides has shown the
thermal decomposition process with the release of molecular iodine.
These results allowed to conclude the possibility of thermodynamic determination of
sublimation enthalpies for SmI2, EuI2, YbI2.
The study was supported by The Russian Foundation for Basic Research (project 12-03-
3132112) and The Ministry of Education and Science of Russian Federation (project
14.B37.21.1192).
SYNTHESIS, STUDY OF THE VAPORIZATION PROCESSES

AND THERMODYNAMIC PROPERTIES OF Y3Al5O12
IN THE TEMPERATURE RANGE 2200-2800 К
Sevastyanov V.G.1, Simonenko E.P.1,2, Simonenko N.P.1, Stolyarova V.L.3,
Lopatin S.I.3, Kuznetsov N.T.1
1
N.S. Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy
of Sciences, Moscow, Russia, e-mail: v_sevastyanov@mail.ru
2
Lomonosov Moscow State University of Fine Chemical Technologies, Moscow, Russia
3
Chemical Department, Saint Petersburg State University, Saint Petersburg, Russia
A powder of yttrium aluminum garnet Y3Al5O12 (YAG) - a promising component for
the creation of new optical materials, lasers, for obtaining phosphors and high-temperature
materials and thermal barrier and protective coatings - synthesized using glycol-citrate
method, followed by purification of the excess carbon at 973±50K. Elemental and phase
composition of the product, the microstructure and thermal behavior were investigated.
Particle agglomeration during heat treatment in various conditions was studied.
Vaporization process investigation in the temperature range 2200-2800 K was carried
out by high-temperature differential mass spectrometry (mass spectrometer MS-1301, the
energy of ionizing electrons 30eV). In the isothermal exposure process of the sample with
initial concentration Al2O3 0.60 mol. rate., corresponding to Y3Al5O12, there was a
simultaneous transition to a vapor of aluminum oxides in the form of atomic aluminum, Al2O
and AlO, and yttrium as YO, with preferential removal of aluminum oxide from the melt,
which corresponds to the volatility ratio of individual oxides Al2O3 and Y2O3. With
decreasing Al2O3 mole fraction in the melt from 0.60 to 0.59 its activity at first increases from
0.17 to 0.53, and then begins to decline, probably due to the fact that the Al2O3 concentration
0.60 mol. rate. in the melt corresponds to thermally stable compound Y3Al5O12, that melts
congruently at 2213 K. Al2O3 activity increases at the outlet of the homogeneity Y3Al5O12.
Further, as the concentration
Temperature, К
2673 2800 2950 of aluminum oxide in the melt
Mass vaporized substances, mg
1,2 decreases, the amount of

Al2O3 activity decreases until
1,0 its complete removal from the
2 system. Y2O3 activity values
0,8
in the homogeneity area of
0,6 YAG are so small that the
3 output of the Al2O3-Y2O3
0,4 1 system from the Y3Al5O12
homogeneity area are almost
0,2 invisible. The dependence of
components activity, the
0,0 Gibbs energies of formation
0 20 40 60 80 100 120 140 160 180 200
and excess Gibbs energies of
The evaporation time, min formation from the
The dependence of the mass loss of the melt in the form concentration of the
of Al2O3 (1), Y2O3 (2) and system Al2O3 - Y2O3 (3) components in the melt
in the vacuum of the evaporation time. indicates that there are
significant negative deviations from ideal behavior in this system at 2700K in homogeneous
melt area.
THERMOCHEMICAL PROPERTIES OF GASEOUS TITANIUM MOLYBDATES

AND TUNGSTATES
Shugurov S. M., Lopatin S. I., Panin A.I., Emelyanova K.A.
Department of Chemistry, St. Petersburg State University, St. Petersburg
e-mail: lab-mass@yandex.ru
Gaseous molybdates and tungstates of alkaline-earth metals and europium and their
thermodynamic characteristics have been known so far. In these salts TiO2 is anionforming
oxide. There is no information concerning gaseous titanium salts. Titanium oxide Ti3O5 when
heated evaporates in the form of TiO and TiO2. To synthesize gaseous titanium salts it is
necessary to create favorable conditions for both titanium oxides and oxide with more acid
properties in vapor to exist.
The Knudsen effusion technique with mass spectrometric analysis of the vapor
composition was employed. The molybdenum and tungsten twin effusion cells heated by
electron bombardment were used. The temperature was measured with an accuracy of ±5 K
using an optical pyrometer EOP-66 of high precision. The appearance energies (AEs) of ions
were obtained by the vanishing current method with Au as an energy standard, which was
found to be accurate within 0.3 eV. The analysis of the vapor mass-spectra showed that XO2,
XO3, TiXO3, TiXO4 and TiXO5 (here and further X = W, Mo) exist in vapor along with TiO
and TiO2. The evaporation of Ti3O5 produced gaseous TiO and TiO2, gaseous molybdenum
and tungsten oxides being formed during the reaction of SiO2 with the material of the cell.
The partial vapor pressures of the gaseous species were determined by the method of ion
current comparison using Au as internal pressure standard. To determine the standard
enthalpies of formation for indium molybdate and tungstates, we derived the equilibrium
constants Kp and enthalpies for gaseous reactions (1-4) using eqn (5).
TiO + XО3 = VXO4 (1)
TiO2 + XO2 = VXO4 (2)
TiO + XО2 = TiXO3 (3)
TiO2 + XO3 = TiXO5 (4)
∆rH0 (0) = T [∆rФ0 (T) – R ln Kp (T)] (5)
The free-energy functions and heat capacities of gaseous oxides TiO, TiO2, XO2, and
XO3 necessary for the calculation of the enthalpies of reactions were taken from the reference
book. The free-energy functions and heat capacities of gaseous titanium salts were calculated
by the statistical thermodynamic method in the rigid rotor-harmonic oscillator approximation
on the base of molecular parameters and vibrational frequencies obtained by quantum
chemistry computation.
Using the enthalpies of reactions (1-4) recalculated to temperature 298 K, together with
the reference values of gaseous oxides TiO, TiO2, XO2, and XO3 formation enthalpies, we
determined standard formation enthalpies for gaseous TiXO3, TiXO4 and TiXO5.
MELTING BEHAVIOR OF CoFeBSiNb ALLOYS WITH Ga AND Sb ADDITIONS

Sidorov V.E., Rojkov I.V., Mikhailov V.A., Hosko J., Svec P.
Ural State Pedagogical University, Ekaterinburg
Institute of Physics SAS, Bratislava
e-mail: vesidor@mail.ru
Bulk metallic glasses (BMG) is a novel group of engineering materials with unique
mechanical, thermal, magnetic and corrosion properties. Nowadays BMG samples of several
cm in size were obtained in Zr-, Ti-, Pd, Co, Ni-based alloys. It was discovered, in particular,
that Co-based amorphous wires and ribbons exhibit the giant magneto-impedance effect,
which has been subsequently developed in high-sensitivity sensor materials. However, due to
the low glass forming ability (GFA), it is difficult to produce Co-based bulk amorphous
alloys; therefore it is still necessary to develop a Co-based BMG with high GFA.
In this work we investigated the influence of gallium and antimony additions on
melting, crystallization and electronic structure of Co47Fe20.9B21.2Si4.6Nb6.3 alloy. These 2
elements were chosen because they match rather well the criterion of increased GFA given by
A. Inoue: differences in atomic radii against the main elements of the alloy (cobalt and iron)
are about 12%; the systems Co-Ga and Co-Sb are characterized by the negative heat of mixing
(ΔH is up to -11 kJ/mol in case of Co-Ga pair and up to -14 kJ/mol for Co-Sb).
Magnetic susceptibility measurements were performed on an equipment using relative
variant of Faraday’s method. The values of magnetic susceptibility were obtained during
heating and subsequent cooling with the steps for 5–10 K and isothermal expositions for 4–5
min at each temperature or during continuous scan with a rate of 2 K/min. The total
uncertainty of the determined values of magnetic susceptibility was below than ± 2%.
This property was found to be rather informative for obtaining the characteristics of
melting/solidification. In particular, using χ-1 = f(T) dependences it is easy to determine
liquidus temperature at heating (TLH) and subsequent cooling (TLC) by fixing the curve bends.
Afterwards the undercooling can be obtained as ΔT = TLH – TLC. It was found that the
additions of gallium raise remarkably the liquidus both at heating and at cooling, but the latter
increases faster and hence undercooling decreases. On the contrary, 2% of antimony lifts
liquidus temperature as much as 3 % of gallium at heating but not the same for cooling and so
the undercooling reaches rather high value. However, both Ga and Sb additions shift the
beginning of crystallization to elevated temperatures in comparison with the base
composition.
Fitting the experimental χ(T) curves by the generalized Curie-Weiss law one can obtain
some characteristics of electronic structure of the alloys. It was stated, in particular, that the
additions of gallium shift paramagnetic Curie temperature θ to higher values and hence
strengthen the interatomic interaction in the melt, because θ is proportional to the overlap
integral between the neighboring atoms. Thus the addition of Ga leads to slowing-down of the
formation and growth of nucleus and hence to a decrease of the embedded crystalline particles
sizes. In the case of antimony additions, θ goes down. It means that Sb atoms “do not want” to
be incorporated into the existing short-range order of the melt, but distort it. Maybe because of
this, the solubility of antimony in base metals (Co and Fe) is very low.
The suggestions on optimal content of Ga and Sb additions to BMG forming alloy are
discussed.
ENTHALPIES OF FORMATION OF RC●(O) FREE RADICALS

Sitnikov V.N., Chernova E.M., Orlov M.Y., Turovtsev V.V., Orlov Y.D.
e-mail: VitalySitnikovN@yandex.ru
One of the key characteristics of free radicals (R●) is the enthalpy of formation at
standard conditions ΔfH0(R●). Experimental determination of thermodynamic properties of R●
is very difficult, time consuming and expensive, due to their high reactivity and short lifetime.
Expansion of a quantitative base of thermochemistry of free radicals includes the
development of effective methods for predicting ΔfH0(R●), incorporation new classes of R●,
refinement of known values ΔfH0(R●) and establishment the «structure-property (enthalpy of
formation)» quantitative correlation [1].
This work presents ΔfH0(R●) of acetyl radical (RC•(O)), where R is an aliphatic alkyl
moiety (containing oxygen in some cases). ΔfH0 values for RC•(O) were found by the
expression (1)
ΔfH0(RC•(O)) = D(RC(O)-Н) - ΔfH0(H) + ΔfH0(RC(O)Н). (1)
Here D(RC(O)-Н) is the С-Н bond breaking enthalpy taken from [2], ΔfH0(H)=218 kJ/mol is
the enthalpy of formation of a hydrogen atom, and ΔfH0(RC(O)Н) is enthalpy of formation of
the parent molecule [3].
In some cases, in the literature the same compounds have got different values of
ΔfH0(R•). All of them were included in the review. The analysis of whole set of ΔfH0(R●) was
performed within of the additive-group approach using the found "structure-enthalpy of
formation" quantitative correlation. It has allowed us to classify 5 of 15 values ΔfH0(RC•(O))
as «recommended» (in other words «preliminary»).
As a result enthalpies of formation of three acetyl organic radicals were determined,
enhanced data base of ΔfH0(R•) (15 values were added) and found the ΔfH0 group parameters
for the homologous series RC•(O). The comparison ΔfH0(RC•(O)) obtained in the framework
of the additive-group approach with the experimental data showed a good agreement.
References
[1] Yu. D. Orlov, Yu. A. Lebedev, and I. Sh. Saifullin, Thermochemistry of Organic Free
Radicals (Nauka, Moscow, 2001) [in Russian].
[2] J.-R. Luo, Comprehensive handbook of chemical bond energies .L., N.-Y.:CRC Press,
Boca Raton.2007.
[3] NIST, Scientific and Technical Databases, version 2008.
(http://webbook.nist.gov/chemistry/form-ser.htm)
THERMODYNAMIC PROPERTIES OF HARD POLY(PHENYLENE-PYRIDYL)

DENDRIMERS IN THE RANGE FROM T → 0 TO 550 K
Smirnova N.N.a, Zakharova Yu.A.a, Markin A.V.a and Shifrina Z.B.b
a
Lobachevsky State University of Nizhni Novgorod,
National Research University, Nizhni Novgorod
e-mail: smirnova@ichem.unn.ru
b
Nesmeyanov Institute of Organoelement Compounds,
In the last decades the new field of chemistry and physico-chemistry of macromolecular
compounds such as synthesis and study of different properties develops actively. The objects
of this research are hard poly(phenylene-pyridyl) dendrimers which combine both high
stability to external conditions changes and low density with ability to carry along internal
particulars in their moving. This properties combination makes good conditions for
encapsulation of different agents which can be used to create new hybrid (dendrimer – metal)
nanostructural systems with catalytic properties.
In the present research the heat capacity and thermodynamic characteristics of the
physical transformations of hard poly(phenylene-pyridyl) dendrimers of the first – fourth
generations and different structures, containing phenylene rings were studied for the first time
with the methods of adiabatic vacuum calorimetry and differential scanning calorimetry over
the range from 6 to 550 K. The thermal stability for objects under study was determined by
TG-analysis.
о
heat capacity C p (T), enthalpy H°(T)−H°(0), entropy S°(T), residual (zero) entropy S°(0), and
Gibbs function G°(T)−H°(0) in the range from T → 0 K to 550 K. It was revealed, that the
dendrimer of first generation in the range under study is exists in the glass and high-elastic
states, for this the thermodynamic characteristics of devitrification and glassy state were
estimated.
The qualitative, analytical and graphical dependences of thermodynamic properties vs
both molecular weight of dendrimers and number of phenylene and pyridyl fragments were
revealed and analyzed. The linear character of these dependences was established. These
equations permit to predict in some limits the physico-chemical properties for hard
poly(phenylene-pyridyl) dendrimers not yet studied.
14.В37.21.0799).
THERMODYNAMIC PROPERTIES OF CARBOSILANE DENDRIMER

OF THE THIRD GENERATION G-3(Si-O-Si, 3EtOx)32
Sologubov S.S.a, Smirnova N.N.a, Muzafarov A.M.b
a
Nizhni Novgorod, e-mail: smirnova@ichem.unn.ru
b
Enikolopov Institute of Synthetic Polymeric Materials
of the Russian Academyof Sciences, Moscow
The synthesis, study and application of dendrimers are one of new and rapidly
developing directions of polymer science. The dendrimers are individual hyper branched
macromolecules with a high degree of order. The synthesis of dendrimers is realized by
repeating subsequent of chemical reactions, this makes possible to effective control of
molecular weight of dendrimers, topology and chemical character of their functional groups.
The combination of structural perfection of dendrimers and possibilities of modification of
their groups are basis of development of functional nanosized materials with unique
electronic, optical, magnetic and chemical properties, that is necessary for development up-to-
date nanotechnologies.
о
In the present research the temperature dependence of heat capacity C p = f(T) of a
carbosilane dendrimer of the third generation G-3(Si-O-Si, 3EtOx)32 was measured for the
first time with adiabatic vacuum calorimeter over the range from 6 to 350 K and differential
scanning calorimeter over the temperature range from 330 to 580 K.
The compound devitrified at T = (176 ±1) K. Also we revealed reproducible anomaly of
the curve of the temperature dependence of heat capacity of G-3(Si-O-Si, 3EtOx)32 over the
interval from 40 to 80 K. The anomaly was plotted as positive deviation from normal
о
(interpolated) trend of curve. It reproduced every time on cooling and subsequent C p
measurement over this range. This anomaly was hypothetically conditioned with vibration
excitation of shielded groups of repeating fragments (for example, methyl ones) in
macromolecules on their heating and vibration freezing on their cooling.
Interesting thermal behavior was revealed within high-temperature range for
G-3(Si-O-Si, 3EtOx)32. In heating run an exothermic peak was observed from 440 to 470 K.
The effect was not reproduced on subsequent cooling and heating of the dendrimer.
о
heat capacity C p (T), enthalpy H°(T) - H°(0), entropy S°(T), residual (zero) entropy S°(0), and
Gibbs function G°(T) - H°(0) in the range from T → 0 K to 580 K for different physical states
of the dendrimer, and standard entropy of formation of the compound under study was
estimated at T = 298.15 K.
The low-temperature (20 K ≤ T ≤ 50 K) heat capacity data were analyzed based on
Debye's the heat capacity theory of solids. The fractal treatment of the heat capacity was made
and the values of characteristic temperature and fractal dimension were determined, some
conclusions about structure topology of the dendrimer were drawn.
The values were analyzed subject to composition and structure data and were compared
with corresponding values for other carbosilane dendrimers studied earlier.
14.В37.21.0799).
DETERMINATION OF ENTHALPY OF SUBLIMATION AND VAPORIZATION

OF CHEMICAL COMPOUNDS FROM THE ENTHALPY OF SOLUTION
Solomonov B.N.а, Novikov V.B.а, Varfolomeev M.A.а, Verevkin S.P.b
a
Kazan Federal University, Kazan, Russia
e-mail: boris.solomonov@ksu.ru
b
University of Rostock, Rostock, Germany
e-mail: sergey.verevkin@uni-rostock.de
Enthalpies of sublimation and vaporization are the fundamental characteristics of
chemical compounds. Reliable methods for the determination of these quantities were
developed early. However, the results obtained by different authors differ significantly,
especially for the low-volatile substances of large molecular weight. In this paper, we propose
a method for determining the enthalpies of sublimation and vaporization of chemical
compounds, which don’t have limitations of classical methods.
It is well-known, that enthalpy of solution of solute Аi in solvent S at infinite dilution
( ∆ soln H Ai / S ) can be presented as the sum of sublimation enthalpy ( ∆ crg H mAi ) (solid solute) or
vaporization enthalpy ( ∆ lg H mAi ) (liquid solute) and enthalpy of solvation ( ∆ solv H Ai / S ):
∆ soln H Ai / S = ∆ crg H mAi (∆ lg H mAi ) + ∆ solv H Ai / S (1)
Early, one of the authors [1] found a correlation between the enthalpy of solvation of a
wide range of non-electrolytes in cyclohexane and their molar refraction:
−∆ solv H Ai / С=
6 H12
5.09 + 1.03 ⋅ MR Ai (2)
This equation is possible in some cases to simplify the determination of the enthalpy of
the phase transition of a substance at 298.15 K, since, according to equations (1) and (2) it
requires only measurement of enthalpy of solution at 298.15 K in cyclohexane and evaluation
of the molecular refraction. Determination of molar refraction for liquids is not complicated
task, for solids well-known techniques can be used.
The method based on the equations (1) and (2) has one important limitation. It is low
solubility of organic compounds in cyclohexane. Therefore, this paper discusses how to
determine the enthalpies of sublimation and vaporization from the enthalpies of dissolution in
other solvents.
Enthalpies of solution of various organic compounds (aromatic hydrocarbons, their alkyl
and halogen derivatives) in a series of solvents were determined by method of solution
calorimetry at 298.15 K. Obtained enthalpies of phase transitions were compared with the
literature data.
Reference
1. Solomonov B.N. et al. Dokl. AN SSSR, 1979, V.247, P. 405-408.
ACCURATE PREDICTION OF ENTHALPIES OF FORMATION

OF NITRO COMPOUNDS BY QUANTUM CHEMICAL CALCULATIONS
Suntsova M.A., Dorofeeva O.V.
Chemistry Department, Lomonosov Moscow State University, Moscow, Russia
e-mail: suntsova.m@gmail.com
Numerous nitro compounds have explosive properties and attract considerable attention
in the modeling of new high energy materials with projected characteristics. Important
characteristics of explosives and propellants may be calculated from the enthalpy of
formation, which is closely related to the stability and sensitivity of these compounds. The
experimental enthalpies of formation for many important nitro compounds are often unknown
or identified with relatively large uncertainties. Therefore, it would be useful to apply a
reliable theoretical method to calculate the enthalpies of formation of energetic nitro
compounds.
In this study the accuracy of different composite Gaussian-n and ccCA methods was
analyzed to calculate the enthalpies of formation of various nitro compounds in the gaseous
phase. To check the accuracy of values obtained from atomization energies, the method of
isodesmic reactions was also employed. It was found that the last version of Gaussian theory,
the G4 method, underestimated the enthalpy of formation values by 5-20 kJ/mol. Much better
agreement with experimental values show the G3 and ccCA methods (see table below).
∆ f H 298

(exp) - ∆ f H 298

(calc), kJ/mol
G4, Isodesmic
ccCA-PS3 *
∆ f H 298

ccCA-S3 *
G3MP2B3
ccCA-P *
(exp),
reactions
G4MP2
Compound
G4
G3
kJ/mol
CH2(NO2)2 -38.5 ± 1.3 14.2 2.8 6.2 2.8 0.0 9.2 4.6 -1.9
C(NO2)4 82.4 ± 1.7 16.8 -8.5 4.5 -3.9 -24.7 -9.6 -17.2 0.4
* K.R. Jorgensen, G.A. Oyedepo, A.K. Wilson, J. Hazard. Mater. 186 (2011) 583.
However it is impossible to choose one of them as the most reliable, whereas the
isodesmic reactions give a good agreement with the experimental values in all cases. Thus, the
isodesmic reaction method was used in this study to check the available experimental data on
nitro compounds and predict the enthalpies of formation of new energetic compounds. Special
consideration was given to use of the internally consistent values of enthalpies of formation of
reference compounds.
The results of enthalpy of formation calculation are given in this work for more than 60
nitro compounds. Among the two widely-used experimental values for nitromethane (-74.5
and -81.0 kJ/mol), our calculations strongly support the first one. The theoretical value for
nitrobenzene (62.8 kJ/mol) is slightly lower than the experimental one (67.5 kJ/mol). Since
the theoretical value is based on about 100 isodesmic reactions with 26 different reference
nitro compounds, new measurements of enthalpy of formation of nitrobenzene would be
extremely valuable as a check on the accuracy of the theoretical calculations. On the basis of
theoretical evidence, the enthalpies of formation of some nitro compounds (CH(NO2)3,
CH3N(NO2)2, CH3C(NO2)3, 5-nitrouracil and others) may also not be as accurate as cited
experimentally.
SOLVATES OF FELODIPINE: A SYSTEMATIC INVESTIGATION

OF ARCHITECTURE AND ENERGY
Surov A.O., Perlovich G.L.
G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo
e-mail: aos@isc-ras.ru
Felodipine is a calcium-channel blocking agent, widely used for treatment of
hypertension and prevention of angina. Two polymorphs of felodipine as well as one solvate
are established in the literature so far. In the present work we describe solvates of felodipine
with three structurally related, high-boiling point liquids, N,N-dimethylacetamide (DMAA),
1,1,3,3-tetramethylurea (TMU) and 1,3-dimethyl-2-imidazolidinone (DMEU) (Fig. 1). We
report here on the crystallization, single-crystal structures, solution
O
calorimetry, differential scanning calorimetry (DSC) characterization,
H3C
N CH3 and stability studies of the felodipine solvates.
CH3
The crystalline materials were grown and scaled-up by slow
evaporation of saturated solutions of suitable solvents. All solvates
DMAA
were also obtained using solvent-drop grinding technique during 30
O
min. The felodipine solvate structures were confirmed by single
H3C CH3 crystal crystallography. The felodipine·DMAA and felodipine·DMEU
N N
crystallize in P21/n and C2/c space groups, respectively. Whereas the
CH3 CH3
felodipine·TMU solvate has triclinic crystal system (Pī) and contains
TMU
4 felodipine and 4 TMU molecules in asymmetric unit. There were no
O
intermolecular hydrogen bonds found except felodipine-solvent.
H3C CH3
N N DSC curves of solvates show one endothermic peak, caused by
desolvation of the solvates, while felodipine melting does not occur.
DMEU The melting points were found to increase in the following order: 92.5
ºC for felodipine·TMU, 95.0 ºC for felodipine·DMEU and 110.2 ºC
Fig. 1. Molecular for felodipine·DMAA. Solvates destruction during desolvation
structures of solvate
process was confirmed by hot-stage microscopy. It was established
formers.
that melting points of the solvates are directly related to van der
Waals volumes of the respective “guest” molecules. In addition, crystal lattice energy
calculations showed a strong relationship between Fel-Fel interaction energy in the crystal and
the melting temperature of the solvate.
In order to estimate a heat of formation of solvates under study the enthalpy of
dissolution of felodipine and respective solvates were measured using isoperibolic solution
calorimeter. The enthalpies of formation of different solvates derived from solution
calorimetry are found to be nearly equal (considering experimental errors), which indicates an
important role of entropy factor for the process of solvate formation.
Dissolution profiles of felodipine solvates in water are virtually identical as well.
Concentration of felodipine increases up to 6 times (on average) compared to pure drug during
the first hour. However, solvates under consideration are quite unstable in water medium
which leads to rapid felodipine precipitation and concentration decreasing as a consequence.
Due to low vapor pressure of solvate formers, all solvates are rather stable on air and able to
keep stability even after two weeks exposure.
This work is supported by BioSol project (2010-1.1-234-069) and a grant from the
President of the RF, no. МК-7097.2012.3.
POSSIBILITIES OF VISCOUS FLOW MODELS FOR CHOLESTERIC LIQUID

CRYSTALLS APPLICATION
Syrbu Sv.А.,1,2 Sadovnikov А.I.,1 Burmistrov V.А.,3 Syrbu А.А.2
1
Ivanovo State University, Ivanovo, e-mail: syrbue@yandex.ru
2
Ivanovo Institute of the State Fire Service of the Russian Emergencies Ministry, Ivanovo
e-mail: syrbуa@yandex.ru
3
Ivanovo State University of Chemical Technology, Ivanovo
e-mail: burmistrov@isuct.ru
Viscosity – the most important property of liquid crystals, as it determines the electro-
optical effects engaging time, that is the time interval between the signal feeding and the
representation appearance.
To describe the temperature dependence of the rotational viscosity in the nematic phase,
which has no analogue in the isotropic liquid and the associated energy dissipation director
reorientation, there are two models. These are the activation model and the free volume
model. Thus far there are no sufficiently true criterions for the applicability of a particular
approach.
The cholesterogens are sterically and thermodynamically very similar to the
nematogens. Therefore, to establish their preferential flow regime was held approximation of
the rotational viscosity temperature dependences in the cholesteric phase by the activation
Arrhenius equation and the free volume theory, which is described by the Fulcher - Vogel –
Tamman equation.
The objects of investigation were cholesterol esters of saturated carboxylic acids: 3-(β-
n-alkanoyloxy)holestens-5 homologous series (n = 2, 3, 4, 9, 11, 12, 13, 15) and cholesterol
esters of the aromatic carboxylic acids: benzoic, cinnamic, p-chlorobenzoic, p-n-
hexylbenzoiс, p-n-alkyloxybenzoic acids (n = 8, 12).
All substances used in work purified by recrystallization from isopropyl alcohol
followed by vacuum under 1.3 kPa pressure from the isotropic phase to constant weight.
Temperature dependence of dynamic viscosity were obtained using a programmable
viscometer «Brookfield RVDV II +» with error 0.02 sPs. Accuracy of temperature was 0.2 K.
Revealed that saturated carboxylic acids cholesterol esters have higher values of
dynamic viscosity than the aromatic carboxylic acids cholesterol esters.
It is shown that the free volume model best approximates the dynamic viscosity
temperature dependence of homologous series of cholesterol esters of saturated carboxylic
acids containing more than 10 carbon atoms in the terminal substituent chain and cholesterol
esters of aromatic carboxylic acids containing aliphatic fragments.
It is established that fluctuation free volume reduction of cholesterol esters of saturated
carboxylic acids, compared with the geometric free volume.
THERMOCHEMICAL PROPERTIES OF CUPRATES OF ALKALINE-EARTH

AND RARE-EARTH ELEMENTS
Tiphlova L.A., Monayenkova A.S., Alyoshin V.A.
Lomonosov Moscow State University, Chemistry Department, Moscow, Russia
e-mail: tiphlova@thermo.chem.msu.ru
This work is a part of systematic investigations of thermochemical properties of copper-
containing metal-oxides materials. It carried out at Luginin’s thermochemistry laboratory and
Inorganic Synthesis Laboratory of Inorganic chemistry division. It is devoted to the study of
thermochemical properties of cuprates of calcium, stroncium, barium and lanthanum and also
the solid solutions La2-xМхCuOy (M=Ca, Sr, Ba). The choice of object of reseach is caused by
the discovery of new possibilities of practical application of complex cuprates as cathode
material for fuel cells and catalysts. These materials have high catalytical activity and also
high electronic and oxygen-ion conductivity.
All of the samples were obtained by a method of solid state synthsis and were tested by
X-ray analysis at Inorganic Synthesis Laboratory. The formal copper valence and extra oxygen
content in samples were determinated by iodometric titration. The composition of samples
was confirmed by ICP-MS method.
The enthalpies of formation of investigated cuprates from elements and oxides were
determined by solution calorimetry method. The enthalpies of reaction of cuprates with 1 N
hydrochloric acid were measured at 298.15 K in hermetically sealed swinging calorimeter
with a isothermal coat. The enthalpies of formation of cuprates from the elements and oxides
were calculated on the basis of the experimental data and the reliable literature data on
thermochemical properties of simple oxides of copper, lanthanum and alkaline-earth elements.
The enthalpies of formation of alkaline-earth cuprates on oxides decrease with increase
in ionic radius of alkaline-earth elements. It should be noted that barium cuprate is the stablest
compound in the series Ba2CuO3> Sr2CuO3 > Ca2CuO3.
The choice of La2-xМхCuOy (where M = Sr) for reseach in details is caused by the
widest homogeneous region of this system: 0<Sr(x)<1.2. It was estimated that the dependence
of ∆oxH(La2-xSrхCuOy) on Sr(x) has a minimum in the range of Sr(x)=0.6-0.8. This minimum
correlates with maximum of the dependence of the copper oxidation state on Sr(x) in this
system.
THERMODYNANICS OF ALTERNATING COPOLYMER

OF CARBON MONOXIDE WITH ETHYLENE AND BUTYLENE
Tsvetkova L.Ya.a, Kulagina T.G a, Zakharova Yu.A.a, Golodkov O.N.b, Belov G.P. b
a
Nizhni Novgorod State University, Nizhni Novgorod, Russia
e-mail: smirnova@ichem.unn.ru
b
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
Chernogolovka, Moscow region, Russia
e-mail: gbelov@cat.icp.ac.ru
At present problem of recovering of polymeric industry is burning issue in the result of
ubiquitous application of polymers and polymeric compositions. In the XXI century
environmental situation in all the world, rates and the directions of development of synthetic
plastics production will depended on this question solution. Production of biodegradable
polymers is one of the means for solving of this problem.
Polyketones are biodegradable polymers, the new generation of the functional polymers
with complex of perspective characteristics, that induce big scientific and applied interest in
its research. The researchers pay significant attention to investigations that seek to draw up
and to refine technology of synthesis and to study the specificities of physicochemical
properties of a given class of copolymers for the purpose of broadening of area for its
application. The present research is proceeding of authors investigations of polyketones
thermodynamic characteristics.
For the first time the heat capacity of the alternating copolymer of carbon monoxide
with ethylene and butylene with 14.9 mol.% of butane fragments was studied over the 6–500
К range by methods of adiabatic vacuum and dynamic calorimetry. The thermodynamic
parameters of its physical transitions were determined. The energy of the alternating
copolymer combustion was measured calorimetrically at 298.15 K. The experimental data
were used to calculate the standard thermodynamic functions C po (T), Н°(T)–H°(0), S°(T)–
S°(0) и G°(T)–H°(0) in the temperature range from Т → 0 to 320 K, the standard enthalpy of
combustion and thermodynamic characteristics of the studied copolymer formation at T =
298.15 K and po = 0.1 MPa.
The thermodynamic parameters of carbon monoxide with ethylene and butylene
copolymerization with formation of the alternating copolymer with 14.9 mol.% of butane
fragments were calculated in the 0−350 K range. It was shown that Gibbs function of the
alternating copolymerization has large negative values at room and more low temperatures. It
means that process of the alternating copolymerization has displaced forward to formation of
copolymer. Limiting temperature of the alternating copolymerization was estimated.
MATCHING METHOD AND ESTIMATES OF THERMODYNAMIC PROPERTIES

OF INDIVIDUAL SUBSTANCES IN THE CONDENSED STATE
Tupitsyn A.A., Bychinsky V.A., Mukhetdinova A.V.
Vinogradov Institute of Geochemistry Siberian Branch of the Russian Academy of Science,
Irkutsk, altfr@mail.ru
The way of coordination and evaluation of the thermodynamic properties of individual
substances in the condensed state, used in the calculation of phase equilibria is presented by
minimizing the thermodynamic potentials. Interconsistency standard entropy, heat capacity,
enthalpy of formation from simple substances, dependences of a thermal capacity on
temperature, fusion heat is defined.
The coordination of thermodynamic properties of the isostructural studied substances is
carried out by the additive methods defining the contribution of structures making substance
in numerical size of the investigated thermodynamic parameter. The size of contributions pays
off with the help linear multifactorial regression analysis, allowing considering average sizes
of superfluous functions at formation of investigated substances from structural components.
Taking into account an error of experimental data factors regression equations establishing
dependences on number of structural components for sizes standard entropy, a thermal
capacity and enthalpy of formation from simple substances are calculated.
On the basis of the consistent values according to the temperature for the entropy,
enthalpy increments and Gibbs energy of these substances in the solid and liquid state are
calculated. For the purpose of reception of the equations for these dependences with step 50-
100 К carried out regression analysis. The received correlation dependences allow to execute
interpolation and extrapolation of thermodynamic properties for limits of experimental
researches for substances on which basis correlations, and isostructural with it of the not
studied substances are received. A linear character regression equation guarantees absence
casual oscillation design value. By means of received regression equations functions from
temperature for entropy, increments enthalpy and energy of Gibbs of not studied substances
are calculated.
The melting temperature of the unexplored substances evaluated by comparing the
functions increment Gibbs energy of matter in the solid and liquid state, heat of fusion – an
independent comparison of the functions of the entropy and enthalpy increments. Dependence
of the temperature of the unexplored materials is determined by separate differentiation of
functions of entropy, enthalpy increments and energy of Gibbs. Results of differentiation are
exposed to joint processing for the purpose of receptions of the best reproducibility
simultaneously all three initial functions.
The offered way was used for the coordination and an estimation of thermodynamic
properties of silicates of alkaline metals (K, Li, and Na) and has shown comprehensible
accuracy. For example, the error of an estimation of temperature of fusion K2Si3O7 has made
1,4 %. In the table estimated thermodynamic properties of some not studied silicates in a
crystalline state are presented.
∆ f H ° ( 298,15 K ) S ° ( 298,15 K ) C °p ( 298,15 K ) ΔH°melt

Compound Tmelt, К
kJ⋅mole–1 J⋅К–1⋅mole–1 kJ⋅mole –1
Li2Si3O7 –3475,885 164,499 188,383 1172 65,168
Li4Si3O8 –4198,052 204,672 245,795 1303 83,338
Li6Si3O9 –4920,219 244,845 303,207 1405 101,508
ESTIMATION OF THE INTERNAL ROTATION CONTRIBUTION

TO THE THERMODYNAMIC PROPERTIES. COMPARISON OF MODELS
Turovtsev V.V, Orlov Yu.D
Tver State Medical Academy, Tver State University, Tver
e-mail: turtsma@tversu.ru
Internal rotation is one of an essential contribution in the thermodynamic properties in
the model of separation of intramolecular motions. However, such calculation is very
expensive, so it is usually estimated as a harmonic oscillation (seldom anharmonic one).
We found the solution of the Schrödinger’s equation (1) for the asymmetric internal
rotation
 ∂ ∂ 
− ∂ϕ F (ϕ ) ∂ϕ + V (ϕ )ψ (ϕ ) = Eψ (ϕ ) (1)
 
by means of the wave function ψ(φ) decomposition in a series of plane waves
+∞
ψ (ϕ ) = ∑ Ck e ikϕ . (2)
k = −∞
On the basis of obtained expressions the program suit for calculation of that contribution to
the thermodynamic properties (enthalpy, entropy, heat capacity and Gibbs free energy) was
created.
Studying of the internal rotation contribution was performed on the example of
mononitroalkane series n-CH3(CH2)nNO2, with n ≤ 7. The rotations of tops about all bonds C-
C and C-N were considered. Expressions for the potential function V(φ) and the rotation
constant F(φ) were represented as follows
( )
∞
V (ϕ ) = V0 + ∑ Vm/ cos(mϕ ) + Vm// sin (mϕ ) (3)
m =1
∞ ∞
F (ϕ ) = F0 + ∑ Fm/ cos(mϕ ) + ∑ Fm// sin (mϕ ) . (4)
m =1 m =1
The estimations of the contribution to the thermodynamic properties at T = 298 K were

made a) in the framework of the harmonic oscillation model, and b) by the classical statistical
physics relationship
2π V (ϕ )
−
∫ V (ϕ )e kT
dϕ
Eвн.вращ ∝ 0
2π V (ϕ ) , (5)
−
∫e
0
kT
dϕ
c) by direct summation of torsional energy levels εi (quantum approach) from the solving of
equation (1)
∞ εi
−
Евн.вращ ∝ ∑ ε i e kT
(6)
i =1
Comparison of models was carried out and recommendations on their choice, based on
the specified accuracy of calculation, are made.
SUBLIMATION ENTHALPIES AND MOLECULES PACKING FACTORS

OF AMINO ACIDS, PEPTIDES AND THEIR ACETYL DERIVATIVE AMIDES
Tyunina E.Yu., Badelin V.G.
G.A. Krestov Institute of Solution Chemistry,
Russian Academy of Science, Ivanovo
e-mail: tey@isc-ras.ru
The developments in nanotechnology are intensively growth to create new structured
materials in last decades. The molecules of biological nature can be serving as a basis for the
creation of nanostructures. Such systems can act as biosensors, the optical filters, carriers of
drugs. The energy of the crystal lattice is required parameter for a theoretical analysis of the
stability of different types of nanostructures. Under certain conditions one can be regarded as
the enthalpy of sublimation. Furthermore, the thermodynamics study of phase transitions of
amino acids, peptides and their derivatives contributes to a better understanding of the
characteristics of the crystalline state of polar organic compounds with donor and acceptor
groups which is capable to form the hydrogen bonds. Based on the structural characteristics of
39 crystalline amino acids, dipeptides and amides of N-acetyl derivatives and the
experimental data on the thermodynamic properties (enthalpy of sublimation, heat capacity),
the effects of the molecular form, the packing density of the molecules and their electronic
characteristics into the sublimation enthalpies of the organic crystals are investigated. The
standard molar enthalpies of sublimation at 298.15 K are calculated by using the values of the
heat capacity of the solid phase. The multiparameter correlation between the sublimation
enthalpies and molecular descriptors of the substances is suggested.
There are estimated the contributions of the volume, the electrostatic interaction
zwitterions and the hydrogen bond in crystals to the sublimation enthalpy of the compounds. It
is shown that the more compact molecules with small molecular volumes have a high density
packing. Introduction the alkyl, acetyl and amino groups into the structure of molecules result
in a decrease the efficiency of packing and the enthalpies of sublimation in a number of
aliphatic amino acids, dipeptides and their derivatives. The effect of electrostatic interaction
zwitterions decrease in the series: aliphatic dipeptides, substituted and cyclic dipeptides,
aliphatic amino acids, amino acids with polar and heterocyclic fragments, amides of acetyl
derivatives of amino acids. It is found that among the compounds studied with different side
radicals, the denser crystals do not always have a higher enthalpy of sublimation. The
presence of hydrogen bonds that increase cohesion in crystals of amino acids, peptides and
their derivatives increases the enthalpy of sublimation in the series: substituted and cyclic
dipeptides, amino acids with polar and heterocyclic fragments, amides of amino acids,
aliphatic amino acids and dipeptides. The results obtained can be used as basis for modeling
of complex high-temperature processes, including phase transformations of biologically active
substances.
The work was supported by the RFFI (grant №11-03-00013а).

MASS SPECTROMETRIC AND THERMODYNAMIC INVESTIGATION

OF L-ALANYL-L-TRYPTOPHAN
Tyunina V.V., Krasnov A.V., Girichev G.V.
e-mail: isuct-studlab@mail.ru
Enthalpy of sublimation is a one of the main thermodynamic parameters of organic
compounds. Dipeptides are the models of proteins and take part in many important
biochemical processes such as neuroregulation, enzyme catalysis, etc. These substances are
well-known to exist as zwitterions in the solid state and aqueous solution. Hydrogen bonds,
electrostatic and Van-der-Waals interactions are existed between these molecules. But
dipeptides have a molecular form in the gas phase. Moreover, these molecules have a low
symmetry and many rotational degrees of freedom. Thus, dipeptides have a large number of
different low energy conformers on the potential energy surface. Knowledge of sublimation
enthalpies of these compounds is necessary
14 to develop the synthesis of new medicine.
Usually peptides are decomposed in the
process of sublimation which makes some
ln (IT)
12 troubles in the experimental study. But in

this work the sublimation of L-alanyl-L-
tryptophan (Ala-Trp) was studied by
Knudsen’s effusion method with mass-
10 spectrometric vapor control. Mass spectra
observed have a typical fragmentation for
2.1 2.2 3 2.3 amino acids and dipeptides, e. g. elimination
10 /T, K-1 of side chain R and carboxylic group,
registration of ions: COOH+, NH2CHCO+,
NH2CH+. The location of charge on R (ions R+) is a typical for aromatic compounds. Enthalpy
of sublimation was found by thermodynamics law II. Kirchhoff’s equation was applied for
calculating standard enthalpy of sublimation (T=298 K, p=1atm). Sublimation enthalpy of
Ala-Trp was compared with enthalpies of other dipeptides. Thus, enthalpies are increased
with size of molecule: Gly-Ala<Ala-Ala<Ala-Val<Ala-Trp. Formation of cyclic dipeptide
from linear dipeptide is a typical process at heating. Quantum chemical calculations
(B3LYP/6-31G**) are confirmed these processes in a gas phase. Structures of linear and
cyclic molecule and frequencies of vibrations were calculated. Imaginary frequencies are
absent and value of Gibbs free energy is negative. Thus, these structures are the minima on the
potential energy surface. Lattice energy of Ala-Trp was estimated on the base of sublimation
enthalpy and energy of proton transfer between molecular and zwitterionic forms of dipeptide.
This study was supported by Russian Foundation for Basis Research (project № 12-03-
31758mol_а).
CRYSTAL STRUCTURE AND PROPERTIES OF OXIDES BaCo1-yYyO3-d

Urusova А.S., Aksenova T.V., Cherepanov V.А.
Department of Chemistry, Institute of Natural Sciences, Ural Federal University,

Ekaterinburg, e-mail: anastasiyapodzorova@yandex.ru
The crystal structure and physicochemical properties of B-site substituted complex

cobalt oxides BaCo1-yYyO3-d.(0≤y≤0.6) were studied in present work.
Powder samples of the cobaltites under investigation were synthesized by means of
conventional ceramic technique and glycerol-nitrate method. Final annealing was performed
at 1373 K in air with subsequent slow cooling to room temperature.
According to the XRD results BaCoO3-δ was shown to have hexagonal layered structure
(S. G. P63/mmc) whereas XRD patterns of single phase solid solutions BaCo1-yYyO3-δ
(0.1≤y≤0.4) were indexed using Pm3m space group. The refined cell parameters and volumes
of BaCo1-yYyO3-δ were shown to increase with yttrium content probably due to large ionic
radius of Y3+ comparing to that of Co3+. At large yttrium contents (0.4<y≤0.6) oxide mixture
of the nominal composition BaCo1-yYyO3-δ consists of three phases: BaCo0.6Y0.4O3-δ solid
solution, BaCoO3-δ and BaY2O4.
Oxygen nonstoichiometry of BaCo1-yYyO3-δ solid solutions with 0.1≤y≤0.4 was
measured by means of thermogravimetric technique within the temperature range 298–1273 K
in air. The absolute values of oxygen content were determined using two methods: iodometric
titration of the slowly cooled samples and reduction in the TGA cell by hydrogen.
Thermal expansion of BaCo1-yYyO3-δ (0.1≤y≤0.3) solid solutions was studied using
Netzsch DIL 402C dilatometer within the temperature range 298 – 1200 K in air. Monotonous
shape of ∆L/L=ƒ(T) curves proves absence of phase transitions within studied temperature
range in air.
The average TEC values for BaCo1-yYyO3-δ are given in Table 1. TEC values were
shown to decrease with increasing of yttrium content. This tendency can probably be
explained by the decrease of cobalt content that causes the decrease of the oxygen exchange
capacity of the samples.
Table 1. Thermal expansion coefficients for the BaCo1-yYyO3-δ
y ∆T, K КТР×106, K-1
0.0 24.14
0.1 298 – 1200 18.60
0.2 17.65
0.3 13.68
This work was supported by the Federal Agency of Education of the Russian Federation
and grant RFFI № 12-03-91663-ERA_а.
THERMODYNAMICS OF ESTERS OF HIGHER CARBOXYLIC ACIDS

Varushchenko R.M., Agafonova L.E., Druzhinina A.I.
e-mail: varusch@thermo.chem.msu.ru
Carboxylic esters of fatty acids are widely used in the world as biofuels and effective phase
change materials. A mixture of three esters of unsaturated fatty acids C18 - methyl oleate (MO),
methyl linoleate (ML) and methyl linolenate (MLn) are used as a motor and boiler fuel in the
European Union (EN14214/590 and EN14213 standards). The use of renewable biofuel is
environmentally preferable to usual fuel.
Literature data on the thermodynamic properties of the fatty acid esters are scarce: there are
data on enthalpies of formation, vapor pressures at temperatures of (390/429 - 440/480) K and
low pressures (0.015/0.139 - 0.26/2.0) kPa and the enthalpies of vaporization, found by
chromatography.
This work is devoted to further accumulation of data on key thermodynamic properties of
esters: determination of low-temperature heat capacities and characteristics of the phase
transitions crystal–liquid, extrapolation of vapor pressures to temperatures of triple points, Ttp,
and 298.15 K and the establishment of the thermodynamic functions S°m(T) and ∆T0 H m for
condensed and ideal gas states, including the functions of formation ΔfSmo(T), ΔfHmo(T) and
ΔfGmo(T) at T = 298.15 K.
The study of esters of fatty acids is a difficult task due to the low volatility, high boiling
points and thermal instability of the compounds. Therefore, studies were conducted using
experimental and computational methods, including the principle of additivity. Possibilities of the
methods were tested on the lower carboxylic acid esters C3-C5, more suitable for the experiment.
The heat capacities, characteristics of solid-phase transitions and melting of methyl stearate
(MS), MO, ML and MLn were measured by vacuum adiabatic calorimetry in the temperature
region (5/7-372) K. The saturated vapor pressures for ethyl propanoate (EPr) and methyl
butanoate (MBut) were determined by comparative ebulliometry in the «atmospheric» pressure
range of (4/11-101.7) kPa. Extending of the vapor pressures to region of triple points and T =
298.15 K was performed by simultaneous processing pT data and low-temperature heat
capacities, ΔСр,m= С°р,m(g) - Ср,m(liq):
ln ( p / p ) = A′ + B ′ / T + C ′ ln T + D ′ ⋅ T ,
( ∆C p ,m / 2 ) / R= (1/ 2 ) ⋅ C p0,m ( г ) − С p ,m ( ж)  / R= C ′ / 2 + D′ ⋅ T ,
Heat capacities of ideal gas of С°р,m(g) are calculated by the additive method using
literature data on the heat capacities of real gases (vapors) of methyl and ethyl acetate (Connett
J.E., Counsell J.F., Lee D.A., J. Chem. Thermodynamics. 1976. V. 8. p. 1199-1203). The vapor
pressures of the esters of fatty acid at T = 298.15 K are (1.20 - 2.15)•10-3 Pa, the error in
calculating is p (298.15) ≤ 10%.
The series of data on the thermodynamic properties of esters of higher and lower carboxylic
acids are received and discussed. As shown in the table, the values of S°m(g)(exp.)
Entropy (298 K); J/( K∙mol) EPr MBut
S°m(g)(exp.) 402.1 ± 2.0 399.5 ± 2.0
S°m(g)(addit.) 402.3 400.7
obtained by the third law of thermodynamics on the basis of experimental data for esters MBut
and EPr are consistent within the error limits with those found by the additive method,
S°m(g)(addit.). Coincidence of the considered values confirms reliability of the used calculation
procedures.
SOLID AND LIQUID STRUCTURE OF 2-(METHOXYCARBONYL)PYRROLIDINIUM

CHLORIDE: AN EDXD, DSC AND SIMULATION STUDY
Vecchio S.a Sferrazza A.a, Caminiti R.a, Gontrani L.b
a
b
CNR-ISM, Rome, Italy
In the present work, we discuss the structural and thermodynamical features of 2-
(methoxycarbonyl)pyrrolidinium chloride, the chiral ionic liquid (CIL) derived from L-proline
esters with the shortest alkyl chain. This compound belongs to a family of ionic liquids that
have recently shown very good capabilities in chiral discrimination studies [1], such as
separations and asymmetric syntheses. The physical state of the system depends on the
thermal history of the sample, and shows peculiar transitions between liquid, glass and crystal
forms. To our knowledge, this is the first structural study of this compound, and the first
structural determination of a glass obtained solidificating an ionic liquid. Energy-Dispersive
X-Ray patterns were recorded in glass and liquid phase and compared with theoretical curves
calculated from molecular dynamics trajectories [2].
The spatial arrangement of the ions giving origin to these patterns is discussed.
Its thermal behavior between room temperature and 250°C was studied using
thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques, operating
simultaneously at a heating rate of 2 K/min with nitrogen as purge gas. The occurrence of
melting, in a relatively small temperature range around 31-32°C, and the presence of other
thermal effects related to the structural changes observed by EDXD experiments are also
discussed.
References
[1] D.M. Kroupa, C.J. Brown, L.M. Heckman, T.A. Hopkins, J. Phys. Chem. B 2012, 116
(16), 4952–4958.
[2] L. Gontrani, E. Bodo, A. Triolo, F. Leonelli, P. D'Angelo, V. Migliorati, R. Caminiti, J.
Phys. Chem. B 2012, 116 (43), 13024–13032; M. Macchiagodena, L. Gontrani, F. Ramondo,
A. Triolo, R. Caminiti, J. Phys. Chem. 2011, 134, 114521-114535.
THERMODYNAMIC PROPERTIES MILSTONE THERMODYNAMICS

OF THE RENEWABLE FUELS AND HYDROGEN STORAGE
Verevkin S.P., Emel’yanenko V.N.
University of Rostock, Germany
e-mail: Sergey.verevkin@uni-rostock.de
Biofuels derived from biomass are a promising alternative energy source due to the
potential for such fuels to be carbon neutral. Efficient process design requires accurate
thermodynamic property information. We set an establishing benchmark thermodynamic
properties and prediction of feasibility for the renewable fuel processing and alternative to
conventional hydrogen storage technologies as a main goal of this project. The complex of
modern thermochemical and theoretical methods was designed, developed and established in
the Thermochemical lab at the University of Rostock. The procedure included extended
experiments, critical evaluation of available data, and prediction of the missing
thermodynamic properties in order to provide the best possible property values as the
milestones for the assessment of the feasibility of processes intended for valorisation of the
natural products and the optimal hydrogen storage using favourable chemical reactions. Focus
of our studies has been on thermodynamic analysis of the following processes: production of
dimethylfuran for liquid fuels from biomass, utilization of building block chemicals produced
from sugars and lignocellulosic biomass via biological or chemical conversions, and
utilization, as well as we discuss a thermodynamic analysis and selection of liquid organic
heteroaromatics for hydrogen storage as an auspicious alternative to conventional
technologies.
THERMAL PROPERTIES OF VOLATILE CESIUM-CONTANING COMPLEXES

Vikulova E.S., Zherikova K.V., Zelenina L.N., Sysoev S.V., Semyannikov P.P.,
Trubin S.V., Morozova N.B., Igumenov I.K.
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk
e-mail: lazorevka@mail.ru
Doping film material by cesium compounds provides better electronic and electrical
characteristics of the material [1]. A convenient technique for such doped film formation is
Metal Organic Chemical Vapor Deposition (MOCVD). The aim of the present work is
synthesis of Cs-containing volatile precursors and investigation of their thermodynamic
characteristics to optimize film growth conditions.
Bimetallic cesium-containing compounds Cs[MLn] were found to transfer in the gas
phase within 423-523K [2]. Among them Cs[Y(hfac)4] [2a] (1, hfac = CF3COCHCOCF3)
demonstrate sufficient volatility and stability for use in MOCVD process. Nevertheless, high
fluorine content causes formation of corrosive products at thermal decomposition and should
be reduced. Thus, we synthesized the analogous, but less-fluorinated complexes using ptac
(2, tBuCOCHCOCF3), tfac (3, CH3COCHCOCF3) and btfac (4, PhCOCHCOCF3) as ligands.
The influence of the structure of MI[YL4] complexes (MI = Na 5 [3], K 6, Rb 7, Cs, L = ptac)
on their thermal properties was studied.
Thermal behavior of the complexes in the solid state was investigated by means of
thermogravimetric analysis. Standard enthalpies and temperatures of phase transitions of the
complexes obtained were measured by means of differential scanning calorimetry. The
temperature dependences of saturated vapour pressure were measured by flow (transmission)
method (F) or Knudsen’s effusion method with mass spectrometric registration of the vapour
composition (K). Thermodynamic values for gas phase transfer calculated from the data
obtained are presented in Table 1. The row of volatility was found to be 4 << 3< 1<2 ≈ 6<< 5
(T = 463K).
Table 1. Thermodynamic parameters of vaporization processes for complexes 1-6, normalized
to the mean temperature (T°) in the examined interval (∆T).
lnPatm = A-B/T -ΔHT°, ΔS°T°,
Complex Method ΔT, K Process N*
A B kJ/mol J/mol·K
1 F 423 – 483 sub. 12 30.67 18701.7 155.5±3.2 255±7
F 433 – 483 sub. 11 28.59 17374.7 144.5±1.7 238±4
2
K 375 – 437 sub. 11 31.35 18417.6 153±2 261±4
3 F 463 – 478 sub. 7 26.42 17470.9 145±5 219 ±11
K 451-484 sub. 6 34.10 23067.0 192±3 283.5±6.1
4
K 484-510 evap. 4 27.21 19728.0 164.0±6.5 226±13
5** F 418-503 sub. 18 26.30 15560.0 130±1 219±2
6 F 425-465 sub. 10 31.82 18799.5 156±4 265±8
*N – number of points, ** co processing with data [3]
References
1. (a) B. Thomas, S. Benoy, K. K. Radha. Sensors and Actuators B, 133, 404 (2008) (b)
A. M. E. Raj, M. Jayachandran, C. Sanjeeviraja. CIRP J. Manufact. Sci. Tech., 2, 92 (2010).
2. (a) M. Z. Gurevich, B. D. Stepin, V. V. Zelentcov. Zh. Neorg. Khim., 15, 890 (1970) (in
Russian) (b) S. J. Lippard. J. Am. Chem. Soc., 88, 4800 (1966) (c) M. Z. Gurevich, B. D.
Stepin, V. V. Zelentcov. Zh. Neorg. Khim., 15, 1996 (1970) (in Russian).
3. S. V. Sysoev, A. N. Golubenko, L. D. Nikulina et al. Thermocim. Acta, 225, 137 (1993)
The work was supported by the RFBR Grant № 12-03-31277.
THERMODYNAMICS OF THE REACTIONS FOR THE SYNTHESIS

OF LEVOGLUCOSAN FROM CARBOHYDRATES
Voitkevich O.V., Kabo G.J., Blokhin A.V., Kohut S.V., Edimecheva I.P.
Belarusian State University, Minsk, Belarus
e-mail: voi-olga@mail.ru
Levoglucosan is a raw material for biodegradable polymers, antibiotics and other drugs.
Levoglucosan synthesis using the carbohydrate components of plant biomass is possible in the
processes of catalytic thermal processing.
The comprehensive study of the physicochemical properties of levoglucosan was carried
out in this work. Chromatographic analysis was performed on a chromatograph-mass
spectrometer Shimizu GCMS-QP2010Plus. The purity of the sublimed sample was close to
100 mol. % (no peaks of impurities were found in the chromatogram). The heat capacity of
levoglucosan in the temperature range of 5 to 370 K was measured in a low-temperature
adiabatic calorimeter. The heat of combustion was determined in an isoperibolic bomb
combustion calorimeter. TG-DSC analysis of the sample was carried out in a nitrogen
atmosphere with a Netzsch STA 449 Jupiter instrument. According to DSC results
levoglucosan forms plastic crystal in the range of Ttr = 391 K to Tfus = 455.5 K. The
thermodynamic properties of crystalline levoglucosan were calculated from the experimental
data. The standard entropy in the gas state So(364.25 K) = 452.3 J·mol-1·K-1 was calculated
using the vapor pressure of levoglucosan determined by Oja [1].
Geometric parameters and frequencies of the normal vibrations of a levoglucosan
molecule were obtained from quantum chemical calculations. The standard entropy of the
substance in the ideal gas state calculated by statistical thermodynamics was in a good
agreement with the experimental value. The group of the reactions that can be used to
calculate the enthalpy of formation for levoglucosan in the ideal gas state was justified. The
proposed procedure for ∆fHom calculation was found to have error comparable to the
experimental one.
The analysis of the thermodynamic parameters of the levoglucosan synthesis from
microcrystalline cellulose, starch and glucose based on previous studies of the thermodynamic
properties and the DSC-TG results for these substances in the range (300 – 900) K [2, 3] was
performed. Despite significantly different behavior the onset of intensive thermal degradation
was observed at 570 – 650 K for all these compounds.
Based on the DSC-TG and thermodynamic analysis we found that the best raw material
for the levoglucosan synthesis is microcrystalline cellulose. The equilibrium constant of the
reaction
microcrystalline cellulose (cr) = levoglucosan (g)
(C6H10O5)n(cr) n C6H10O5(g)
was calculated. The equilibrium pressure of levoglucosan in this reaction was found to be
3.4 kPa at 650 K.
References
[1] V. Oja, E. M. Suuberg, J. Chem. Eng. Data 44 (2000) 26 – 29.
[2] A.V. Blokhin, O.V. Voitkevich, G.J. Kabo, Y.U. Paulechka, M.V. Shishonok, A.G. Kabo,
V.V. Simirsky, J. Chem. Eng. Data 56 (2011) 3523 – 3531.
[3] G.J. Kabo, O.V. Voitkevich, A.V. Blokhin, S.V. Kohut, E.N. Stepurko, Y.U. Paulechka,
J. Chem. Thermodynamics 59 (2013) 87 – 93.
SOLID SOLUTIONS Sr1-xSmxCoO3-d: SYNTHESIS

AND PHYSICOCHEMICAL PROPERTIES
Volkova N.E., Gavrilova L.Ya., Cherepanov V.A.
Ural Federal University, Institute of Natural Sciences, Yekaterinburg, Russia
e-mail: vnadezhdochka@yandex.ru
Polycrystalline samples of Sr1-xSmxCoO3-d were synthesized using a conventional
ceramic route and glycerin nitrate technique. In both methods rare earth oxide Sm2O3 (with
99.99% purity), BaCO3 and Co3O4 (both of “pure for analysis” grade) and metallic cobalt
were used as starting materials. Metallic cobalt was obtained by reducing of cobalt oxide in
the hydrogen flow at 500–600°С.
Phase identification was performed by x-ray diffraction (XRD) analysis using a DRON-
6.0 diffractometer with CuKα radiation. Unit cell parameters were refined using the Fullprof
package.
It was found that single-phase Sr1-xSmxCoO3-d samples were obtained within the range
0.05≤х≤0.50. It should be noted that the Sr0.5Sm0.5CoO3-δ sample prepared by ceramic
technique after annealing during 240 h besides the main phase contained small amount of
impurity phases, whereas the sample obtained by glycerin-nitrate technique was single phase.
XRD patterns of the single phase samples were refined by Rietveld method within the
tetragonal structure (I4/mmm sp. gr.). Gradual substitution of strontium by samarium leads to
the decrease of the unit cell parameters and unit cell volume that can be explained by the size
factor.
All samples with x>0.5 were multiphase and consisted of saturated solid solution having
an approximate composition Sr0.5Sm0.5CoO3-δ and SmCoO3-δ.
The changes of oxygen content in the Sr1-xSmxCoO3-δ solid solutions were measured by
thermogravimetric analysis within the temperature range 25≤T,°С≤1100 in air. The absolute
oxygen content in the samples was determined using a direct reduction of the samples in the
TG cell by hydrogen and chromatometric titration. An introduction of samarium into the
strontium cobaltate and strontium ferrite increases the oxygen content.
Thermal expansion of Sr1-xSmxCoO3-d samples was studied within the temperature range
25-1100°С in air. The bend on the ∆L/L=ƒ(T) curve for the Sr0.9Sm0.1CoO3-δ sample indicates
the presence of phase transition at temperature ∼ 335°С. The decrease of average values of
TEC with the increase of Sm content is probably related to the reduction of the unit cell
volume and diminishing of oxygen exchange.
Chemical stability of the Sr1-xSmxCoO3-d (0.1, 0.4) relative to the electrolyte materials
Zr0.85Y0.15O2 and Ce0.8Sm0.2O2 has been checked within the temperature range 900-1100°С,
by means of annealing of the corresponding mixtures with 1:1 weight ratio during 24 h in air
with following XRD analysis. It was found that all samples interacts with the Zr0.85Y0.15O2
even at 900°С and cannot be recommended as electrode materials for this electrolyte. In
contrast Sr1-xSmxCoO3-d solid solutions were chemically stable in contact with Ce0.8Sm0.2O2 at
T≤1100°C.
This work was financially supported in parts by the Ministry of Education and Science
of Russian Federation within the Federal Target Program “The scientific and scientific-
education personnel of Innovative Russia for 2009–2013.”
THERMODYNAMIC STABILITY COMPLEXING CONSTANTS

OF IIIA-SABGROUP ELEMENTS WITH IMINODISUCCINIC ACID
Yakovlev A.A., Tolkacheva L.N., Nikolskiy V.M.
Tver State University, Tver, Russia
e-mail: innovation_support@tversu
The iminodisuccinic acid (IDS, L) is the novel generation of chelators, which has the
properties corresponding to the modern requirements of the environmental situation. Such
forward-ligand requires a comprehensive study.
pH-potentiometric research of systems IDS - M3+ - water at constant temperature of 298
K and several ionic strengths were made. The data obtained were processed using computer
software system AUTOEQUIL. At high pH values the degree of hydrolysis complexonates
increases. This leads to complete decomposition complexonates, accompanied by the release
of the solid phase. The calculation was performed only for those values of pH at which the
condition of the homogeneous solution is satisfied.
The formation of protonated, medium and hydroxocomplexes were identified. The
concentration and thermodynamic stability constants of these complexes were calculated. The
obtained values are presented in the table. Thermodynamic complexing constants have been
calculated by extrapolation of data, obtained at the specified ionic strength to null ionic
strength according to the equation with one individual parameter:
∆Z 2 Aγ I 1 / 2
lg β c − = lg β 0 + bI
1 + 1.16 I 1 / 2
I
Complex
0,8 0,6 0,4 0,1 0
Al3+ + L4‾ AlL‾ 12.73 ±0.06 12.84 ±0.07 13.01 ±0.06 14.00 ±0.03 16.48 ±0.07
AlL‾ + H+ AlHL 4.13 ± 0.09 4.10 ± 0.09 3.93 ± 0.08 3.96 ± 0.04 4.10 ± 0.05
AlL‾ + OH‾ AlOHL2‾ 7.40 ± 0.06 7.36 ± 0.06 7.28 ± 0.06 7.20 ± 0.03 7.43 ± 0.06
Ga3+ + L4‾ GaL‾ 15.58 ±0.06 15.81 ±0.08 15.60 ±0.05 16.67 ±0.06 19.03 ±0.15
GaL‾ + H+ GaHL 3.36 ± 0.07 3.35 ± 0.10 3.31 ± 0.06 3.32 ± 0.10 3.55 ± 0.07
GaL‾ + OH‾ GaOHL2‾ 8.86 ± 0.05 8.82 ± 0.07 8.81 ± 0.04 8.70 ± 0.05 9.15 ± 0.06
In3+ + L4‾ InL‾ 15.27 ±0.07 15.32 ±0.08 15.43 ±0.05 16.32 ±0.04 18.77 ±0.04
InL‾ + H+ InHL 3.80 ± 0.09 3.74 ± 0.09 3.71 ± 0.06 3.72 ± 0.06 3.91 ± 0.06
InHL + H+ InH2L+ 2.33 ± 0.2 2.31 ± 0.2 2.25 ± 0.1 2.20 ± 0.2 2.19 ± 0.2
InL‾ + OH‾ InOHL2‾ 8.32 ± 0.08 8.24 ± 0.08 8.07 ± 0.05 7.91 ± 0.04 8.05 ± 0.04
Stability of the complexes increases with the rise of the covalent component in the
M3+─ligand bond. This well explains the increase in stability of the complexes of aluminum
to indium and gallium. Approximately equal lgβ values for the complexes Ga3+ and In3+ with
IDS can be explained on the basis of structural correspondence of the central ion and the
ligand. For example, for a relatively small gallium fluoride complexes are especially strong,
and for larger indium and thallium - chloride and bromide complexes are especially strong.
Probably, gallium ion that is small enough can form with small-sized ligand IDS more stable
complexes than bigger indium ion.
The work was supported by the Federal Program "Scientific and scientific-pedagogical
personnel of innovative Russia in 2009 - 2013 years." (Project № 14.B37.21.0653) and the
program "User Youth Science Innovation Competition – UMNIK-2012".
THERMODYNAMIC PROPERTIES OF CHALCOGERMANATES

AND CHALCOSTANNATES OF SILVER
Yusibov Y.A., Alaverdiev I.J, Alieva Z.M., *Bagheri S.M., *Babanly M.B.
Ganja State University, Ganja
*Baku State University, Baku
Using of solid superionic conductors as a solid state electrolyte significantly extending
the measurements capacity of the EMF methods that one of the most widely used
experimental electrochemical methods in the thermodynamic studies. This is due to primarily
to the fact that the conductivity in solid electrolytes is carried by ions of the same element and
a well-defined charge that makes it possible to directly measure the activity of the
corresponding component in multicomponent alloys, regardless of whether it is the least noble
metal system or not.
In this work, we report the results of experimental investigations of solid state
equilibriums and thermodynamic properties of the system Ag-AIV-X (AIV-Ge, Sn; X-S, Se) by
means of EMF measurements with aid of superionic conductors Ag4RbI5. For the EMF
measurements we constructed the following concentration chains:
(-) Ag (s) / Ag4RbI5(s) / (Ag in alloys) (s) (+)
EMF was measured by the compensation method in the temperature range of 300–430 K
(for sulfur containing systems 300-380 К). Preliminary synthesized alloys from different
phase areas were exploited as right (positive) electrodes.
From the EMF measurements, the partial molar functions of silver in alloys were
calculated.
Based on constructed solid state phase equilibria diagrams potential-forming reactions
for ternary compounds are found, which standard thermodynamic functions of formation and
standard entropies were calculated (see Table).
Corresponding thermodynamic data for germanium and tin chalcogenides have been
used in the calculations.
Table
Standard integral thermodynamic functions of chalcogermanates and chalcostannates of silver
kJ∙mol-1 J∙mol-1∙К-1
Ag2GeS3 206±2,1 198±2,2 239,1±8,8
Ag4GeS4 254±2,1 235±2,4 393,2±14,1
Ag8GeS6 345±2,2 310±2,6 680,4±23,1
Ag2GeSe3 145±2,1 139±2,2 262,2±10,4
Ag8GeSe6 288±2,3 255±2,8 734,6±30,4
Ag2Sn2S5 358,8±2,3 339,5±12,6 397,9±16,3
Ag2SnS3 213,3±1,6 202,7±8,8 260,7±16,8
Ag8SnS6 351,7±2,6 328,9±18,0 652,9±16,3
Ag8SnS5 355±3,2 330±3,8 628,43±23,6
AgSnSe2 146,4±0,5 148±3 162±7,2
Ag8SnSe6 350,3±1,8 320,4±8,1 736,6±23,8
THE EFFECT OF THE ALKYL CHAIN LENGTH ON THE ENTHALPY

OF VAPORIZATION FOR MOLECULAR AND IONIC COMPOUNDS
Zaitsau Dz.H.a, Verevkin S.P.a, Yermalayeu A.V.a, Pimerzin A.A.b
a
Universität Rostock, Rostock, Germany
e-mail: zaitsaudz@gmail.com
b
Samara State Technical University, Chemical Technology Department,
Samara, Russia
Group-additivity (GA) methods are well recognized approaches to prove consistency of
the experimental data on thermochemical properties of molecular compounds. One of the best
indicators of possible experimental errors is a large deviation between experimental values
and those calculated by GA – especially if other, closely related compounds show no such
discrepancy. The GA methods have been developed for the moderate size of molecules. Are
these methods also valid for very large molecules? The simplest manifestation of the GA is
the alkyl chain dependence of any thermodynamic property. It was well established that e.g.
vaporization enthalpies of homologous series of molecular compounds like n-alkanes, n-
alcohols, n-alkyl-nitriles etc. show the linear dependence with the growing chain length up to
10 C-atoms in the chain. In contrast to the molecular compounds, the ionic compounds
possess also large amount of the Coulomb interactions. Is there any impact of these specific
interactions on to the chain length dependence in ionic liquids?
In order to answer this question we have developed a new very sensitive method for
measuring vaporization enthalpy of extremely low volatile compounds based on method
combination of Langmuir type of vaporization from the open surface and the the Quartz
Crystal Microbalance as a sensor. Using this technique we measured vaporization enthalpies
for different homologous series of ILs with long alkyl chain on the cation. The linear
dependence of the enthalpy of vaporization on the alkyl chain length was obtained for series
of 1-alkyl-3-methyl imidazolium based ionic liquids with NTf2, PF6, BF4 anions, as well as for
N-alkyl pyridinium (NTf2), N-methyl-N-alkyl pyrrolidinium (NTf2) ionic liquids.
Surprisingly, for the imidazolium based ILs with symmetrical alkyl chains in 1 and 3 position
(1,3-dialkyl imidazolium NTf2) – the enthalpy of vaporization significantly deviates from the
GA rules.
Looking for explanation of this finding we have studied the long chained methyl esters
of the saturated fatty acids (C10 to C20) as well as triglycerides with the long alkyl chains (till
C16). Also in this case the significant deviations from the linear behavior have been observed
for the compounds with the chain length larger than C16. Some possible reasons for deviation
from the GA rules will be discussed.
THERMODYNAMIC STUDY OF DESORPTION PROCESSES

OF GUESTS MOLECULES FROM METAL-ORGANIC POLYMERS
AND MACROCYCLIC COMPOUNDS
Zelenina L.N., Chusova T.P., Sapchenko S.A., Fedin V.P., Bakovets V.V.
Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk
e-mail: zelenina@niic.nsc.ru
Metal-organic polymers (also referred as metal-organic frameworks or MOFs) and
macrocyclic compounds (cucurbit[n]urils) have attracted considerable attention in recent
years. These porous substances can be used as nanoreactors for synthesis of nanoparticles and
photochemical transformations within the framework’s cavities and channels. By controlling
the size and shape of nanocavities, it is possible to get the unique high-ordered ensembles of
nanoparticles, and also to achieve a selective course of reactions with the formation of
products which are difficult or impossible to obtain with the methods of solution chemistry.
Thermodynamic properties of these compounds are weakly studied. Meanwhile the
knowledge of their thermal stability and the nature of host-guest interactions play a crucial
role in the future use of these substances as functional materials. This information can be
obtained by investigating desorption processes of guests molecules from these compounds.
The synthesis and analysis of Zn(II)-containing MOF [Zn4(dmf)(ur)2(ndc)4] (ndc2– =
2,6-naphtalenedicarboxylate, ur = urotropin, dmf = N,N'-dimethylformamide) involving
benzene or dmf or ferrocene as a guest were described in our previous paper [1].
The synthesis of cucurbit[n]urils (CB[n], n = 6, 8) was realized as described in [2]. The
samples obtained were characterized by IR spectroscopy and elemental analysis on C, H, and
N performed on a Euro EA 3000 CHN Elemental Analyzer. According to the analyses results
CB[6] and CB[8] samples corresponded to C6nH6nN4nO2n*xH2O (n = 6 or 8, x = 3-8)
composition.
The temperature dependences of saturated and unsaturated vapours of quests were
measured by static method, using glass membrane-gauge manometers. The pressure and
temperature measurement errors were less than 40 Pa and 0.5 K accordingly [3].
As a result of this study thermal stability ranges of investigated compounds were
established, temperature dependences of pressure for vaporization processes were obtained,
enthalpies and entropies of desorption were determined and Gibbs energy of bonding guest
with host was calculated.
On the base of this information, conclusions about the nature of the interactions between
host and guest molecules were made.
References
1. Sapchenko S.A., Samsonenko D.G., Dybtsev D., Melgunov M.S., Fedin V.P. Dalton
Trans. 2011, 40: 2196-2203.
2. Day A.I., Arnold A.P., Blanch R.J., Snushall B., J. Org. Chem. 2002, 66: 8094-
8100.
3. Zelenina, L.N., Chusova, T.P., Vasilyeva I.G. J. Chem. Thermodyn. 2013, 57: 101-
107.
This work was financially supported by the Russian Foundation for Basic Research
(project № 11-03-00112-a and № 11-03-00219-a).
DETERMINATION OF THERMODYNAMIC CHARACTERISTICS

OF ETHERS OF GLYCEROL AND ALCOHOLS C1-C5
Zhabina A.A., Krasnykh E.L.
e-mail: aazhab@gmail.com
The methods of synthesis of glycerol ethers based on the glycerol and linear and
branched out alcohols C1-C5 were developed, the optimal conditions of reaction and the
catalyst were selected. Mono-, di- and triethers were synthesized in this work. The structure
of compounds was proved with using of mass-spectrometer analysis.
Kovac’s indexes were determined for identification of all derived substances. Analysis
compounds and estimation of holding time were realized on program apparatus complex
based on gas chromatograph “Cristal-2000M” with FID. Experimental
values of Kovacs indexes were determined from 5-7 measures, the confidence interval of
accounts was no more 1,0. Kovac’s indexes were calculated at 403 К (130 °С) – I130 based
on experimental values.
The temperature dependence of Kovac’s indexes is linear for all taken ethers it means,
that they can be used for the identification of these compounds at any temperatures.
The partition constants, Henry’s constants, the entropy and the enthalpy of sorption for
various compounds were calculated in this work for all derived substances on
the non-polar liquid stationary phase OV-101.
The vapor pressure and the enthalpy of vaporization were measured for monoethers of
glycerol and linear alcohols C2-C4 by used the method of transpiration.
The comparison of the existent prediction methods of the enthalpy vaporization for
ethers was proposed and the recommendations for their using were given.
VOLATILE SCANDIUM BETA-DIKETONATE DERIVATIVES – VIABLE

PRECURSORS FOR OBTAINING OXIDE COATINGS BY CVD
Zherikova K.V., Zelenina L. N., Chusova T.P.
Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk
e-mail: ksenia@niic.nsc.ru
Chemical Vapor Deposition (CVD) is widely applied in modern industry for fabricating
various metallic, oxide and composite layers with assigned structural and functional
properties. Being multiparameter complicated process, one of the important factors of
successful realizing CVD technology is the usage of suitable precursors satisfying the
requirements on volatility and thermal stability. Exactly these physico-chemical properties are
important features of the metal beta-diketonates making them very popular in the CVD
process and leading to more research in synthesis and thermal behaviour. The last one
includes vaporization and melting process investigation, thermodynamic characteristics’ and
saturated vapor pressure definition, thermal stability study. This set of the fundamental
researches serves a basis for purposeful choice of the precursors and optimal coating
deposition condition. This approach will be demonstrated by an example of developing
technology of oxide film obtainment by CVD with the usage of scandium beta-diketonates.
A series of scandium complexes with acetylacetone Sc(acac)3, 2,2,6,6-tetramethyl-3,5-
heptanedione Sc(thd)3, 2,2,6,6–tetramethyl-4-fluoro-3,5-heptanedione Sc(tfhd)3,
pivaloyltrifluoroacetone Sc(ptac)3, trifluoroacetylacetone Sc(tfac)3, and
hexafluoroacetylacetone Sc(hfac)3 was synthesized for performing the thermodynamic
investigation. The compounds obtained and purified by vacuum sublimation were identified
by elemental analysis, IR and NMR spectroscopy, mass spectrometry, and X-ray structural
diffraction analysis.
Thermal behaviour of the complexes in the condensed phase was investigated by the
method of difference-scanning calorimetry (DSC) in vacuum (the errors in the heat effect
measurements were less than 1.5%). As a result the thermodynamic characteristics (m.p.,
enthalpy and entropy) of the melting processes were determined.
The temperature dependencies of saturated and unsaturated vapour pressures of the
chelates were studied by static method with membrane-gauge manometer. The pressure and
temperature measurement errors were less than 0.3 Torr and 0.5 K respectively. The average
molar gas weight calculated from the experimental data on unsaturated vapours using ideal
gas law was defined; in our case it was close to the molecular weight of monomers.
Temperature of complexes’ decomposition beginning was defined as the temperature above
that pressure changes became irreversible. The information about melting and decomposition
processes were taken into account at measuring saturated vapour pressure of complexes. The
row of volatility (at p=10-2 Torr Sc(hfac)3 > Sc(ptac)3 > Sc(tfac)3 > Sc(dpm)3 ≥ Sc(tfhd)3 >
Sc(acac)3) and thermodynamic characteristics (enthalpy and entropy) of vaporization
processes were determined from the data obtained.
Based on research carried out the precursor (Sc(thd)3) and deposition conditions were
chosen for performing experiments to obtain oxide films of Sc2O3.
ТЕРМОДИНАМИЧЕСКИЕ СВОЙСТВА АЛКИЛБЕНЗОХИНОНОВ

Емельяненко В.Н.1, Веревкин С.П.2, Гарист И.В.1, Роганов Г.Н.1, Пимерзин А.А.3
1
Могилевский государственный университет продовольствия,
Могилев, Республика Беларусь
e-mail : vladchimic@tut.by
2
Университет города Ростока, Германия
3
Самарский государственный технический университет, Самара, Россия
пара-Бензохинон и его алкильные производные были и продолжают оставаться
интересными объектами как для химической термодинамики, так и для химии новых
материалов и биохимии. Тем не менее, существующая в настоящее время совокупность
экспериментальных данных по термодинамическим свойствам хинонов является
неполной и ненадежной.
В представленной работе с использованием метода калориметрии сгорания были
определены стандартные молярные энтальпии образования ∆fH0m(298.15 К)
кристаллических диметил-, моно-трет-бутил и ди-трет-бутилбензохинонов-1,4 с
различными положениями заместителей. Энтальпии сублимации и испарения
указанных соединений найдены из температурных зависимостей давления пара,
определенных методом переноса.
Квантово-химические расчеты энергетических характеристик алкил-
бензохинонов выполнены с использованием композитных G3MP2 и G4 методов.
Величины энтальпий образования соединений в состоянии идеального газа оценены с
использованием процедур «из реакций атомизации» и «из изодесмических реакций».
Для диалкил-производных оценен энергетический эффект взаимодействия алкильных
заместителей. Получено хорошее согласие экспериментальных и расчетных данных.
На основании имеющихся литературных и полученных нами данных
сформирована надежная совокупность величин энтальпий образования и сублимации
производных бензохинона-1,4.
По экспериментальным и расчетным молекулярным и спектральным данным
определены величины термодинамических функций ряда алкильных производных
пара-бензохинона для веществ в состоянии идеального газа, и выполнена
температурная экстраполяция величин ∆ f H mo и ∆ f Gmo в интервале 298.15-1000 К.
ТЕРМОДИНАМИЧЕСКИЕ СВОЙСТВА Ba2Cu3O6-x.

ИСТОРИЯ ОШИБОК И УСПЕХОВ
Ковба М.Л.
Московский государственный университет имени М.В. Ломоносова, Москва
e-mail: max@td.chem.msu.ru
Соединение Ba2Cu3O6-x, впервые надёжно описанное в работе Томпсона, является
типичным примером низкотемпературной фазы существующей в тугоплавкой оксидной
системе. Этим объясняется большое количество ошибок допущенных при определении
её состава, изучении фазовых равновесий в данной области диаграммы и измерении её
термодинамических свойств. Основные трудности связаны в первую очередь с
синтезом однофазных, хорошо закристаллизованных образцов Ba2Cu3O6-x (без
рентгеноаморфных примесей) с фиксированной кислородной стехиометрией. В
результате в литературе неоднократно сообщалось об обнаружении фаз иного
катионного состава, существующих как альтернативно фазе 2:3 так и одновременно с
ней. В данной ситуации основным преимуществом метода ЭДС является возможность
ограничиться синтезом гетерогенных смесей равновесно сосуществующих фаз. Так для
определения термодинамических свойств Ba2Cu3O6-x нами были измерены
температурные зависимости ЭДС ячеек:
(–) O2, Pt │ Ba2Cu3O6-x, CuO, BaF2 │ BaF2 │ CaO,CaF2 │ Pt, O2 (+) (I),
(–) O2, Pt │ Ba2Cu3O6-x, BaCuO2, BaF2 │ BaF2 │ CaO,CaF2 │ Pt, O2 (+) (II).
Электроды ячеек были синтезированы из BaCO3 и CuO, взятых в соотношении
2:4 и 3:4, через стадии разложения в вакууме, получения соответствующих закисных
фаз (900оС) и их окисления в токе очищенного кислорода (600оС).
Очевидно, что при температуре выше температуры распада Ba2Cu3O6-x электроды
ячеек (I) и (II) имеют одинаковый состав, а измеряемые величины ЭДС совпадают с
данными, полученными для ячейки (III).
(–) O2, Pt │ BaCuO2, CuO, BaF2 │ BaF2 │ CaO,CaF2 │ Pt, O2 (+) (III)
Попытки расширить интервал измерений ячейки (III) в область низких температур
не достигли успеха. Разница измеряемых значений ЭДС превышает 10-15 мВ, при
статистическом разбросе ±1,5 мВ. При этом количество Ba2Cu3O6-x, образовавшееся на
поверхности электрода оказалось ниже чувствительности метода РФА, что и привело к
ошибочной интерпретации полученных в 1990 году данных. По данным
термогравиметрии Ba2Cu3O6-x сохраняет состав близкий к стехиометрическому (х≤0,05)
вплоть до температур ≈ 1000К. Это позволяет аппроксимировать низкотемпературные
данные для ячейки (I) линейной зависимостью E = a + b T, и рассчитать значения
термодинамических функций реакции образования Ba2Cu3O5,96 из простых оксидов и
кислорода.
ΔfGoок(Ba2Cu3O5,96) (±0,24) = – (168,1±0,9) – (9,2 ±0,9) 10-2Т (кДж/моль).
Аппроксимация всего массива данных полиномом E = a + bT + cTlnT \приводит к
значениям энергии Гиббса образования Ba2Cu3O6-x, хорошо согласующимся с
термодинамическими моделями, предложенными в работах Г.Ф.Воронина,
С.А.Дегтерёва и В.А.Лысенко.
ЭНТАЛЬПИИ ОБРАЗОВАНИЯ ГЕТЕРОЦИКЛИЧЕСКИХ РАДИКАЛОВ

Коробейников П.А, Чернова Е.М., Туровцев В.В., Орлов Ю.Д.
Тверской государственный университет, Тверь
Понимание механизмов превращений кислородсодержащих органических
соединений циклического строения имеет большое практическое значение.
Существенная часть этих реакций идет через стадию образования радикалов (R•).
Управление подобными процессами в экологии, биохимии и химической технологии
требует детального изучения строения и физико-химических свойств R•.
Информация о термодинамических свойствах кислородсодержащих органических
радикалов циклического строения крайне скудна и носит предварительный характер
[1,2]; среди них только семь кислородсодержащих гетероциклических радикалов
охарактеризованы величинами стандартных энтальпий образования (∆fH0(R•)).
Расчетные оценки ∆fH0 таких соединений на основании феноменологических методов
затруднены неопределенностью Ес - энергий циклического напряжения (энергий
напряжения циклов) [1], а квантовые методы весьма ресурсоемки и пока эффективны
лишь для простейших R• с числом атомов менее 5 – 7 [3].
В представленной работе развит теоретический подход по определению новых
значений ∆fH0(R•), исходя из количественных корреляций «строение-энтальпия
образования» [1] и энтальпии разрыва связи (D), применительно к
кислородсодержащим гетероциклическим соединениям. Новые значения ∆fH0(R•) были
вычислены по известному термохимическому соотношению (1)
D(R-Н) = ∆fН°(R•) + ∆fН°(Н) - ∆fН°(RН), (1)
•
где ∆fН°(R ), ∆fН°(Н), и ∆fН°(RН) – стандартные энтальпии образования соответственно
свободного радикала, атома водорода и исходной молекулы.
В результате был сформирован фонд данных по ∆fН° кислородсодержащих
гетероциклических радикалов, содержащий 61 значение. Установленные в рамках
аддитивно-группового подхода взаимосвязи между строением и энтальпийными
характеристиками R• являются подтверждением надежности рекомендованных
ΔfH°(R•). Установленные параметры модели (в том числе Ес) позволяют рассчитывать
ΔfH° новых соединений, пока не охарактеризованных этими величинами.
Представленные результаты в совокупности заметно углубляют количественную и
методологическую базу термохимии органических свободных радикалов.
[1] Орлов Ю.Д., Лебедев Ю.А., Сайфуллин И.Ш. Термохимия органических свободных
радикалов. М.: Наука. 2001, -304 с.
[2] J.-R. Luo, Comprehensive handbook of chemical bond energies. L., N.-Y.: CRC Press,
Boca Raton, 2007
[3] K. Raghavachari, L.A. Curtiss, in Theory and Applications of Computational Chemistry.
The First Forty Years. / C.E. Dykstra, G. Frenking, K.S. Kim and G.E. Scuseria (Ed.).
Amsterdam, Boston: Elsevier, 2005, p. 785.
ТЕРМОДИНАМИКА СТРУКТУРНЫХ ЕДИНИЦ СИЛИКАТНОГО РАСПЛАВА

Королева1 О.Н., Тупицын2 А.А., Бычинский2 В А.
1
Институт минералогии УрО РАН, Миасс
e-mail: koroleva@mineralogy.ru
2
Институт геохимии им. А.П. Виноградова СО РАН, Иркутск
e-mail: val@igc.irk.ru
Структурными единицами силикатных расплавов являются кремнекислородные
тетраэдры, состоящие из центрального атома кремния и четырех атомов кислорода,
объединяющиеся в анионные группировки. Экспериментальная информация о
содержании структурных единиц стекол и расплавов, получаемая методами
колебательной спектроскопии и ЯМР, представляет собой распределение структурных
единиц Qn – кремнекислородных тетраэдров с различным числом мостиковых атомов
кислорода n, в зависимости от состава и температуры. Для сопоставления результатов
спектроскопических исследований с данными термодинамического моделирования
предполагаем, что свободные энергии образования (ΔGf˚) кристаллических силикатов
могут использоваться для оценки термодинамических характеристик структурных
единиц Qn. Поэтому в список вероятных компонентов моделей литиево- и
натриевосиликатного расплавов включены силикаты, стехиометрически
соответствующие структурным единицам Q . Исходя из предположения о
n
квазикристалличности, термодинамические функции кремнекислородных тетраэдров

Q0-Q3 приняты равными термодинамическим функциям M2SiO3, 0,5M2Si2O5, M4SiO4 и
0,5M6Si2O7, тогда как структурная единица Q4 характеризуется термодинамическими
функциями чистого SiO2. Получены зависимости термодинамических свойств от типа
структурных единиц, позволившие согласовать существенно различающиеся величины
термодинамических потенциалов, а также рассчитать термодинамические свойства и
оценить температуры плавления неисследованных ранее силикатов щелочных
металлов. Расчетные данные включают в себя термодинамические характеристики
силикатов лития, натрия и калия в диапазоне температур от 298,15 до 6000 K. В
физико-химической модели рассматривалось влияние исходного химического состава
(соотношения SiO2/M2O) и температуры на компонентный состав силикатного
расплава. Состав расплава менялся от чистого кремнезема до ортосиликата лития (67
мол. % М2O), температурный диапазон задавался от 298 до 1473 K. Для оценки
взаимодействия кремнекислородных тетраэдров Q0-Q3 в расплаве в модель вводятся
известные из экспериментальных данных ограничения на содержание индивидуальных
компонентов (Q0-Q3), и на основе результатов расчетов вынужденных равновесий
производится корректировка термодинамических функций. Полученные
термодинамические функции компонентов расплава могут быть использованы в
качестве исходных термодинамических свойств. В результате введения поправок
скорректирована исходная база термодинамических данных силикатов лития и натрия.
В этом случае результаты расчета в модели без ограничений, но с новыми
термодинамическими данными, с высокой точностью описывают результаты
экспериментальных исследований.
Работа выполнена при поддержке грантом РФФИ 12-05-00294-а и гранта
Президента Российской Федерации для поддержки молодых российских ученых (МК-
109.2011.5).
ПОЛИМЕРМЕТАЛЛИЧЕСКИЕ КОМПЛЕКСЫ ИОНОВ МЕДИ И КОБАЛЬТА

Оспанова А.К., Ашимхан Н.С., Сейлханова Г.А., Бердибек Г.Б.
Казахский национальный университет имени аль-Фараби, Алматы, Казахстан
e-mail: nazgul8080@mail.ru
Водорастворимые полимеры благодаря удачному сочетанию физико-химических
свойств высокомолекулярных соединений и электролитов завоевали прочное
положение во многих областях науки и техники. Наибольшей практической ценностью
обладают водорастворимые полимеры с комплексообразующими группами, способные
образовывать устойчивые хелатные комплексные соединения с ионами переходных
металлов. В последние годы установлено, что применение водорастворимых
комплексообразующих полимеров перспективно в качестве гомогенных и
гетерогенных катализаторов, лекарственных препаратов, термо- и механостойких
материалов.
Целью настоящей работы являлось определение термодинамических параметров
процессов комплексообразования поли-4-винилпиридина (П4ВП), полиакриловой
кислоты (ПАК) с ионами металлов кобальта и меди, а также установление составов
образующихся полимерметаллических комплексов (ПМК). С этой целью системы
полимер – ион металла были исследованы потенциометрическим, кондукто-
метрическим, вискозиметрическим методами.
При смешении водных растворов полимерами с солями металлов происходит
уменьшение рН среды, а электрическая проводимость систем увеличивается. Вероятно,
процессы комплексообразования в исследуемых системах сопровождаются выделением
протонов, обладающих высокими значениями электропроводности в водных растворах.
На основании экспериментальных данных установлено, что в системе П4ВП – Cu2+
образуется комплексная частица состава 4:1, а в результате взаимодействия ионов
кобальта с полиакриловой кислотой ПАК – Cо2+ образуется комплекс состава 2:1.
Потенциометрическим методом Бьеррума определены термодинамические константы
устойчивости образующихся полимерметаллических комплексов. Рассчитаны
стандартные термодинамические характеристики (∆rG0, ∆rH0, ∆rS0) процессов
комплексообразования поли-4-винилпиридина (П4ВП), полиакриловой кислоты (ПАК)
с ионами металлов кобальта и меди. На основе рассчитанных термодинамических
характеристик установлено, что процессы образования полимерметаллических
комплексов протекают самопроизвольно, являются экзотермическими, поэтому
повышение температуры приводит к снижению констант устойчивости
координационных соединений меди и кобальта. Важным для понимания природы
устойчивости комплексов является анализ изменения энтропии в ходе реакций их
образование. Изменение энтропии систем при комплексообразовании связано с
разрушением гидратных оболочек лигандных групп полимеров, вытеснением молекул
воды из первой координационной сферы иона металла и образованием хелатных
структур. Таким образом, положительный вклад первых двух факторов в уменьшение
упорядоченности систем перекрывает уменьшение энтропии вследствие образования
достаточно стабильных полихелатных структур.
Совокупность полученных экспериментальных данных позволила предположить
схемы взаимодействия поли-4-винилпиридина (П4ВП), полиакриловой кислоты (ПАК)
с ионами металлов кобальта и меди.
ТЕРМОДИНАМИЧЕСКИЕ ИССЛЕДОВАНИЯ ФОСФАТОВ

СТРУКТУРНОГО ТИПА КОСНАРИТА
Петьков В.И., Асабина Е.А., Маркин А.В., Смирнова Н.Н.
Нижегородский государственный университет им. Н.И. Лобачевского,
Нижний Новгород
e-mail: petkov@uic.nnov.ru
В работе обобщаются данные собственных исследований и работ других авторов о
термодинамических свойствах фосфатов структурного типа минерала коснарита
KZr2(PO4)3, изоструктурного с большим классом твердых ионных проводников NASICON,
Na1+xZr2SixP3−xO12, и NZP, NaZr2(PO4)3. Представляет интерес использование
представителей данного семейства в качестве твердых электролитов, керамик с низким
тепловым расширением, материалов для инкорпорирования радиоактивных отходов,
катализаторов, биоматериалов, совместимых с костной тканью.
Фазовый и химический состав изученных нами кристаллических фосфатов
MeE2(PO4)3 (Me = Li, Na, K, Rb, Cs, Zr0.25; E = Ti, Zr, Hf), Na5E(PO4)3, Me0.5E2(PO4)3 (Me =
Mg, Ca, Sr, Ba, Ni) и CaNi0.5Zr1.5(PO4)3 подтверждены методами порошковой
рентгенографии, ИК- спектроскопии, микрозондового и химического анализов.
Содержание примесей в образцах не превышало 0.5 мас.%. Изобарная теплоемкость
фосфатов в интервале температур 6−370 K изучена в адиабатическом вакуумном
калориметре (БКТ−3), в области 300–650 K − с использованием дифференциального
сканирующего калориметра (DSC204F1 Phoenix). Для всех соединений рассчитаны
стандартные термодинамические функции: теплоемкость, энтальпия, энтропия и функция
Гиббса в области от T → 0 до 650 K. Стандартные энтальпии образования цирконий
содержащих фосфатов при 298.15 K получены с использованием калориметрии
растворения в водном растворе фтористоводородной кислоты (микрокалориметр ДАК-1-1-
А).
Для различных представителей семейства коснарита удельная теплоемкость
составляет 0.5–1.2 Дж·г–1∙К–1 в интервале 273–650 К и при Т > 500 К меняется незначительно.
При переходе от фосфатов NaE2(PO4)3 к Na5E(PO4)3 С 0p увеличивается, то есть
соблюдается общая закономерность, согласно которой увеличение числа атомов в
элементарной ячейке приводит к росту теплоемкости соединений. Уменьшение
рассчитанной по данным С 0p (Т) температуры Дебая в рядах NaE2(PO4)3→Na5E(PO4)3 (E = Ti, Zr,
Hf) позволяет сделать заключение о более жестких кристаллических решетках фосфатов
NaE2(PO4)3 по сравнению с Na5E(PO4)3, структурные каркасы которых, наряду с EО6-октаэдрами,
включают более деформируемые NaO6-полиэдры. Меньшая жесткость структуры приводит к
размораживанию решеточных колебаний у соединений Na5E(PO4)3 при более низких
температурах. На кривых теплоемкости LiZr2(PO4)3, Na5Zr(PO4)3 и Na5Hf(PO4)3 наблюдаются
фазовые переходы, связанные с изменением позиционной упорядоченности катионов Li+, Zr4+,
Hf4+ и Na+; для остальных фосфатов фазовых превращений в изученной температурной области
не выявлено.
Сведения о теплоемкости, энтальпии, энтропии и функции Гиббса образования
позволили установить, что процессы твердофазного синтеза термодинамически разрешены
при 430 К для NaZr2(PO4)3, 410 К для CsZr2(PO4)3 и 570 К для Na5Zr(PO4)3. Синтез этих
фосфатов обычно проводят при более высоких температурах (≥1273 К для CsZr2(PO4)3). По
осадительной методике за счет оптимизации температурного режима удалось получить
CsZr2(PO4)3 при 1023 К.
Работа выполнена при финансовой поддержке Российского фонда
фундаментальных исследований (проект № 11-03-00032).
ТЕРМОДИНАМИЧЕСКИЙ АНАЛИЗ ВОЗМОЖНОСТИ

ПЕРЕРАСПРЕДЕЛЕНИЯ УГЛЕРОДА В РЕШЁТКЕ ЦЕМЕНТИТА
Сафронова Н.А., Васюкова Е.С., Окишев К.Ю.
Южно-Уральский государственный университет, Челябинск
e-mail: k.okishev@inbox.ru
Цементит Fe3C — одна из основных фаз углеродистых сталей и чугунов — имеет
орторомбическую решётку с 16 атомами в элементарной ячейке. Ряд опубликованных в
последние годы экспериментальных работ, использовавших методы ЯГР, EELFS и др. для
анализа ближайшего атомного окружения, показал, что при подкритическом (700 °C)
отжиге стали с перлитной структурой наблюдаются изменения ближайшего окружения
атомов железа и углерода в цементите перлита, причём существенных изменений картины
рентгеновской дифракции, создаваемой в основном атомами железа, при этом не
происходит (Изв. РАН. Сер. физ. 69 (2005) 1292 и др.). Одно из возможных объяснений
состоит в перераспределении атомов углерода по различным позициям железной
подрешётки цементита.
Как показано в (ФММ 96 (2003) 3, 75), в железной подрешётке цементита можно
выделить четыре типа пор, в которых могли бы располагаться атомы углерода:
«нормальные» призматические и октаэдрические и «искажённые» призматические и
октаэдрические. Число пор каждого типа одинаково и равно стехиометрическому числу
атомов углерода. Их радиусы при неискажённой железной подрешётке составляют 2,01;
1,84; 1,62 и 1,25 Å, а число атомов железа в первой координационной сфере 6; 6; 4 и 2.
Обычно считается, что углерод занимает самые крупные, «нормальные» призматические
поры, хотя в литературе обсуждался и вариант «нормальных» октаэдрических пор.
Имеются две работы, где делалась оценка полной энергии цементита для указанных двух
вариантов размещения атомов углерода при помощи расчётов «из первых принципов».
Разность этих энергий в расчёте на один атом углерода по их данным составляет 0,68 эВ
(ФММ 96 (2003) 5, 16) и 0,27 эВ (J. Phys.: Cond. Matter 19 (2007) 196214).
На основе результатов второй, более поздней работы, нами получены приближённые
оценки изменения энергии атома углерода при переходе из «нормальных» призматических в
остальные три типа пор, которые составили 0; 0,27; 0,42 и 0,42 эВ. Разработана статистическая
теория, позволяющая рассчитать равновесную концентрацию атомов углерода, находящихся в
порах каждого из четырёх типов. Результаты расчёта показывают, что при 700°C равновесная
доля атомов углерода, находящихся в «нормальных» призматических порах, составляет 0,80, в
«нормальных» октаэдрических: 0,14, а в «искажённых» призматических и октаэдрических — по
0,03. Интересно отметить, что в классической работе Липсона и Петча (1940) для первых двух
позиций было получено (рентгеноструктурным методом) очень близкое соотношение
0,86 : 0,14, но впоследствии этот результат был забыт. Найденные величины не так уж малы, но
всё же они не позволяют полностью количественно объяснить наблюдавшейся авторами
(ФММ 98 (2004) 3, 72) картины изменения EELFS-спектров цементита при отжиге; в то же
время при варьировании значений энергий согласие может быть улучшено. Поэтому для
точного ответа на вопрос, возможны ли в действительности переходы атомов углерода из
«нормальных» призматических пор в поры других типов, или наблюдавшиеся изменения
ближайшего окружения атомов при отжиге цементита обусловлены другими процессами
(образованием вакансий в углеродной подрешётке, дефектов упаковки и т.п.), в настоящее
время проводятся прямые первопринципные расчеты энергий соответствующих состояний
цементита.
ПОЛИАКРИЛАМИДНЫЕ КОМПЛЕКСЫ
ИОНОВ МЕТАЛЛОВ ПОДГРУППЫ ХРОМА
Сейлханова Г.А., Оспанова А.К., Ашимхан Н.С., Муханова А., Усипбекова Е.Ж.
e-mail: g_seilkhanova@mail.ru
Полимерные сорбенты, как известно, образуют более прочные комплексы с
ионами металлов по сравнению с их низкомолекулярными аналогами, так как
образующиеся полимерметаллические комплексы (ПМК) стабилизируются не только за
счет ковалентных связей и электростатических сил, но и за счет гидрофобного
взаимодействия. Поэтому с целью разработки эффективных способов извлечения,
концентрирования токсичных соединений были проведены исследования по
установлению термодинамических характеристик процессов образования
полимерметаллических комплексов ионов металлов подгруппы хрома. В качестве
высокомолекулярного лиганда использован полиакриламид (ПАА), содержащий в
своем составе два донорных атома – кислород и азот, что обеспечивает его
возможность образовывать координационные соединения. Кроме того, данный
полимер, в силу экономической доступности, широко используется в промышленности.
Системы, содержащие ионы металлов подгруппы хрома, полиакриламид, были
исследованы потенциометрическим, кондуктометрическим, вискозиметрическим
методами в водной и водно-органической средах. Результаты указывают на
образование соединений ПАА-Cr3+- = 4:1, а для систем ПАА-WO42- = 2:1, ПАА-MO42- =
6:1. Исследуемые процессы сопровождаются понижением рН и вязкости растворов, а
также повышением их электропроводности, это обусловлено образованием
полиакриламидных хелатов с выделением протонов, в результате чего
гидродинамические размеры высокомолекулярного лиганда умешьшаются.
Предложены схемы формирования ПМК ионов хрома, молибдена, вольфрама.
В работе были рассчитаны концентрационные константы устойчивости
полиакриамидных комплексов ионов металлов при различных значениях ионной силы
раствора и температурах. На основе анализа зависимости контант равновесия
процессов комплексообразования от ионной силы раствора установлены
термодинамические константы исследуемых реакций. Практически во всех
исследуемых системах прочность комплексов выше в водно-спиртовой среде. Это,
вероятно, обусловлено тем, что в органической среде энергия сольватации ионов
металлов меньше, что приводит к повышению доступности функциональных групп
лиганда при комплексообразовании. В водной среде, как известно, диполи молекул
воды более сильно связаны с центральным ионом комплексообразователя и
конкурируют за лигандные места во внутренней координационной сфере иона металла.
Кроме того, вероятно, система тратит больше энергии на разрушение связей с
гидратной оболочкой у ионов металлов по сравнению с их сольватной в С2Н5ОН.
Процессы связывания ионов металлов сопровождаются отрицательными значениями
энергии Гиббса, что свидетельствует о термодинамической разрешенность данных
реакций в прямом направлении. Исследуемые реакции – эндотермические, для которых
характерно положительное значение изменения энтропии, которое обусловлено
разрушением гидратных оболочек лигандных групп полимерного лиганда,
вытеснением молекул воды из первой координационной сферы иона металла-
комплексообразователя, в результате формирования прочных хелатных
координационных соединений.
ТЕРМОДИНАМИКА ПРОЦЕССОВ ОБРАЗОВАНИЯ ПОЛИЭТИЛЕНГЛИКОЛЕВЫХ

КОМПЛЕКСОВ СЕРЕБРА И ЗОЛОТА
Сейлханова Г.А., Усипбекова Е.Ж., Бектуров Е.А., Турганалы Р.М.
e-mail: g_seilkhanova@mail.ru
Как известно, макромолекулы, находящиеся в растворе, образуют различные
соединения с низкомолекулярными веществами, в частности, с ионами металлов,
поверхностно-активными веществами, красителями /1-3/. В настоящее время
повышенный интерес придается физико-химическим исследованиям процессов
комплексообразования полимерных лигандов с ионами металлов. Это обусловлено
широким практическим применением полимерметаллических комплексов в качестве
катализаторов, медицинских препаратов, материалов, обладающих специфическими
характеристиками (высокая электропроводимость, повышенные механические,
термические свойства и т.д.). Кроме того, сами реакции комплексообразования с
формированием устойчивых координационных соединений могут быть основой
химико-технологического процесса очистки промышленных вод от ионов различных
металлов, извлечения ценных компонентов из производственных растворов. В этом
отношении результаты физико-химического исследования процессов взаимодействия
полиэтиленгликоля (ПЭГ) с ионами серебра и золота являются актуальными.
В работе потенциометрическим, кондуктометрическим, вискозиметрическим
методами установлены составы образующихся полимерметаллических комплексов
ПЭГ:Ag+ = 6:1, ПЭГ:Au3+ = 6:1. Потенциометрическим методом Бьеррума рассчитаны
координационные числа ионов металлов, константы устойчивости комплексов при
нескольких значениях ионной силы раствора, что позволило нам графическим
способом установить термодинамическую константу равновесия реакции образования
соединений ПЭГ: Ag+, ПЭГ:Au3+. Установлено, что с повышением ионной силы
растворов, константы устойчивости полиэтиленгликолевых комплексов серебра и
золота увеличиваются, что обусловлено усилением донорно-акцепторной способности
реагентов. Эксперименты были проведены при трех значениях температуры с целью
определения термодинамических характеристик исследуемого процесса, а именно,
изменения энергии Гиббса, энтальпии, энтропии. Рассчитанные параметры указывают
на термодинамическую разрешимость исследуемого процесса, комплексообразование
сопровождается выделением теплоты, ростом энтропии, которое, вероятно,
обусловлено высвобождением молекул растворителя из внутренней координационной
сферы иона металла. С ростом температуры константы устойчивости
полиэтиленгликолевых комплексов повышаются, что обусловлено смешением
химического равновесия в сторону образования конечных продуктов –
координационных соединений серебра и золота. На основе анализа результатов
эксперимента предложены схемы формирования комплексов ПЭГ:Ag+, ПЭГ:Au3+.
1. Бектуров Е.А., Бимендина Л.А., Мамытбеков Г.К. Комплексы водорастворимых
полимеров и гидрогелей. - Алматы:Гылым, 2002. - 220 с.
2. Бектуров Е.А. Полимерные электролиты, гидрогели, комплексы и катализаторы.
– Алматы, 2007. - 241 с.
3. Будтов В.П. Физическая химия растворов полимеров. - Санкт-Петербург, 1992. -
231 с.
Section 3
Thermodynamics
of solutions and
heterogeneous systems
THERMODYNAMICS OF INTERACTION OF POLYELECTROLYTE HYDROGELS

ON THE BASIS OF ACRYLIC AND METHACRYLIC ACIDS
Adamova L.V., Blokhina A.S.
Ural Federal University, Yekaterinburg
e-mail: Lidiya.adamova@usu.ru
The polyelectrolyte hydrogels are able to absorb and retain a huge amount of solvent,
considerably exceeding the mass of polymer. They are employed as water-absorbing and water-
retaining substances. The chemical nature of the polymer, type of the counter-ion, degree of
ionization and degree of cross-link influence on the adsorptive characteristics of gels and define
the thermodynamic affinity of polymers with water.
The purpose of the present work is determination of the thermodynamic parameters of the
interaction with water of the polyelectrolyte h ydrogels on the basis of acrylic acid and potassium
acrylate (PAA\PPAA), methacrylic acid and potassium methacrylate (PMAA\PPMAA). Gels were
made by free-radical polymerization of partially neutralized acrylic and methacrylic acids,
respectively with N,N’-methylenediacrylamide as a cross-linker in aqueous solution. The degree
of ionization ranged from 0 to 100%. The overall monomer (acid and its potassium salt)
concentration was 2.7 m, while the cross-linker to monomer concentrations were set at 1:100.
Potassium persulfate (0.5 g l-1) was used as initiator. Polymerization had been carried out during
two hours at the temperature of 700С
The influence of the degree of ionization on the parameters of the thermodynamic affinity
and sorption capacity of gels with water was examined.
The kinetics end equilibrium of the interval isothermal vapor sorption of the water on
polymers was studied, the gravimetric version of the sorption method was used. The temperature
was 298 К and the residual pressure was 10-3 Pa The chemical potentials of water ∆µ1, polymer
component ∆µ2, the average Gibbs energy of swelling of the polymers in water ∆gm and Flory-
Huggins parameter of interaction of polymers with water χ1 have been determined over the wide
concentration range. The diffusion coefficient of water vapor in polymer matrix D was calculated.
The sorption capacity of gels and Gibbs energy of swelling ∆gm are increased as the degree
of ionization and dependent of packing density and thermodynamic affinity to water. Therefore
gel PMAA\PPMAA is possessed bigger sorption capacity then PAA\PPAA with same degree of
ionization in the wide range of relative pressure. This is due to less density packing, and as a
result of the higher accessibility of the polar groups of the polymer for water molecules. This is
evidenced by the values of the inaccessibility factor of the gels. Gels on the basis of acrylic acid
are sorbs greater amount of water at high relative pressure because of prevalent role of the
thermodynamic affinity.
Flory-Huggins parameters χ1 was calculated as the residual chemical potentials. They
depend strongly on the water content in gel, correlate with sorption isotherms and .decreased with
the increase in the degree of ionization of polymers.
When considering the parameter χ1 as constants describing the interaction of polymer-
solvent, and taking into account the contribution of the initial non-equilibrium glassy state of
polymer containing meta vacancies, it is established that the χ for gels PAK/КПАК decreases with
the degree of ionization, and for gels ПМАК/КПМАК - remains constant.
For all degrees of ionization at low water contents in a polymer matrix the diffusion
coefficient D increases significantly with the increasing concentration of water and then stays
constant. This is the result of a simultaneous increase the flexibility of the polymer chains in their
plastification, which leads to the growth of the value of D, and reduce the water mobility due to
the interaction with the polymer, which leads to a decrease of the diffusion coefficient.
Section 3 — Thermodynamics of solutions and heterogeneous systems ♦ 199
THE PHASE BEHAVIOUR OF THE SYSTEM {CO2 + CAFFEINE}

AT HIGH PRESSURES STUDIED WITH SCANNING TRANSITIOMETRY
AND EQUATIONS OF STATE
Agafonova E.V.1, Randzio S.L.2, Deiters, U.K.3
1
e-mail: eugeniasa@mail.ru
2
Polish Academy of Sciences, Warsaw, Poland
e-mail: stanislaw.randzio@ichf.edu.pl
3
University of Cologne, Cologne, Germany
e-mail: ulrich.deiters@uni-koeln.de
The phase behaviour of the binary system {CO2 + anhydrous caffeine} was
experimentally studied with scanning transitiometry up to c. 550 K and 200 MPa. New
experimental data were obtained for mixtures with higher caffeine content. The system
exhibits a solid–solid phase transition at c. 410 K and rather complex solid–fluid equilibria at
higher temperatures.
Previous work [1] showed that it is in principle possible to model the phase diagram by
coupling a suitable equation of state for the fluid state (here the Peng–Robinson equation
proved to be sufficient) consistently to equations for the solid phases. With the new
experimental data it became evident that the customary quadratic mixing rules proposed by
Peng and Robinson are no longer sufficient. A significant improvement could be obtained,
however, by switching to a “fractal” mixing rule, which is more appropriate for nonspherical
and rigid molecules like caffeine [2].
References
1. U. K. Deiters and S. L. Randzio, Fluid Phase Equilib. 260 (2007) 87–97.
2. U. K. Deiters, Fluid Phase Equilib. 48 (1989) 185–196.
CONDUCTOMETRIC INVESTIGATION AND MOLECULAR DYNAMICS

SIMULATION OF THERMODYNAMICS AND STRUCTURE
OF ME(II) – 3-HYDROXYFLAVONE COMPLEXES IN ACETONITRILE
Agieienko V.N., Kalugin O.N.
V.N. Karazin Kharkiv National University, Kharkiv, Ukraine
e-mail: vira.agieienko@gmail.com
Recent interest to investigation of unsymmetrical electrolytes solutions has been
associated with the development of high-performance fluorescent probes for double-charged
cations such as biologically important (Mg2+, Ca2+, Co2+, Zn2+), noxious (Ba2+, Hg2+, Cd2+),
and radioactive (Sr2+). Flavonol derivatives, polyphenolic compounds, can be regarded as
promising candidates for such probes. Despite the diversity of spectroscopic methods and
huge amount of experimental works relating to investigation of the flavonol-like systems a set
of questions remains unanswered. Up to now it has not been published any fundamental
thermodynamic characteristics of the complexes formed by Me(II) cations with flavonol
derivatives and detailed information about the structure and the composition of these
complexes in liquid media. Characterisation of such important properties of flavonoids and
their complexes is prerequisite both for successful analytical determination of above
mentioned cations and for understanding the structure/activity relationships in biological
systems.
When complex particle is formed in solution, its size, parameters of solvation and in
some cases charge are changed. Hereupon, its mobility is changed as compared with
corresponding cation. It is well known that conductivity is very sensitive to change in
concentration, size and charge of the ion species in solution. Therefore a conductometry
technique can be successfully used for the determination such important characteristics as
thermodynamic constants of association (KA) and complex formation (KL).
In the present work the structural and thermodynamics characteristics of acetonitrile
solutions containing perchlorates of group II A and nickel perchlorate and 3-hydroxyflavone
have been investigated. The values of limiting electrical conductivities for all types of charged
particles as well as thermodynamic constants of association and complexation were
determined in wide temperature range. It was shown that strong first step association between
cation and anion are observed for all investigated salts. For example, the logarithms of
primary association constants at 298 K are found as following: lgKA(MgClO4+) = 2.37,
lgKA(CaClO4+) = 2.44, lgKA(SrClO4+) = 2.58, lgKA(BaClO4+) = 2.69, and lgKA(NiClO4+) =
2.40. The process of complexation between Ni2+, Ca2+, Sr2+ and flavonol in acetonitrile is
accompanied by the formation of [Ktflv]2+ complex particles (lgKL[Niflv]2+= 1.93,
lgKL[Caflv]2+= 1.70, and lgKL[Srflv]2+= 1.38 at 298 K). In case of Mg2+ and Ba2+ the singly
charged [KtClO4flv]+ cation is formed (lgKL[MgClO4flv]+ = 1.75, lgKL[BaClO4flv]+ = 1.94 at
298 K).
For deeper examination the behaviour of particles on microscopic level an intensive
molecular dynamics simulation has been performed.
OXYGEN NONSTOICHIOMETRY AND THERMODYNAMIC STABILITY

OF La2-xSrxCuO4-δ SOLID SOLUTIONS IN La2CuO4 – Sr2CuO3 SYSTEM
Alyoshin V.A., Tiphlova L.A., Monayenkova A.S.
Department of Chemistry, Lomonosov Moscow State University, Moscow
e-mail: alyoshin@inorg.chem.msu.ru
The solid solutions La2-xSrxCuO4-δ (0 < x(Sr) <1.2) in the La2CuO4 - Sr2CuO3 system,
formed by heterovalent substitution of La on Sr, have the properties of high-temperature
superconductivity, exhibit catalytic activity and are considered as a material for low
temperature fuel cells.
The heterovalent substitution of La on Sr increases the copper oxidation state and led to
forming of oxygen vacancies in CuO2 layer, which reduce the stability of the La2-xSrxCuO4-δ
crystal lattice. The increasing of copper oxidation state is dominated at small substitutions
x(Sr), and oxygen vacancies formation is preferable at higher x(Sr). These structure violations
are accompanied by changing of lattice energy, and prediction of stability these solid solutions
on the base of structure data and thermodynamic properties is the main purpose of the work.
The determination of enthalpy of formation La2-xSrxCuO4-δ (ΔoxH°298) on oxides was
performed by solution calorimetry technique. Copper oxidation states were calculated from
results of iodometrc analysis, interatomic distances were taken from x-ray structure data. The
dependence of ΔoxH°298(La2-xSrxCuO4-δ) on copper oxidation state V(Cu), strontium content
x(Sr), interatomic distances and oxygen vacancies concentration δ was revealed, and a crystal
energetic model, satisfactory fitted this dependence, was proposed. In the employed model the
change of lattice La2-xSrxCuO4-δ energy was described as a function of structural factors
variations, such as location and concentration of oxygen vacancies δ. The energy contributions
of {La2O2} layer and CuO6 octahedral layer were treated separately, and the interlayer
interaction was added. The correlation coefficients in the final equation were estimated by
fitting experimental data on enthalpies ΔoxH°298 to model dependence. The ΔoxH°298(La2-
xSrxCuO4-δ) of x(Sr) has a minimum, corresponding to x(Sr) = 0.6, caused by lattice instability.
It was revealed that the main contribution in the energy variation was made the CuO6
octahedral layer because the significant copper oxidation state changing, interatomic distances
variations and oxygen vacancies concentration increasing. The discrepancy between the
calculated and experimental thermodynamic data did not exceeds 4 kJ/mol, which indicates
the adequacy of the used model and accuracy of obtained values of ΔoxH°298.
In order to assess the thermodynamic stability of La2-xSrxCuO4-δ solid solutions, the
ΔoxG°298 - x(Sr) diagram was plotted. Dependence ΔoxG°298(La2-xSrxCuO4-δ) on x(Sr) has a
minimum at x(Sr) = 0.6, Sr2CuO3 was considered as a point phase. According to
thermodynamic analysis of the La2CuO4 - Sr2CuO3 system, the La2-xSrxCuO4-δ solid solutions
thermodynamically stable only at x(Sr) < 0.6 under standard conditions. In the range 0.6 <
x(Sr) < 1.2 this phase unstable relatively La1.4Sr0.6CuO4-δ and Sr2CuO3 and may exist in
metastable state only.
The problem of synthesis of metastable La2-xSrxCuO4-δ are discussed also in regard to
the thermodynamic and kinetic properties of La2CuO4 - Sr2CuO3 with recommendations for
obtaining uncontaminated samples.
This work was supported by RFBR grants № 12-08-01258-a and 07-03-00973-a.
THERMODYNAMIC ASPECTS OF SELECTION OF FLOTATION REAGENTS

FOR THE ENRICHMENT OF POLYMETALLIC ORES
Amerkhanova Sh.K.
E.A. Buketov Karagandy State University, Karagandy
e-mail: amerkhanova_sh@mail.ru
As is known, Kazakhstan ore, containing non-ferrous metals, are complex, have
complex structural and mineralogical composition. At the same time, structure, physical-
chemical and other characteristics of Kazakhstan ores at the extraction, concentration and
processing demand individual technology for each fields [1]. In this regard, the most urgent
needs to be addressed the problem of establishing criteria for selective flotation reagent
according to preliminary calculations, takes into account the physical-chemical and
morphological properties of the flotation reagent.
Based on the results of thermodynamic parameters’ calculations of complex formation
of d-metals ions and physical-chemical properties of the metal ions in aqueous solution have
been new correlation ratio ∆ r H 298
o
= f ( S 298
0
( M n + )) , ∆ r S 298
o
= f (∆ f H 298
0
( M n + ))
,
− ∆ r G 298
o
= f (− ∆ h S 298
0
( M n + )) , the tangents of the angles are equal to -22.61, -6.98, -3.65,
respectively .
So in the first case, the angle of inclination characterizes the influence of the metal
cation’s structure in solution on the thermal effect. In quantitative terms, the value is equal to
the difference in temperature compensation for metal cation when moving from free to bound
in the complex [2]. In the second – it is the value of the energy stability of the metal cation as
a result of the transfer from the solution to the complex, due to the distortion of the ion’s
electrostatic field by ligand’s effect. In the third – it is shown to increase the degree of cation’s
structure reduces the stability of the complex in result of hydration, i.e., the most structured
cation is less reactive with respect to the ligand, in this case it is nickel (II) ion [3].
Further, at various ionic strengths were obtained values of the slope dependence of the
enthalpy of the transfer dibuthyldithiophosphate complexes of iron, cobalt (II) and nickel (II)
from aqueous medium in the electrolyte solution on the function of ionic strength in the
temperature range 298-318 K: for complexes iron (II) ion at ionic strengths 0.075-0.25 is 0.32,
at ionic strength 0.5-0.75 equal to 326.10, for the cobalt (II) ions 0.04 and -35.66, for nickel
(II) ions - 0.29 and 297.07 respectively. It was established that dominant influence on the
behavior of the complexes has a primary salt effect (tgα>0) at ionic strength of 0.5 to 0.75; at
0.075-0.25 - secondary (tgα<0), except Co2+ ions [4]. The obtained relations can be used in
the selection process with contributions from the metal ion-chelator and influence of
indifferent salt.
References
1. Flotation reagents (Phlotatsionnye reagenty). Ed. by V.А. Kremer. М.:
Nedra,1974.-240 p.
2. Ospanov Kh.К. Thermodynamics and kinetics of heterogeneous
(nonequilibrium) chemical processes (Termodinamika i kinetika geterogennykh
(neravnovesnykh) khhimicheskikh processov.-Almaty: Complex, 2006.- 328 p.
3. Bakeev M.I. Theory and hydration properties of electrolyte solutions (Teoriya
gidratatsii i svoistva rastvorov electrolitov).-Karagandy: Publ. House KarSU,
2007.- 221 p.
4. Tsiparis I.N., Dobroserdov L.L., Kogan V.B. The salt fractionation (Solevaya
rektifikatsiya).- М.: Khimiya, 1969.- 164 p.
IMPLEMENTATION OF EQUILIBRIUM FLOTATION IN SOLUTIONS

Amerkhanova Sh.K., Shlyapov R.M.
E.A Buketov Karagandy State University, Karagandy
e-mail: amerkhanova_sh@mail.ru
Recently the attention of the leading scientists in the field of coordination chemistry and
technologists processing industry focused on issues relating to the assessment structure of
physical and chemical properties of collectors in the complexing ability [1], but the work on
the analysis of the thermodynamic functions of the process of binding of metal ions by various
flotation reagents and their relation to the practical outputs highly conditional concentrates in
the literature almost never occur. It is therefore highly relevant is the determination of the
thermodynamic characteristics of complex formation of economic and strategic metals with
sulfur collectors. The results of the pH-metric studies are summarized in the table.
Table - Changing of stability constants of metal ion complexes of mixed-subgroup of copper

Mn+ lgβ1,2 (С4H9O)2PS2K (i-С3H7O)2PS2Na
I
298 К 303 К 308 К 313 К 318 К
2
Cu 0.1 16.87±0.036 16.50±0.033 16.15±0.031 15.80±0.028 15.44±0.027
+
0.5 14.14±0.013 14.00±0.013 13.80±0.012 13.63±0.011 13.45±0.010
0.75 9.60±0.044 9.74±0.041 9.86±0.038 10.00±0.036 10.14±0.033
+
Ag 0.1 15.87±0.031 17.35±0.033 18.67±0.035 19.84±0.076 20.86±0.038
0.5 10.21±0.011 11.42±0.012 12.67±0.012 13.98±0.013 15.31±0.014
0.75 5.82±0.041 6.95±0.043 8.22±0.047 9.63±0.048 11.23±0.050
As seen from the data (table) the introduction of another ligand significantly increases
the stability constants at low ionic strengths. It is shown that the presence of potassium
dibuthyldithiophosphate strengthens the structure of the complex due to the lower basicity, at
the same time, the presence of isopropyl radical increases the strength of the metal-ligand to a
lesser extent. However, in sum, this leads to positive deviations from additivity, indicating a
more energetically favorable interaction of copper cations with different ligands than with the
same name [2]. In [3] describes the possibility of the existence along with the 1:1 complexes,
complexes - 1:2 with tryptophan. From the data of the table that the introduction of an
additional ligand strengthens the inner-sphere complex with dibuthildithiophosphate anion,
but the presence of high ionic strengths of the second ligand is energetically favorable and the
balance shifts toward mono ligand dibuthyldithiophosphate complexes of silver (I).
References
1. Gorger J.A., Klassen V.I., Ryskin N.I. new methods to improve the efficiency of mineral
processing - Moscow Gostortehizdat, 1968.-188 p.
2. Lukachina V.V. Ligand-ligand interaction and stability of ternary complexes. Kiev: Nauk.
Dumka. -1988.-184 p.
3. Legler E.V., Kazbanov V.I., Kazachenko A. Complexation in the system Ag (I) - tryptophan
/ / J. Inorg. Chem.. - 2002. - V.47, № 2. - P.341-343.
THERMODYNAMICS OF PHASE TRANSFORMATIONS IN THE SYSTEM Cu2S-Cu2Se

Andreev O. V., Shchurova M. A., Matigorov A. O., Elyshev A. V.
Tyumen State University, Tyumen
e-mail: andreev@utmn.ru, margarita.shurova@list.ru
System Cu2S-Cu2Se at high temperatures is a system with unlimited solubility in the
solid and liquid state. The purpose of this research is the thermodynamic analysis of the
system Cu2S-Cu2Se in the liquidus-solidus. Samples of a given composition with defined
mass fraction of each copper chalcogenide synthesized with using the ampoule method. For
plotting the phase diagramm the method of thermal analysis with using the experimental
aggregate SETSYS Evolution with applying the computer programm SETSOFT 2000, which
was specifically designed for this aggregate, was used. The melting and crystallization heat
were determined (see Table). During the experiment argon was flushed at a rate 25 ml/min.
Heating was produced at a rate of 10 K/min. For each sample melting and crystallization
points were determined , which are imaged on the phase diagram (Fig.).
To calculate the mixing energy in solid Us and liquid Ul phases from the regular
solutions attitude in the system Cu2S-Cu2Se
the Pines-Kamenetz equations were used:
ln((1-y)/(1-x)) = x2*U' – y2*U'' – (q(Cu2Se)
/(RTm(Cu2Se))*(1 – (Tm(Cu2Se)/T))
ln(y/x) = (1-x)2*U' – (y-1)2*U'' – (q(Cu2S)
/(RTm(Cu2S))*(1 – (Tm(Cu2S) /T))
where q(Cu2Se) = 18 kJ/mol - Cu2Se
melting heat; Tm(Cu2Se) = 1415 K - Cu2Se
melting point; q (Cu2S) = 11,3 kJ/mol -
Cu2S melting heat; Tm (Cu2S) = 1403 K -
Cu2S melting point; R = 8,314 J/mol*K; x, y
– mole fraction of component in the liquid
and solid phases at a temperature T.
Reduced mixing energies in the solid U'' and
liquid U' phases at a given temperature T
was calculated using these equations.
Finding these values, Us and Ul was
calculated: Us = U''*RT; Ul = U'* RT.
composition, mol Heating, ΔHm, Cooling, ΔНc, Having carried out the calculations,
% J/g J/g we obtained Us = 35902 J/mol; Ul =
15Cu2Se-85Cu2S 14,0 -11,9 49221 J/mol. Phase equilibrium in
25Cu2Se-75Cu2S 25,8 -24,2 this system is adequately described
by the regular solution model.
44Cu2Se-56Cu2S 13,1 -12,7
The work was financially supported
50Cu2Se-50Cu2S 27,0 -27,2
by the research work of the state task
56Cu2Se-44Cu2S 24,0 -27,6
(code 3.3763.2011 (7-12)).
60Cu2Se-40Cu2S 11,1 -11,9
75Cu2Se-25Сu2S 29,4 -30,9
Reference:
Glazov V. M., Burchanov A.S., Saleeva N.M. // J. Phys. Chem. 1975. Vol. 49. P. 1658.
ENTHALPIES OF INTERACTION OF GLYCINE WITH NaCl AND KCl

IN AQUEOUS SOLUTIONS AT DIFFERENT TEMPERATURES
Antonova O.A., Korolev V.P., Fedotova M.V.
G.A. Krestov Institute of Solution Chemistry of RAS, Ivanovo
e-mail:mvf@isc-ras.ru
Amino acids are used as a model compounds for research of the thermodynamic
behaviour of proteins in aqueous solutions. It is known, that electrolytes can destroy or
strengthen water structure. This property is widely used for studying of their influence on
structure and functions of proteins in aqueous solutions. The purpose of the present work is to
investigate the features of interaction of glycine with NaCl and KCl in aqueous solution at
different temperatures on the basis of solution enthalpies.
Enthalpies of solution of glycine (Gly) in mixtures of water with NaCl (m≤5 mol/kg)
and KCl (m≤4 mol/kg) at 288, 298 and 313 K have been measured by calorimetrimetric
method. The concentration of Gly is 0.01-0.03 mol/kg. The standard enthalpies of transfer of
Gly from water to aqueous NaCl or KCl solutions have been determined from experimental
and standard values of solution enthalpies. The enthalpic parameters of pair (hGE) and triple
(hGEE) interactions of Gly with NaCl and KCl have been calculated within the limits of
McMillan-Mayer formalism for a quantitative estimation of interaction character of Gly with
electrolytes:
∆trH0(W→W+E) = 2 hGE mE + 3 hGEE mE2.
Table. Enthalpic parameters of pair (hGE, J kg/mol2) and triple (hGEE, J kg2/mol3) interaction of
glycine with NaCl and KCl in aqueous solution.
T, K W - NaCl W - KCl
h GE h GEE h GE h GEE
288.15 -732±26 59.7±4.5 -688±10 46.2±2.0
298.15 -524±7 41.1±1.1 -459±7 31.1±1.5
1 1 2
-504±8 43±25 -470
-480 2 -490±10 1
313.15 -170±3 14.8±0.5 -219±2 11.9±0.4
The general equations of dependence of enthalpies of transfer of Gly vs. electrolyte
concentration and temperature have been obtained. These equations allow predicting the
values of enthalpies of transfer of Gly from water to saturated aqueous NaCl or KCl solutions
in the interval of temperatures 273-323 K. Partial molar heat capacities of Gly in aqueous salt
solutions have been defined. It is positioned, that in the range of T=288-313 K these values do
not depend on temperature and increase with growth of electrolyte concentration (mE=0-5 mol
kg-1).
Using the obtained data the changes of the reduced enthalpy, Gibbs energy and entropy
of transfer have been calculated at the temperature rise from 273 to 323 K. It has been shown
that the entropy-enthalpy compensation, known, as Barclay-Butler rule [3] takes place.
Work is carried out at financial support of the Russian fund of basic researches (the
grant № 12-03-97508-r_center_а).
References
1. T.H. Lilley, E. Moses, I.R. Tasker // J Chem Soc Faraday I. 1980, 76, 906-914.
2. B. Palecz // Thermochim Acta. 1991, 180, 199-202.
3. I.M. Barclay, J.A.V. Butler. // Trans. Faraday Soc., 1938, 34, 1445-1454.
THE HOMOGENEITY REGION OF Tl5Te2I AND THERMODYNAMIC PROPERTIES

OF SOLID SOLUTIONS Tl5Te3-xIx
Babanly D.M., Alievв A.Sh.
Institute of Chemical Problems, Azerbaijan National Academy of Science, Baku, Azerbaijan
Chalcohalides of thallium possess semiconductor, photo-and thermoelectric properties.
Some of those attract more attention for radiation detection materials [1]. For the development
of synthesis methods and crystal growth of these phases requires reliable data on the phase
diagrams and fundamental thermodynamic properties.
The results of experimental investigation of phase equilibriums in the ternary Tl-Te-I
system shown that it is characterized by formation of ternary Tl5Te2I compound, which is non-
stoichiometric phase with a wide range of homogeneity.
In this paper, we studied the homogeneity region of Tl5Te2I and thermodynamic
properties of Tl5Te3-xIx solid solutions by means of EMF measurements. For the EMF
measurements we constructed the following reversible concentration chains:
(-) Tl (s) / glycerin, Tl+ /(Tl-Те-I) (s) (+) (1)
In this chains, saturated glycerin solution of KI with the addition of TlI was used as the
electrolyte. EMF was measured by the compensation method in the temperature range of 300–
430 K. Preliminary synthesized alloys from TlI-Tl2Те-TlTe composition area were exploited
as right (positive) electrodes.
From EMF measurements for various compositions of right electrode obtained
temperature-concentration dependences of EMF values and relative partial thermodynamic
functions of thallium in the alloys, which showed that this compound has a wide homogeneity
region, almost completely covering Tl2Te-Tl5Te3-Tl5Te2I subsystem.
From partial thermodynamic functions of thallium in alloys and solid state phase
diagrams the integral thermodynamic functions of Tl5Te2I and Tl5Te3-xIx solid solutions were
calculated (see Table).
Table
kJ∙mol-1 J∙ mol⋅К-1
Tl5Te2I 300,4±1,3 301,1±2,3 475,8±6,6
Tl5Te2,2I0,8 288,0±1,5 287,8±2,4 477,0±7,0
Tl5Te2,4I0,6 274,6±1,6 271,6±2,5 483,1±7,4
Tl5Te2,6I0,4 257,3±1,6 253,9±2,5 484,3±7,8
Tl5Te2,8I0,2 236,9±1,7 235,5±2,6 475,2±8,2
Tl5Te3 213,5±1,4 216,6±2,4 459,1±8,1
Reference
1. Johnsen S, Liu Z, Peters J.A., Song J.H., Nguyen S, Malliakas C.D., Jin H, Freeman A.J.,
Wessels B.W., Kanatzidis M.G. / J Am Chem Soc. 2011, 133(26):10030-3
THERMODYNAMIC PROPERTIES OF SOLID SOLUTIONS YbxSn1-xTe

Babanly M.B., Ibadova G.I., Aliev Z.S., Ilyasli Т.М.
Baku State University, Baku, Azerbaijan
Binary and ternary tellurides of heavy p-elements and Rare Earth (RE) as well as
muliticomponenet nonstoichiometric phases based on them are low-gap semiconductors,
which are deemed as “matrices” for design of new and better thermoelectric materials [1].
These systems attract more attentions because many ternary phases in these systems are
promising high-performance 3D topological insulators which have potential materials in
nanoelectronics, quantum computing and spintronics [2].
In this work, we report the results of the complete investigation of phase equilibriums in
the YbTe-SnTe system and of thermodynamic properties of the solid solutions YbxSn1-xTe.
The synthesis of all samples was performed in sealed (~10-2 Pa) silica ampoules from
preliminary synthesized compounds. In order to get a complete homogenization all alloys
were ground into fine powders, mixed thoroughly and pressed into pellets, then subjected to a
homogenizing annealing at 1000 K for 600 h.
Differential thermal analysis (DTA) was performed using the NTR-72 pyrometer
equipped with chromel–alumel thermocouples. X-ray powder diffraction (XPD) analysis was
done with the X’Pert MPD Difractometer (Cu-Kα radiation). Scanning electron microscope
Philips-XL30FEG was employed for the microstructure analysis. Electromotive force (EMF)
measurements were performed for the reversible concentration chains
(−) YbTe (s) | liquid electrolyte, Yb+3 | YbxSn1-xTe (s) (+) (1)
In the chains (1), saturated glycerin solution of KCl with the addition of YbCl3was used
as the electrolyte. EMF was measured by the compensation method in the temperature range
of 300–400 K. The construction of the electrochemical cell and the measuring procedure are
described in detail elsewhere [3].
The phase diagram of the system YbTe-SnTe was constructed. It is clear that the system
is quasi-binary and characterized by the field of continus solid sloutions with the NaCl-type
cubic crystal structure.
The linear least-square treatment of the EMF data was performed to the obtained data
and the results were expressed as E=a+bT±tSE(T), which partial thermodynamic functions of
YbTe in the solid solutions were calculated. By integration of the Gibbs–Duhem equation the
thermodynamic functions of dissolution of YbTe in SnTe were calculated on the system
YbTe-SnTe. By combining them with the corresponding thermodynamic data for YbTe and
SnTe the standard integral thermodynamic functions of formation for the solid solutions
YbxSn1-xTe were calculated.
This work was supported by Science Development Foundation under the President of
the Republic of Azerbaijan - Grant № EIF-2011-1(3)-82/69/4-M-50.
References
1. Shevelkov A.V., Chemical aspects of creation of thermoelectric materials // Russ. Chem.
Rev. 2008, v.77, pp. 1–19.
1. Eremeev S.V., Landolt G., Aliyev Z.S., Babanly M.B. et al. Atom-specific spin mapping
and buried topological states in a homologous series of topological insulators. Nat.
Commun. 3:635. Doi: 10.1038/ncomms1638 (2012).
2. Babanly M.B., Yusibov Y.A. Electrochemical methods in thermodynamics of inorganic
systems. Baku, 2011, 306 p (ISBN 978-9952-453-17-1).
THERMOCHEMISTRY OF SOLUTION AND IONIC ASSOCIATION

OF THREE IONIC LIQUIDS IN ACETONITRILE AT 298,15 К
Belov A.V., Solov’ev S.N., Art’emkina Y.M.
Mendeleyev University of Chemical Technology of Russia, Moscow
e-mail: snsol@muctr.ru
Ionic liquids (ILs) actively take attention of researchers and empirics by reason of its
unique dissolving ability caused by ionic structure of molecules close to that of organic
substances. Certain thermodynamic characteristics of solution and ionic association in water,
nonaqueous and mixed solvents are specific for ordinary electrolytes. In General and
Inorganic Chemistry Subdepartment in order to identify these characteristics for ILs as well as
to compare their values with values of analogous characteristics for ordinary electrolytes
thermochemical research of solutions of three ILs in water, nonaqueous and mixed solvents is
being carried out.
Subjects of research are
– 1-Butyl-3-methylimidazolium trifluoromethanesulfonate
{[bmim][TfO]}, IL-1;
–1-Butyl-3-methylimidazolium bis(trifluorome-
thylsulfonyl)imide {[bmim][Tf2N]}, IL-2;
– 1-butyl-3-methylpyridinium bis(trifluoromethyl-
sulfonyl)imide {[bmpy][Tf2N]}, IL-3.
The purity of ILs used in thermochemical research exceeded 99 % and residual quantity
of water didn’t exceed 0.1 %.
In article being reported solution enthalpies of IL-1, IL-2 and IL-3 in water and
acetonitrile at various concentrations at 298.15 К were measured. In addition enthalpies of
dilution of water and acetonitrile IL-1 solutions in these solvents from three different
concentrations for each system to nearly the same concentration were measured.
Measurements were taken in airtight highly sensitive isothermal calorimeter. Its thermometric
and calorimetric sensitivities are 8·10-6 К and 0.007 J, respectively; accuracy of shell constant
temperature control is ±0.005 К.
Calorimeter constant was determined by electric method with systematic error to a
maximum of 0.1 %. Thermochemical measurements were taken in extremely severe
conditions, viz. in the most experiments amount of heat being measured didn’t exceed 1 J.
According to results of measurements of enthalpies of dissolution of IL solutions in
water and acetonitrile by the procedure [1] enthalpies and ionic association constants in
specified solvents were calculated. These values as well as solution enthalpies of IL-1, IL-2
and IL-3 in water and acetonitrile allowed to identify standard enthalpies of solution of three
ionic liquids in water and acetonitrile.
Reference
1. Solov’ev, S. N.; Khekalo, T. V. Proceedings of D.Mendeleyev Institute of Chemical
Technology of Moscow. 1989, 158, 129-138.
THERMODYNAMICS OF SORPTION OF FLUORINATED TOLUENES

IN PERFLUORINATED, FLUORO-CONTAINING AND ‘HYDROCARBON’ POLYMERS
ABOVE AND BELOW GLASS TRANSITION TEMPERATURE
Belov N.A., Nizhegorodova Yu.A.
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow
e-mail: belov@ips.ac.ru
In the middle of the 20th century, Scott turned his attention to some unsolved problems
of chemical thermodynamics, including the problem of solutions of fluorocarbon compounds.
The behavior of fluorocarbon FC and hydrocarbon HC mixtures is often in contradiction with
the predictions of the theory of regular solutions that are based on their solubility parameters.
Later, similar relationships were found for solute–polymer systems.
Recently, Inverse Gas Chromatography has been used to study infinite dilution sorption
in several polymers with different fluorine concentrations: the tetrafluoroethylene–
perfluoromethyl vinyl ether copolymer, and tetrafluoroethylene-perfluoromethoxidioxole
copolymer, a partially fluorinated hyperbranched Si-containing polymer (HBP), dendrimer
7.5G, and the ‘hydrocarbon’ rubber poly(pentenamer) (PPM). Thermodynamic parameters of
sorption of fluoro-containing derivatives of toluene (toluene, p-fluorotoluene, 2,3,4,5,6-
pentafluorotoluene, and octafluorotoluene), namely, solubility coefficients, excess partial
molar enthalpies and entropies, Flory-Huggins parameters etc., have been determined.
In this report one makes an attempt from two points of view to embrace the
experimental results having been obtained previously: (i) effect of content of the fluorine in
the compounds under consideration and (ii) effect of physical state of the polymer (glassy –
below glass transition temperature (Tg) – and rubbery (>Tg).
The following conclusions can be made:
1) hydrocarbon solutes are characterized by low solubility coefficients in
fluorinated rubbers and rather high one in PPM, whereas in dendrimer, HBP, and linear
polysiloxanes they have intermediate values of S. Opposite behavior is observed for
fluorocarbon solutes.
2) solubility coefficients of the solutes in glassy state polymers are always higher
than those in rubbery state polymers.
3) Excess enthalpies of solute–rubber systems reflect intermolecular interactions
between the solute molecule and the polymer. For solute-glassy polymer system, one needs
additionally to take into consideration glassy nature of the polymer. In the systems containing
C-F and C-H bonds intermolecular interactions are unfavorable (endothermic mixing),
whereas in systems only with C-F or C-H bonds, they are favorable (exothermic mixing).
Similar behavior is observed for Flory–Huggins parameter.
THE EFFECT OF PRESSURE AND IRON CONTENT ON THE GLASS

TRANSITION TEMPERATURES OF SODIUM SILICATE GLASSES
Belova E.V., Dunaeva E.S., Uspenskaya I.A.
e-mail: catrin@td.chem.msu.ru
The glass transition temperature, at which the transition from rubber-like state to brittle
state is observed, depends on the chemical composition and structure of substance. The
structure changes can occur in silicate glasses doped by some oxides (eg., Fe) or under
pressure [1]. The purpose of the present work was to measure glass transition temperature of
the glasses (100-x)Na2O-xSiO2-wFetot (x = 75 and 81 mol.%, w = 0.05 – 13 wt.%) in the
pressure range 1 - 100 bar and to compare obtained results with the trend in structure changes
of silicate glasses vs. total iron content(Fetot) [2].
The measurements were performed by DSC at the 204 HP Phoenix high pressure
calorimeter in argon atmosphere with scanning rate 10 K·min-1. For all samples, the following
thermal treatment and scanning program were used: heating up to 590°C, isothermal
annealing at 590°C within 10 min, cooling to 590°C, isothermal annealing at 400°C within 10
min, and glass transition temperature registration in the heating process of the sample from
400°C to 590°C. The results obtained for glasses with 19 mol.% Na2O are presented on
Fig.1 a. The ratio of isolated and cluster ferric ions vs. total iron content are shown on Fig.1 b.
As can be seen, the maximum on the Tg dependence curve occurs at compositions with
Feisol/Feclast ≈ 1.
Fig.1. Glass transition temperature (a) and ratio Feisol/Feclast (b) vs. total iron content (wt.%) in
glasses 19Na2O-81SiO2-wFetot. Symbols correspond to the high pressure measurements: 1 (♦),
50 (■) and 100 (▲) bar; ● – results of Mössbauer spectroscopy, ○ - EPR
The work is performed at User Facilities Center of M.V. Lomonosov Moscow State
University under financial support of Ministry of Education and Science of Russian
Federation (Contract N16.552.11.7081) within the Lomonosov MSU Development Program
and supported financially by Saint-Gobain Recherché.
Reference:
1. Fukui H. // Phys.Rev. B, 2008, v.78, p.012203
THERMODYNAMICS OF FORMATION OF H+-ASSOCIATE OF (CHLORO)-

(5,10,15,20-TETRAPHENYL21H,23H-PORPHYNATO)RHODIUM(III)
WITH AXIAL COORDINATED OXIGEN
Bichan N. G., Tyulyaeva E. Yu., Lomova T. N.
G. A. Krestov Institute of the Solution Chemistry of Russian Academy of Sciences, Ivanovo
e-mail: bichan-n@rambler.ru
A specific form of some metalloporphyrins (MP) in strong acid media − H+-associate,
similar to protonated benzene [1], was identified and analyzed spectrophotometrically. The
associate formation is of great scientific interest connected with the ability to generate in the
medium aerated acid the metalloporphyrins π-cation radicals - intermediates of many catalytic
redox reactions. H+-associate has an unique UV-Vis spectrum with two broad bands near 540
and 700 nm and the specific Soret band region. Thermodynamics of the associate formation is
unstudied due to experimental difficulties connected with the environment aggressivity, as
well as the fact that MP are often transformed into acid solution only through their association
with H+.
In this paper the system in which it is
possible to observe spectrophotometrically
slow reversible transition of molecular and
H+-associated forms of the MP is detected
and studied. Changing of absorption spectra
of (chloro)(5,10,15,20-tetraphenylporphy-
nato)rhodium(III) in the mixtures of acetic
and sulfuric acids demonstrates the transition Figure 1. Absorption spectra of (Cl)RhTPP in
of one form of the complex into another
AcOH−5 М H2SO4 at 328 К. τ, с: 0 – 1200
having the splited Q-band (Fig. 1). πσ-donor
ligand Cl− in the coordination sphere of
(Cl)RhTPP and π-dative component Rh→N in a coordinating interaction are the conditions of
H+-associate formation [1]. However the observed long-wave band splitting indicates a more
complicated process than the simple H+-associate formation. Taking into account ability of
stable MP to coordinate molecular oxygen in the aerated acid medium (H2SO4, CF3COOH)
[2] we can write an equation reflecting the transformation of spectrum:
K –
+
(Cl)RhTPP + H …R+ O2 (O2)(Cl)RhTPP…H+…R, R = HSO4 (1)
Thermodynamics of the reaction (1) in the AcOH−2÷9 М H2SO4 mixtures at 308 ÷ 338
K was studied by the molar ratios method. The equilibrium and rate constants (K and k) of the
reaction (1) were calculated and their dependences on temperature were studied.
References
1. Lomova T. N., Klyueva M. E, Tyulyaeva E. Yu., Bichan N. G., Saitseva S. V., Zdanovich S.
A. Mendeleev Communicaitions, 2012, 22, 281−28.
2. Lomova T.N., Klyueva M.E., Kosareva O.V., Klyuev M.V. Russian Chemical Bulletin,
2007, 56, № 4, 748-753
LOCATION OF SPINODAL LINE IN THE PbO–B2O3 SYSTEM

ACCORDING LIFGT SCATTERING DATA
Bokov N.A.
Institute of Silicate Chemistry of the RAS, Saint Petersburg
e-mail: bokov@isc1.nw.ru
PbO-B2O3 system is best investigated among the two-component borate systems.
However the information concerning the location of the phase-separation region in this system
do not quite agree with each other. To determine the boundary of the immiscibility region in
these studies was used the method of the visual observation in compliance with the effect of
the arising or the disappearance of opalescence caused by the formation of two-phase
structure.
The present investigation devotes to the experimental determination of the spinodal line
position based on the study of the temperature dependence of the light scattering intensity by
the investigated melts being in the single phase (homogeneous) state.
The intensity of scattered light was measured in high temperature light diffractometer
which was created in our laboratory. The source of light was the laser, which had the power
about 100 mvt and the wavelength of radiation λ = 532nm.
The value obtained experimentally was the values of the polarized, Vv, and depolarized,
Hv, components of scattered light intensity, which were presented in benzene units. The angle
dependences of the scattered components were measured in the range from 400 to 1400.
The melt under investigation put in the cylindrical cell, which was make from the quartz
glass. The cell was covered by the quartz plate and was placed into the diffractometer furnace.
The lead-borate melts were obtained as the result of remelting of the corresponding
glasses prepared earlier directly in the diffractometer furnace at the temperature 850 - 9000С.
The content of PbO was determined by the chemical analysis of the samples.
The scattered intensity features by the PbO-B2O3 melts were studied in the
concentration range from 0.6 to 22 mol. % PbO, being in the single phase state. It was shown
that at these conditions the main part of total scattered intensity by the subjects studied was
due to the concentration component. It was found also that the anisotropic scattering was
negligible.
Based on the data obtained using the theory of the critical phenomena the spinodal
temperatures Тs corresponding to the border of the absolute instability of the melt studied
were determined. The values the spinodal temperatures obtained are presented in the Table.
Table. Spinodal temperatures in the PbO-B2O3 system.
Content PbO,
0.60 1.76 3.56 5.20 5.21 11.59 22.31
mol. %
Spinodal
17 654 713 760 766 790 800
temperature, 0С
This study was carried out based on the financial support by the Russian Foundation
for Basic Research according to the project No. 10-03-00705.
THERMODYNAMIC STABILITY OF MIXED OXIDE ON THE BASIS

OF BITHMUTH, RENIUM, AND GADOLINIUM
Bryzgalova A.N.1, Matskevich N.I.1, Wolf Th.2, Chupakhina T.I.3,
Matskevich M.Yu.1, Anyfrieva O.I.1
1
Nikolaev Institute of Inorganic Chemistry, Siberian Branch
of the Russian Academy of Sciences, Novosibirsk
e-mail: nata@niic.nsc.ru
2
Karlsruhe Institute of Technology, Institute of Solid State Physics, Karlsruhe
3
Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences,
Ekaterinburg
As known, δ-Bi2O3 is the best oxygen ion conductor at temperatures within its stability
range. Unfortunately, the δ –Bi2O3 form is stable between 729 ºC and the melting point 827
ºC. Both isovalent and aliovalent substitution of Bi3+ by other cations can lead to a
stabilization of the fluorite based structure to room temperature. Recently a new family of
stabilised δ – Bi2O3 materials of composition Bi12.5R1.5ReO24.5 (R = Y, La, Nd, Pr, Er, Eu) has
been described. These materials in contrast to the two-dimensional properties of BIMEVOX
(Bi2MeCuxV1-xOy) are isotropic.
In the present paper we report the synthesis of new phase on the basis of bismuth oxide,
rhenium oxide and gadolinium oxides (Bi12.5ReGd1.5O24.5) and its thermodynamic stability.
Polycrystalline samples of Bi12.5Gd1.5ReO24.5 were prepared for the first time from
bismuth oxide (Bi2O3), gadolinium oxide (Gd2O3) and rhenium oxide (Re2O7). Phase purity
and composition of Bi12.5ReGd1.5O24.5 was confirmed by X-ray power diffraction (XPD)
using a STADI-P, Stoe diffractometer, using Cu-Kα1 radiation and a WDX-spectrometer (ARL
ADVANT'XP). The samples were shown to be phase-pure ceramics with a cubic structure
(space group Fm3m).
We used solution calorimetry to determinate the thermochemical characteristics of Bi12.5
Gd1.5ReO24.5. In order to determine the molar enthalpy of formation of bismuth perrhenate
doped by gadolinium oxide we constructed the thermochemical cycles, in which we compare
the enthalpies of dissolution of Bi2O3, Gd2O3 and Re2O7 with the enthalpy of dissolution of
Bi12.5 Gd1.5ReO24.5. We used 2 M HCl as solvent.
The measured enthalpies of dissolution were used to calculate the molar enthalpy of
formation of the investigated phase from binary oxides (∆oxHo). Then, we calculated the
standard molar enthalpy of formation using data of enthalpies of formation of Bi2O3, Re2O7,
Gd2O3.
In order to understand whether the Bi12.5Gd1.5ReO24.5 phase is stable or unstable with
regard to decomposition to the 6.25Bi2O3 + 0.75Gd2O3 + 0.5Re2O7 mixture it is necessary to
know the Gibbs energies (∆G = ∆H - T∆S). There is no entropy data for Bi12.5Gd1.5ReO24.5 in
the literature. But it is known that the entropy of complex oxides is close to sum of entropy of
the binary oxide mixtures. Using this rule we can say that ∆oxG will be close to ∆oxH. So,
bismuth perrhenate doped by gadolinium oxide is thermodynamically stable with regard to its
decomposition into binary oxides at room temperature.
This work is supported by Karlsruhe Institute of Technology (Germany), Russian Fund

of Basic Research (Project № 13-08-00169) and Program of Fundamental Investigation of
Siberian Branch of the Russian Academy of Sciences.
NEAR SOLVATION AND MOBILITY OF PROTON AND HALIDE IONS

IN PROTOLYTIC SOLVENTS
Bulavin V.I.1, V’unnik I.N.2
1
National Technical University «Kharkiv polytechnic Institute», Kharkiv
e-mail: bulavin@kpi.kharkov.ua
2
V.N. Karazin Kharkiv National University, Kharkiv
Limiting molar electric conductance a proton ( λ0 ( MH + ), where M – is a solvent
molecule) and halide ions (Cl -, Br -, I-) in water and primary alcohols from methanol to n-
pentanol are obtained and analyzed at 5 - 55 0С. The method of division of λ0 ( MH + ) values
into hydrodynamic ( λi0 ( MH + ) hydr ) and prototropic (relay) ( li0 ( MH + ) rel ) components is
offered and proved. Oscillation on dependence of a part of a relay component
ll 0 + +
i ( MH ) rel / 0 ( MH ) on the number of carbon atoms in an alcohol molecule is established
[1]. The scheme of assumed mechanism of proton transfer (PT) in n-alcohols by a relay
mechanism is proposed. According to this scheme, PT occurs in the volume of "free" solvent
in which H-bonds are broken [2]. Each molecule in "free" solvent takes part in dipole and
dispersive interactions with the nearest solvent molecules. It is possible to consider the stage
of close approach of an ion MH+- ion and a solvent molecule to a distance, sufficient for their
consideration as a uniform kinetic formation, as a stage of a proton transfer by ion MH+- ion
by a hydrodynamic mechanism.
Attractive coefficient of friction (ζattr) for МН +, Cl-, Br- and I- -ions in water and n-
alcohols from methanol to n-pentanol is calculated and analyzed at 5 - 55 0С. It is shown [2],
that negative value ζattr corresponds to ions with solvation while positive value ζattr – to ions
with positive solvation. Negative solvation of a proton in water and n-alcohols and of halide
ions in water is established. So, negative solvation of a proton is caused by its resolvation
occurring in the course of proton transfer by a relay mechanism. For Cl -, Br -, I - halide ions
positive solvation in n-alcohols and negative solvation in water is observed. However, for Cl–-
ion in water a shift from negative to positive solvation takes place at a temperature of
approximately 300 K, which is in agreement with literature data.
Near solvation of МН +-ion is defines it abnormally high electric mobility. As is known,
it is caused by ion-molecular and intermolecular interactions at short distances. In this
connection attractive coefficient of friction has been presented as a sum of 2 components:
ς=attr ς attr
MM
+ ς attr
IM
. These components take into account short-range molecule-molecule ( ς attr
MM
)
and ion-molecule ( ς attr
IM
) interactions. The calculation procedure of ς attr
MM
and ς attr
IM
values is
offered.
Dependence ζattr for MH+ on dispersion energy (Udisp) of n-alcohols is linear, and on
energy of H-bond is not linear. Thus, the growth of negative solvation of MH +-ion is
promoted by dispersion energy growth in n-alcohols.
Linear dependence ζattr on Udisp allows to predict values of ζattr in other primary alcohols
and, thus, to predict negative solvation of a proton in these solvents.
References
1. Bulavin V.I., V’unnik I.N. //Ukr. Khim. J., 2011. V. 77, № 4. P. 84-91.
2. Bulavin V.I., V’unnik I.N. // Ukr. Khim. J., 2012. V. 78, № 8. P. 82-91.
UNEXPECTED TRANSPORT OF IONIC LIQUIDS

THROUGH CARBON NANOTUBES
Chaban V.V.1, Lipeiko A.V.2, Kolesnik Ya.V.2, Kalugin O.N.2
1
MEMPHYS – Center for Biomembrane Physics, Odense M. Denmark
e-mail: vvchaban@gmail.com
2
e-mail: onkalugin@gmail.com
Because of their outstanding versatility, room-temperature ionic liquids (RTILs) are
continuously exploited in ever increasing number of novel fascinating applications. The
examples include, but are far not limited to reaction medias, chromatography, electrolytes, gas
separations, extractions, nanotechnologies, making RTILs one of the holy cows in materials
science. Most recent studies successfully employed RTILs in carbon nanotubes (CNT) - based
supercapacitors [1], RTIL-CNT composite materials [2], and for dissolution of CNT bundles
[3].
We are the first to report that CNT is able to enhance translational dynamics of certain
types of RTILs, whilst this same CNT hinders mobility of other types of RTILs. The diffusion
increase in confinements, as compared to the bulk phase, is a unique phenomenon, never
observed for any molecular liquid, except for water [4]. We provide a comprehensive RTIL-
centered reconnaissance of the non-covalent energetics and local structure in the RTIL-
containing CNTs and formulate a consistent set of rules, allowing for prediction of ionic
transport behavior based on the input parameters, such as polarity of RTILs, width of CNT,
and electrostatics/dispersion ratio. The analysis has been conducted using the state-of-the-art
atomistic-precision molecular dynamics simulations and ab initio modelling.
Our findings and observations of highly mobile ions inside CNTs open a number of new
avenues for applications of these and relative systems in nanofluidics, electrochemistry, and
separation applications.
References
1. Y. Shim and H. J. Kim, Nanoporous Carbon Supercapacitors in an Ionic Liquid: A
Computer Simulation Study. ACS Nano 4, 2345–2355 (2010).
2. M. Tunckol, J. Durand, P. Serp. Carbon nanomaterial–ionic liquid hybrids. Carbon 50(4),
4303-4334 (2012).
3. J. Wang, H. Chu, Y. Li, Why Single-Walled Carbon Nanotubes Can Be Dispersed in
Imidazolium-Based Ionic Liquids. ACS Nano, 2(12), 2540–2546 (2008).
4. G. Hummer, J. C. Rasaiah & J. P. Noworyta. Water conduction through the hydrophobic
channel of a carbon nanotube. Nature 414, 188-190 (2001).
USING NEW PRINCIPLES OF CLASSIFICATION

OF BIAZEOTROPIC TERNARY SYSTEMS DIAGRAMS
Chelyuskina T.V.
e-mail: tvchelyuskina@mitht.org
One of the trends of thermodynamic-topological analysis of the phase equilibrium
diagrams structures is to work out new principles of classification of vapor-liquid equilibrium
diagrams of systems, which include biazeotropy (the presence of two azeotropes on the
concentration simplex element) in one form or another [1], and the definition of total number
of types of phase portraits of such systems.
This paper deals with investigation of biazeotropic three component systems as the first
representatives of multicomponent systems. Earlier class of three component system was
determined only by number of singular points of different constituents and designated as
3.M2.M3, where M2 - the total number of binary azeotropes, M3 - the total number of ternary
azeotropes. In the presence of biazeotropy diagrams structures with different binary
constituent may correspond to the same class. To account this situation, we have suggested the
principle of differentiation of binary constituents from the number of binary azeotropes in
them. That is, the value of M2 should be presented as a set of numbers of singular points,
belonging to various binary constituents (biazeotropic, monoazeotropic and zeotropic):
M 2(1) + M 2(2 ) + M 2(3 ) = M 2 , where each term M 2(i ) can be 0; 1; 2, and M2, accordingly , 0; 1; 2; 3; 4;
5; 6. Then the class of the mixture can be written as: 3.[M 2(1). M 2(2 ). M 2(3) ]. M 3 .
If we put: N1 (С1) – the number of nodes (saddles) at the vertices of a triangle; N2 (С2) –
the number of binary nodes (saddles); N3 (С3) – the number of ternary nodes (saddles),
obviously that N1 = 0, 1, 2, 3; C1 = 3, 2, 1, 0; N1 + C1 = 3; N2 + C2 = M2; N3 + C3 = M3; М3 = 0,
1, 2.
Based on the above we have given new modification of the equation of azeotropy rule in
the Serafimov’s form for three component systems: 2M 3 + [M 2 + M 2 + M 2 ] + N1 − 1 = 2C3 + C 2 and
(1) (2 ) (3 )
2
created classification and atlas of diagrams structures of vapor-liquid equilibrium of
biazeotropic three component systems (74 types of diagrams). All known and newly
discovered real three-component systems can be put in correspondence to each type.
Thus based on data about vapor-liquid equilibrium from computer simulation, we have
determined characteristics of binary and ternary azeotropes and set classes, types and subtypes
of the diagrams structures of vapor-liquid equilibrium of ternary biazeotropic systems formed
by the base biazeotropic constituent benzene – perfluorobenzene and the third component:
methyl propionate, tert amyl alcohol, ethanol, n-propanol, methyl ethyl ketone.
Wish to thank Professor L.A. Serafimov for discussing of problems of biazeotropy.

The work is carried out at financial support of the Russian Fund of Basic Researches
(the project № 11-03-00295-a).
Reference
1. L.A. Serafimov, T.V. Chelyuskina. Principles of classifying diagrams for different types of
biazeotropic ternary mixtures. The Journal of Physical Chemistry. 2011. V. 85, № 5, p. 854-
863.
THE RESEARCH OF VAPOR LIQUID EQUILIBRIUM AT DIFFERENT PRESSURES

AND REVELATION OF BIAZEOTROPY IN THE SYSTEM
METHYL ETHYL KETONE–PERFLUORBENZENE
Chelyuskina T.V., Perenlei A.
e-mail: tvchelyuskina@mitht.org
At the present time it is actually to extend lots of biazeotropic mixtures containing real
substances. Therefore, the purpose of this work is to study vapor liquid equilibrium at different
pressures in the system methyl ethyl ketone – perfluorbenzene which formed by closely boiling
components. The biazeotropic systems can be found in both field experiments and by
mathematical modeling based on local compositions equations.
As a method of investigation we selected calculating experiment by using of modern
software. Mathematical simulation of vapor liquid equilibrium is carried out with use of Wilson
equation at assumption of ideal behavior of vapor phase.
We evaluated the small parameters of Wilson equation. By means of obtained parameters is
carried out mathematical simulation of vapor liquid equilibrium and azeotropy in this system at
760 mm Hg. It is established that the system methyl ethyl ketone - perfluorbenzene contains
negative azeotrope at atmospheric pressure.
The received data of vapor liquid equilibrium are processed for calculations of distribution
coefficients of a component between vapor and liquid phases. It is found that there is a minimum
in a range of concentration enriched by perfluorbenzene on the graphical chart of distribution
coefficient of methyl ethyl ketone from its concentration. On basis of theoretical knowledge
about regularities of the biazeotropic mixture behavior by varying external conditions, we have
predicted the appearance of second (positive) azeotrope in the field of lower pressure.
For studying of evolution of biazeotropy in the system methyl ethyl ketone -
perfluorbenzene is carried out mathematical simulation of vapor liquid equilibrium at pressures
below 760 mm Hg. The presence of biazeotropy is revealed and identified azeotropic
characteristics of the system methyl ethyl ketone – perfluorbenzene in the pressure range 50-560
mm Hg.
In computing experiment it is shown that positive azeotrope is depleted and negative
azeotrope is enriched by methyl ethyl ketone with increasing pressure, that is in accordance with
the Second Law of Vrevsky and confirmed by the relation of vaporization heats of components.
Thus, we have shown for the first time that the system methyl ethyl ketone –
perfluorbenzene contains biazeotropy under certain pressures.
The work is carried out at financial support of the Russian Fund of Basic Researches (the
project № 11-03-00295-a).
THEORETICAL PREDICTION OF IONIC ASSOCIATION CONSTANT

OF ELECTROLYTES USING RAMANATHAN-FRIEDMAN POTENTIAL
Chernozhuk T.V., Kalugin O.N.
V. N. Karazin Kharkiv National University, Kharkiv, Ukraine
e-mail: tanya.chernozhuk@gmail.com
Ionic association constant (КА) is one of the most reliable thermodynamic characteristic
of non-aqueous electrolyte solutions. Experimentally КА value is determined by concentration
dependence of any solution property in the framework of the chemical model which implies
mass action law application. Since an experimental determination of ionic association
constant is labour- and time-consuming procedure, often quite expensive, prediction of КА
values for a wide range of electrolytes, solvents and conditions is important task for physical
chemistry and electrochemistry of solutions.
The statistical mechanics expression for ionic association constant is defined by the
models of a pair interionic interaction potential, Uij (r), and a weight function of the coupled
state, w( r ) :
∞
4π N A 2  U ij ( r ) 
( )
1000 ∫a
=KA r w r exp −  dr . (1)
 k BT 
In turn, the interionic interaction potential Uij (r) can be presented as the sum of Coulomb and
short-range potentials, Uij (r) = U ijCoul (r ) + U ij* (r ) . Thus, the problem of prediction of КА can be
reduced to the problem of evaluation of the short-range potential which incorporates ion
solvation effects.
In order to ascertain the possibility to predict КА value and to establish the influence of
various factors on short-range potential, we have used Ramanasan-Friedman model [1]:
Uij (r) = U ijCoul (r ) + = U ij* (r ) U ij ( r ) =U ijCoul ( r ) + CORij ( r ) + CAVij ( r ) + GURij ( r ) . (2)
Here the term GURij (r) describes the energy of intersection of the ionic solvation shells. It is
defined by the expression GURij ( r ) = AijV( + ) ( Ri , R j , r ) / Vs , where Аij parameter corresponds to
molar free energy of transfer of solvent molecule from ions solvation shells into the bulk
solvent.
Here we present an original technique [2] for calcualtion of the Аij parameter and present
its values for a large set of 1-1 electrolytes in various non-aqueous solvents in a wide
temperature range by experimental data of КА.
The analysis of the calculated data has shown that Аij practically does not depend on
temperature and depends slightly on properties of electrolyte in a given solvent. The
established regularities allow us to predict КА values with sufficient accuracy for the whole
series of 1-1 electrolytes in the given solvent on experimental data only for one electrolyte.
References
1. Ramanathan P. S., Friedman H. L.//J. Chem. Phys., 1971, Vol. 54, № 3, P. 1086-1099.
2. Kalugin O. N., Afanasova T.V., Kolesnik Ya.V.// Bulletin KhNU, 2000, № 495, P. 85-91.
THERMODYNAMIC ANALYSIS OF THE ROLE OF MAGNESIUM AND CALCIUM

CATIONS IN COMPLEX FORMATION OF α-CYCLODEXTRIN
WITH NICOTINIC ACID
Chibunova E.S., Terekhova I.V., Kumeev R.S.
G.A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences, Ivanovo
e-mail: Katerina.Chibunova@yandex.ru
Encapsulation by cyclodextrins based on the inclusion complex formation and widely
used in pharmacy to prolong the drug activity initiates a serious and comprehensive study of
this process. Investigation of the cyclodextrin inclusion complex formation in conditions close
to the physiological environment is one of the perspective and actual directions in this area. In
this connection, the aim of our research is to examine the effects of inorganic salts, which are
the main components of internal environment of living organisms, on complex formation of
cyclodextrins with aromatic carboxylic acids of biological importance.
In this work, complex formation of α-cyclodextrin with nicotinic acid (vitamin B3,
medicine used in the treatment of pellagra) in water and in 0.2M solutions of CaCl2 and
MgCl2 was studied by 1H NMR. Analysis of the calculated thermodynamic parameters of
complexation showed that presence of Ca2+ и Mg2+ in aqueous solution results in decrease of
binding constants, while the effect of these cations on the enthalpy and entropy changes was
insignificant. The obtained results were discussed in terms of possible interactions between
nicotinic acid and cations, which shift the binding with α-cyclodextrin in the direction of
complex dissociation.
This work was supported by the Russian Foundation for Basic Research (grant 12-03-
97516-r-center-a) and the Ministry of Education and Science of the Russian Federation
(project №8839).
SOME BENZTRIAZOLE DERIVATIVES SORPTION THERMODYNAMIC

FROM WATER – ACETONITRILE SOLUTIONS
Dgyabiyeva Ali kyzy S., Kurbatova S.V., Belousova Z.P.
e-mail: curbatsv@samsu.ru
Acetonitril - water mixtures of different compositions apply under conditions of
reversed-phase high-performance liquid chromatograpy (RP HPLC) as eluents. Last
publications show, that there are substantial deviations from the widely applied known
retention models at chromatography of some polyfunctional organic compounds. The most
sufficient deviations take place under azoles sorption on the octadecylsilicagel from acetonitril
- water solution. In particular, it was established, that on the retention factor dependence of
some azoles from the mobile phase composition (acetonitril – water) graph there are points of
extremums while for most connections these dependences, as is generally known, are linear.
Similar extreme dependences are got when some azoles electric conductivity of water -
acetonitrile solutions was investigated. There are maximum and minimum on the dependence
graph of low polar benzodiazepines derivatives entropy and enthalpy from mobile to
stationary phase transfer from composition of mobile phase. This fact is a result of complex
process, which take place in water – acetonitrile solution and resulting from homo- and
heteroassociates formation [1,2].
At present work sorption thermodynamic of some 12 first synthesized benztriazoles
derivatives with different chemical nature substitutes of the nitrogen atoms was investigated.
It was established, that in addition to analytes structure its retention essentially depends on
the eluent composition. Increase in acetonitrile concentration lead to sufficient decrease of
sorption values, so differences between this magnitudes to come into ntgligible. This fact is
evidence of the sufficient role of intermolecular interaction between benztriazoles derivatives
and mobile phase components. For the investigated compounds phenomenon, similar to
entropy and enthalpy compensation effect was established whereby family graphs, wich
characterise dependence of retention factor and organic component concentration under
extrapolation must be intersected at the same coordinate space. By means of Horvats
solvophobic theory physical meaning of such isoparametric point determines dy such
characteristics of chromatographic system as molar volume, dipole moment, polarisability etc.
3 times diminishing of acetonitril concentration following almost tenfold sorption
increase, because of intermolecular interaction between benztriazoles derivatives and mobile
phase components diminishing.
Confirmation of complication water – acetonitrile solutions processes is a substantial
increase of electric conductivity of these solution with a change the concentration of
acetonitril.
References
1. Kurbatova S.V., Kharitonova O.V., Finkel’stein E.E. Russian Journal of Physical Chemistry.
2008. V. 82. №11. P. 2147-2153.
2. Monakhova Yu.B., Mushtacova S.P., Kolesnikov S.S., Gribov L.A. Russian Journal of
Analytical Chemistry. 2011. V.66. №1. P.56-62.
HEAT CAPACITY AND VOLUME PROPERTIES OF SOLUTIONS OF BARIUM

AND CADMIUM IODIDES IN APROTIC DIPOLAR SOLVENTS AT 298.15 K
Doronin Ya. I., Novikov A.N.
Mendeleev University of Chemical Technology, Institute in Novomoskovsk
e-mail: tangar09@mail.ru
Studies of the partial molal heat capacities volume of electrolytes at infinite dilution
have proved to be useful for examining ion-solvent and solvent-solvent interactions in
aqueous and non- aqueous solvents. The actuality of investigation of non-aqueous solutions
was caused by their wide utilization in industry, science and engineering. However the data of
its properties are limited.
Heat capacity Cp and density ρ of solutions of barium and cadmium iodides in aprotic
dipolar solvents N-methylpyrrolidone (MP), dimethylsulfoxide (DMSO), dimethylformamide
(DMFA) and acetonitrile (AN) at 298,15 K were experimentally investigated. For
measurement of Cp hermetic calorimeter with isothermal shell and platinum thermometer
resistence as a temperature transducer were used. The error of Cp measurements were not
more than ±1·10-3 J(g·K)-1 For measurement of ρ the precision picnometric installation (error
±2·10-5 g·cm3) were used. Aprotic dipolar solvents were dried and distilled twice at low
pressure. Karl Fisher titration indicated that the water content was not more than 0,01-0,02%
by weight. The salts were dried under reduced pressure at 353-423K for 8-10 h. All solutions
were prepared by weight in a dry box.
On the base of the data about Cp and ρ apparent molal heat capacities ФС and volumes
ФV of barium and cadmium iodides in aprotic dipolar solvents were calculated. The standard
partial molal heat capacities C P02 and volumes V20 of BаI2, CdI2 in MP, DMSO, DMFA, AN
at 298,15 K being of interest for the thermodynamics of solutions were determined by the
extrapolation of concentrated dependences of ФС and ФV to the state of infinity dilution. The
separation of the C P02 and V20 values into ionic components was performed on the basis of the
C Pi0 and Viо values for the iodide ion in investigated solvents [1, 2] and using the condition
of the additivity of partial molar values.
The standard partial molar heat capacity and volume of an ion can be presented as the
sum of several contributions: the intrinsic heat capacity (volume) of an ion in solution, the
changes in heat capacity caused by solvate formation (excluding specific solvation), the
changes in volume caused by electrostriction and the changes in heat capacity (volume)
caused by reorganization of the primary structure of a solvent and specific interactions
between ions and solvent molecules.
The influence of various physico-chemical characteristics of aprotic dipolar solvents on
the contributions in standard partial molar heat capacity and volume of an ion is discussed.
References
1. Y. Marcus, G. Hefter. Chem. Rev., 2004, 104, 3405-3452.
2. A.N. Novikov. Zh. Fiz. Khimii. 2009, 83, 414-417.
ANALYSIS OF HYDRATION SHELL STRUCTURE FOR HYDROPHOBIC PARTICLES

IN AQUEOUS SOLUTIONS BY COMPUTER SIMULATION MONTE CARLO METHOD
Dunyashev V.S., Lyashchenko A.K.
N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow
e-mail: vsdn2@yandex.ru, aklyas@mail.ru
Computer simulation is the one of basic method for the study of water structure changes
under the influence of hydrophobic particles (HP). It is determined not only by the
intermolecular interactions, but also the appearance of the volume occupied by particle and
inaccessible for the water molecules. In order to separate these two factors determining the
hydrate shell structures, two series of simulations of aqueous solutions with hydrophobic
particles were carried out. In the first set of simulations, monoatomic molecules of neon,
argon and xenon were reproduced by corresponding Lennard-Jones potentials. In the second
series, the model particles with ”hard sphere” potential were chosen to estimate the influence
of excluded volume. Solutions with the HP of radius 1.6Å, 1.9Å and 2.2Å were simulated. It
reproduces the volume of neon, argon and xenon, respectively.The H2O-H2O interactions were
calculated using SPC potential. Simulations by the Monte Carlo method in NVT ensemble
were performed for the systems consist of 511 water molecules + 1 HP (in the case of neon
and argon) and 505 of water molecules + 1 HP (for xenon) in the cubic cell, that corresponds
to the density of water (1 g/cm3).
The radial distribution functions gHP-O, gO-O, gO-H, gH-H, and partial functions
corresponding to different local densities of water molecule environment in different
coordination spheres of dissolved particle were determined. The method proposed in [1, 2] for
pure water was formulated for different types of particles. The functions describing radial and
spatial correlations between HP and molecules of water with identical or different
coordination numbers were considered. Summary and partial spatial functions describing
distribution of water molecules in the near and distant environment spheres of dissolved
particles were determined. Spatial angular correlations between molecules of water on
distances up to 8-10Å from the dissolved particle were established. As a result, we received
the extensive graphic material characterizing of the HP environment in detail. This allowed us
to distinguish long-range effects of hydrophobic hydration, which are specified by the
presence of particles distinguished from water molecules. This effect is important in the case
of the hydrophobic hydration of nonpolar molecules.
This work was supported by RFBR grant No. 12-03-000-62a.
References
1. A. K. Lyashchenko, L. V. Dunyashev, V. S. Dunyashev. J. Struct. Chem. 2006. V. 47,
Supplement. S32-S49.
2. A. K. Lyashchenko and V. S. Dunyashev. J. Mol. Liquids, 2003. V. 106, № 2/3. P. 199-213.
THERMODYNAMICS OF FORMATION OF SOME COORDINATION COMPOUNDS

OF GOLD (V), NICKEL (IV) AND MANGANESE (IV)
Dupal A.Ya., Korunov A.A., Solov'ev S.N., Firer А.А., Shatalov K.I.
Mendeleev University of Chemical Technology of Russia, Moscow
e-mail: snsol@muctr.ru
There were standard enthalpies of formation of AuF5(к) and hexafluoroaurates (V) of some
alkaline and alkaline-earth metals; six hexafluoronickelates (IV) and two hexafluoromanganates
(IV) earlier defined in thesis works of A.P. Voloshko (1986), А.А. Firer (2009), K.I. Shatalov
(2011), А.А. Korunov (2013) on the basis of enthalpies measurement of investigated substances
interreacting with water and water-soap solutions at the Chair of general and inorganic chemistry.
There is evaluation of standard enthalpies of the above mentioned compounds in this work
performed according to Latimer's increments and on the basis of the additive method using
entropies of crystalline fluorides from which the investigated compound formation can be
presented.
The found values of entropies have allowed appraising Gibbs energies of measures under
discussion. The standard values of enthalpies and Gibbs energies, substances enumerated above
are listed in the table.
All the studied compounds are very persistent thermodynamically (large in absolute
magnitude negative formation Gibbs energy), thereby they are quite energetic oxidizers.
There is stabilization of Au+5 and Ni+4 conditions (electronic configuration 5d6 and 3d6)
cleanly traced in passing from fluorides AuF5 and NiF4 to coordination compounds. It is quite
simply explained with the maximum energy of stabilization in an octahedral ligand field of the
strong field within the limits of the crystal field theory. It is not observed for Mn+4.
Table
Standard enthalpies and Gibbs energies of investigated compounds formation
Compound ∆fH◦, kJ/mol ∆fG◦, kJ/mol
(XeF5)2[MnF6] (к) - 1185 ± 18 ―――
(ClOF2)[MnF6] (к) - 1643 ± 11 - 1323 ± 16
K2[NiF6] (к) - 2006 ± 8 - 1857 ± 12
Ca[NiF6] (к) - 1955 ± 7 - 1815 ± 11
Ba[NiF6] (к) - 1934 ± 8 - 1799 ± 12
(NO2)2[NiF6] (к) - 1096 ± 8 - 802 ± 11
(ClOF2)2[NiF6] (к) - 1154 ± 8 - 831 ± 15
Ni[NiF6] (к) - 1630 ± 9 - 1495 ± 11
AuF5(к) - 473 ± 4 - 360 ± 8
Na[AuF6] (к) - 1095 ± 7 - 957 ± 10
K[AuF6] (к) - 1159 ± 7 - 1021 ± 10
Rb[AuF6] (к) - 1145 ± 7 - 1008 ± 10
Ba[AuF6]2 (к) - 2341 ± 10 - 2047 ± 17
Ba[AuF6]2•4KrF2 (к) - 3036 ± 11 ―――
As is evident from the table enthalpies and Gibbs energies values of hexafluoroaurates (V) and
hexafluoronickelates (IV) of alkaline and alkaline-earth metals are close independent from cation in
terms of the unit charge.
Because of large negative values of Gibbs energies of hexafluoronickelates (IV) formation it is
hardly improbable that they can be used as a fluorine source. From our point of view utilization of these
compounds as fluorinating agents in a non-aqueous media of HF(ж) kind is more promising.
RALEIGH LIGHT SCATTERING IN PHYSICAL CHEMISTRY

OF LIQUIDS AND MIXTURES
Durov V.A.
Faculty of Chemistry, Lomonosov Moscow State University, Moscow
e-mail: durov@phys.chem.msu.ru, http://www.chem.msu.su/eng/people/durov.html
The author’s results [1–7] concerning development of the theory of isotropic and
anisotropic fluctuations in liquids and applications to molecular models of integral Raleigh
light scattering in liquids and mixtures are discussed. The special attention is paid to the
problem of constructing generalized thermodynamic and molecular models of the system with
internal variables of various kind and tensor dimension and applications to fluctuations, light
scattering and relaxation phenomena.
The methods for deriving thermodynamic potentials of the non-equilibrium states of
matter characterized by the internal parameters of various nature and tensor dimension have
been developed. The expressions for the fluctuating parts of Helmgoltz energy F and Gibbs
energy G for the closed systems, as well as the grand thermodynamic potential Ω for the open
non-equilibrium systems were derived [1–2]. Models with discrete and continuous
distributions of parameters of state, described by the scalar, vector, and tensor internal
parameters are presented. General thermodynamic relationships for the fluctuating anisotropic
states of liquids were established. The contributions from fluctuations of internal parameters
to thermodynamic properties (heat capacity, compressibility, thermal expansion coefficient,
etc.) are discussed. The notion of equilibrium and nonequilibrium (according to internal
variables) fluctuations is introduced. It is shown that the fluctuations of extensive variables
(energy, entropy, volume) are defined by classic expressions with equilibrium susceptibilities
(heat capacity, compressibility), related to the constant thermodynamic affinity of internal
process, while the fluctuations of intensive variables (temperature, pressure) are expressed
through instant values of susceptibilities, related to constant extent of internal process.
The theory of Rayleigh light scattering in relaxing media, taking into account the
internal field effects is constructed. The expression for local field for anisotropic states of
matter is given [6]. Theory of anisotropic light scattering is constructed taking into account
the internal field effects with generalized Lorenz-Lorentz formula for weakly nonequilibrium
anisotropic fluctuation states of matter, valid for molecular liquids with molecular
polarizability tensors of general form, not only with axial symmetry [8]. The correlation of the
density and concentration fluctuations in mixtures was established. The new contributions to
Rayleigh light scattering due to fluctuations of the internal parameters were revealed. They
can be comparable with the contributions from density fluctuations.
The relationship between internal parameters and molecular models of liquid systems is
discussed with emphasis on thermodynamic and structural parameters of supramolecular
ordering in liquids. The optic correlation factors [1] (similar to Kirkwood dipole correlation
factor in the theory of dielectrics [1]) are introduced. They reflect correlations of main axes of
polarizability tensors of molecules in liquids. Their relationships with thermodynamic and
structural parameters of supramolecular aggregation in nonideal liquid systems are
established, for various topologic forms of supramolecular species.
The results on modeling supramolecular ordering in molecular mixtures, self-organized
by noncovalent molecular interactions like H-bonding are presented in the framework of
unified approach for describing and analyzing their thermodynamic, dielectric, optic, and
kinetic properties [1–2].
References
1. Durov V.A., In Concentrated and Saturated Solutions; A.M. Kutepov, Ed.; Nauka:
Moscow, 2002, p.170. (In Russian).
2. Durov V.A. // J. Mol. Liquids 2003, 103-104, 41.
3. Durov V.A. // Pure and Appl. Chem. 2004, 76 (1), 1.
4. Durov V.A. In: Novel Approaches to the Structure and Dynamics of Liquids:
Experiments, Theories, and Simulations; / J. Samios, V.A. Durov, Eds. / NATO Science
Series. II. Mathematics, Physics and Chemistry. V.133. Dordrecht, Kluwer, 2004, 17-40.
5. Durov V.A. // J. Mol. Liquids 2004, 113, 81.
6. Durov V.A. // Zh. Fiz. Khim. 2005, 79, 9, 1618.
7. Durov V.A. / Durov V.A., Ageev E.P. Thermodynamic Theory of Mixtures.
(Monograph in Russian). Editions 1-3. Мoscow: 1987, 2002, 2010. Chapter 7.
8. Kielich S. Molecular Nonlinear Optics, Nauka Publishing Co., 1981. (Translated to
Russian, 1981)
KINETIC PARAMETERS OF THERMAL DECOMPOSITION

OF PURE ALIPHATIC ALCOHOLS AND THEIR AQUEOS SOLUTIONS
Dzhapparov T.A., Bazaev A.R.
Institute of Problems of Geothermy, Daghestan Scientific Center of the Russian
Academy of Sciences, Makhachkala, Republic of Daghestan, Russian Federation
e-mail: timur507@mail.ru
Aliphatic alcohols and their water solutions in supercritical conditions are widely used
as solvents in such technological processes as supercritical water oxidation (SCWO) and
supercritical fluid extraction (SCFE). Thermal stability is one of the important requirements
that one must take into account in choice of solvent in supercritical conditions.
Previously we reported about experimental values of starting thermal decomposition
temperatures of aliphatic alcohols (methanol, ethanol, 1-propanol and 1-butanol) in water
solutions and their dependences of composition (0.2, 0.5. 0.8, 1 mol fraction of alcohol) and
number of carbon atom [1,2].
In this work we present polynomial equation which shows dependence of starting
thermal decomposition temperatures (TH) of aliphatic alcohols (methanol, ethanol, 1-propanol
and 1-butanol) and their water solutions on composition (x) and number of carbon atom (C):
T ( x, C ) = 23.622 x 2 − 65.617 x + 1.25C 2 + 7.25C + 551.513 (1)

н
Also by the method of pressure increasing at constant temperature in a closed system we

calculated kinetic parameters (rate constant and activation energy) of thermal decomposition
of pure aliphatic alcohols and their water solutions. Reaction of thermal decomposition of
alcohols has first order, so to calculate rate constants we used next formula [3-5]:
dp =k ⋅p ,
dτ k = 1 ⋅ dp (2)
p dτ
where k – rate constant, p – initial pressure of the system, dp/dτ – change of pressure in time
(rate of reaction).
References
1. Dzhapparov T.A, Bazaev A.R. Teplophizika and aeromechanica. 19 (6). 2012. 793.
2. Dzhapparov T.A, Bazaev A.R., Karabekova B.K. XVIII International Conference on
Chemical Thermodynamics in Russia Samara, Russian Federation, October 3-7, 2011.
3. Zhorov Yu. M. Kinetic of technical organic reactions. M; 1989. P. 384.
4. Kondratyev V.N., Nikitin E.E. Kinetic and mechanism of gaseous reactions. M;. 1984. P.
558.
5. G. R. Freeman, C. J. Danby and SIR Cyril Hinshelwood. Proceedings of the Royal Society
of London. Series A, Mathematical and Physical Sciences, 1958. V. 245, №1240. P. 28
PVTX PROPERTIES OF BINARY MIXTURES OF (WATER + GLYCEROL)

IN THE RANGE FROM 278.15 TO 323.15 K AND FROM 0.1 TO 100 MPA
Egorov G.I., Makarov D.M., Kolker A.M.
e-mail: gie@isc-ras.ru
Variation of a liquid mixture volume with composition, temperature, and pressure, is an
important source of information on peculiarities of interactions between the mixture
components. If, at least, one of the components has the spatial hydrogen-bonds network then
the mixture properties will change in a special way. Glycerol, as well as water, is referred to
such substances. The intramolecular hydrogen bond in glycerol molecule stipulates the
specific character of changes of volume properties of the water – glycerol system.
It is known that glycerol molecule can from 126 theoretically possible conformers [1,2].
The solvent is characterized by intra- and intermolecular H-bonds formation. Glycerol can
exist in liquid, crystal, and glassy state. In liquid state, as supercooled liquid, it is before -86
ºС. Glycerol molecule forms 6 base conformers [1,3,4] and three of them exist in the liquid
phase: αα, αγ, and γγ. At temperatures a little bit higher than the freezing point in the liquid
glycerol only 50% of its molecules are accounted to αα conformation, i.e. that the crystal can
form the transition of other conformations into αα type is required. All conformations
participate in intermolecular H-bond formation, except γγ one where all three hydroxyl groups
are involved in the intramolecular H-bond formation.
Thermal properties of glycerol at temperatures higher than its freezing point characterize
it as a “normal” liquid. However at lower temperatures glycerol, being in supercooled state,
displays some peculiarities. Within the present work the results of experimental study on
compressibility of aqueous glycerol mixtures over the pressure range from 1 to 100 MPa and
at temperatures from 278.15 to 323.15 К, as well as of the density measurements at
atmospheric pressure, are performed. From the data obtained the following molar parameters
were calculated: isothermal compressibility, isobaric expansibility, thermal pressure
coefficient, excess volume, partial molar volumes of the components, and internal pressure.
Also limiting partial molar volumes of the mixture components were calculated. The extremes
observed on “property-composition” dependences in water-glycerol mixture are explained by
the process of water order destruction and the shift of glycerol conformational equilibrium.
This work was supported by the Russian Foundation for Basic Research (project 12-03-
97525-r_centre_а).
References
1. C.S. Callam, S.J. Singer, T.L. Lowary, C.M. Hadad J. Am. Chem. Soc. 2001, 123, 11743-
11754
2. J. J. Towey, A. K. Soper and L. Dougan Phys. Chem. Chem. Phys., 2011, 13, 9397–9406
3. R. Chelli, P. Procacci, G. Cardini, R.G. Della Valle, S. Califano Phys. Chem. Chem. Phys.,
1999, 1, 871-877
4. R. Chelli, P. Procacci, G. Cardini, S. Califano Phys. Chem. Chem. Phys., 1999, 1, 879-885
INFLUENCE OF H-BONDING ON THERMODYNAMICS OF PHASE TRANSITIONS

IN LIQUID CRYSTAL SYSTEM
Efremova E.I.1, Kudryashova Z.A.1,2, Nosikova L.A.1,2, Kiselev M.R.2
1
2
Institute of Physical Chemistry and Electrochemistry of RAS, Moscow
In the present work it is considered thermodynamic of phase transition in system, which
consists of nematogen p-n-heptyloxybenzoic acid (I) and smectogen p-n-octyloxybenzoic
acid(II). Phase diagram was got by metods of thermal analysis (PPM, DSC). Polymorphic
modification of components based on the original acids are observed in the system.
Analysis of the enthalpy of melting into the mesophase mixtures showed a reduction of
the energy barrier as compared to the pure components. So for the initial acid and mixtures
similar in composition to the pure components (70 to 90 mol.%), the total heat of the
transition Cr → Sm is 13-27 kJ / mol. In the range of compositions from 30 to 70mol. % I
enthalpy decreases to 9.8 kJ / mol. It is assumed that the ratio is close to the equivalent system
becomes more thermodynamically stable in the mesophase and the temperature interval of
existence of liquid crystalline phases extends in comparison with initial components. In the
system for other phase transitions, such as Sm → N and N → I no significant differences in
the thermal effects have been observed and the enthalpy of phase transitions are 1 and 3 kJ /
mol, respectively. Hydrogen bonds promote the formation in the system of additional nematic
subphase. Transitions between subphases are recorded in the entire composition of only using
PPM (Fig. 1).
a b
Fig. 1. Texture nematic subphase of a mixture of the p-n-heptyloxybenzoic

and p-n-octyloxybenzoic acids a) N1, b) N2.
THERMODYNAMICS OF DISSOLUTION NONELECTROLYTE WITH THE POSITION

OF THE SCALED PARTICLE THEORY
Fabinskiy P.V., Fedorov V.A.
Siberian State Technological University, Krasnoyarsk
e-mail: pvfab@ngs.ru
Solubility is one of the most important physico-chemical characteristics of the chemical
compounds. However, the modern theory of solutions does not allow sufficiently accurately
predict the magnitude of solubility of a chemical compound, the dependence of the nature of
the solute and the solvent. Therefore, so far, one of the main areas is experimental precise
determination of solubility. Solubility of individual compounds is determined by the
thermodynamic parameters of this process. The most complete quantitative interpretation of
the thermodynamic properties of solutions of non-electrolytes through the mechanism of
formation of a cavity in the solvent developed the theory of scale particles (Scaled Particle
Theory, SPT). In accordance with the theory of SPT, the more the volume of the cavity,
occupied by a molecule in solution, the more deposits («energy costs») from its formation in
∆Hsolv and, thus, in ∆G0solv of process of dissolution of the individual compounds.
In the present work, on the example of ferrocene (Fec), acetylferrocene (AF) and
diacetylferrocene (DAF), shows an approach to the calculation of the volume of the cavity,
occupied by a particle after the dissolution of the source individual crystalline substance of
crystallographic data. From the experimentally obtained by analyze X-ray structure of the data
to calculate the volume of the molecules soluble compounds (V), and, consequently, volume
of the cavities in which they will be placed after the formation of the appropriate chemical
form in solution (Table 1).
Table 1. The volume of cavities molecules ferrocene and its oxygen-containing
derivatives on the analyze X-ray structure data
Molecule Fec АF DAF
3
V, Å 203.1 250.5 287.6
Using the computer program calculated energy Gibbs of formation of the cavity (∆Gºcov,
298.15 K) upon the dissolution of the compounds in alcohols (Table. 2).
Table 2. The calculated values of ∆Gº at 298.15 K
Solvent Fec AF DAF
Methanol 17.7 20.7 22,0
Ethanol 14.9 18.4 19.8
Isopropanol 13.8 17.4 19,0
Propanol 13.2 16.9 18.5
Found satisfactory linear correlation between the values of the ∆(∆Gºsol) and ∆(∆Gºcov)
when you click on substances: Fec > AF > DAF. Energy transfer between alcohols AF and
DAF compared with those for the Fec, get the specifics. It is quite obvious that their cause in a
very high level of compensation of the deposits of values ∆H and T∆Sº (at the level of more
than 90 %) in ∆Gºsolv. Thus, the main defect of the Scaled Particle Theory - the lack of a
correct account of variability in levels of entropy contributions to ∆Gºsol, which is nontrivial
depends on the nature of the solvent and on the nature of the individual substances.
HYDRATION STRUCTURE OF L-PROLINE FROM THE DATA

OF THE INTEGRAL EQUATION METOD IN THE RISM APPROACH
Fedotova M.V. 1,2, Dmitrieva O.A.2
1
e-mail: mvf@isuct.ru
2
Ivanovo State University, Ivanovo
It is known, that amino acids are the moieties of many proteins and peptides as well as
peptide hormones and antibiotics and participate in human regulation of the vital processes
including metabolic ones. Amino acids similar to other biomolecules are functioning in an
aqueous environment in living organisms therefore their hydration plays important role in
many biochemical processes. Among α-amino acids L-proline (molecular form is C5H9NO2)
entering into the composition of almost every protein is one of the coding amino acids with
amino group which is a fragment of heterocycle. One of the most important functions of
proline is protective function. In particular, it participates in cell protection from injuries
caused by freezing and fluid loss [1]. At the same time, for the moment the structural
investigations of L-proline(aq) necessary for understanding of a molecular picture of
biomolecules hydration and for establishing of structural mechanisms of different biochemical
processes in living organisms are practically absent.
We present the results of the hydration features study for L-proline zwitterion (L-Pro-
ZW) in water at ambient conditions (298 K, 0.1 MPa) by the integral equation method. The
calculations of hydration structure have been performed in the 1D- and 3D-RISM (Reference
Interaction Site Model) approaches. According to the results of calculations, the total
hydration number of L-Pro-ZW(aq) is ~25.4. The average number of water molecules in the
nearest surroundings of the –NH2+ group is ~4.5. But only ~1.7 water molecules are H-bonded
with this group. The hydration shell of the –COO- group consists of 7.5 water molecules. The
average number of H-bonds formed by the –COO- group is ~2. The obtained data do not indicate
H-bonding between the nitrogen atom of the amino group and water molecules. Earlier we have
received the similar result for glycine zwitter-ion in water [2]. It has been established that
water molecules are interacting weakly with a hydrophobic pyrrolidine ring of L-proline.
Analysis of the spatial distribution functions shows a preferable arrangement of ~0.5 water
molecule above and under a plane of the ring at the distance of ~0.35 nm from the ring center.
03-97508–r_centre_а).
References
1. Rudolph A.S., Crowe О.Р. Biophys. J., 1986, 50, 423-430.
2. Fedotova M.V., Kruchinin S.E. J. Mol. Liq., 2012, 169, 1-7.
TOPOLOGY OF THE MOLECULAR NANOSTRUCTURES IN ALCOHOLS SOLUTIONS

ACCORDING TO THE MOLECULAR DYNAMICS SIMULATION
Firsov D.A., Khondar O.G., Anuchin K.M., Klimov A.V., Tolmachev A.M.
e-mail: firsoff@mail.ru
We used our original algorithm for processing of trajectories, obtained by molecular
dynamics (MD) using graph theory (MDTG) [1] for the study of associates formed by
hydrogen bonds in alcohols solutions. The classic molecular dynamics (MD) calculations with
periodic boundary conditions were carried out. For the simulations the scalable MD package
NAMD [1] and TINKER [2] and OPLS-AA force field were used. The modeling cell (see
fig.) was a parallelepiped (in most simulations cases with dimensions 40×40×200 Å)
containing two perfectly elastic walls (in z-direction). In x and y directions the periodic
boundary conditions were put in. For
localization of the liquid phase at
one side of the cell the bottom layer
of liquid was frozen.
Thus, after an initial period of
relaxation (200 ps) at thermostating,
the system in thermodynamic
equilibrium, both within itself and Fig. The scheme of the modeling cell for MD simulation.
with the gas phase was prodused. On
the 2nd step (3–5 ns) trajectories of investigated systems were stored and used for the
topological analysis.
The developed method of the molecular dynamic calculations in the model cell
containing two phases: liquid solution and vapor phase, allowed us to determine molecular
nanostructures in solution in the absence of data on their densities. At the analysis using the
original software all molecular nanostructures formed by hydrogen bonds observed in each
snapshot were identified and stored. Then, the data on the whole trajectory were averaged, and
the average concentrations of molecular nanostructures (dimers, trimers, and so on) in the
solutions were obtained. At the next step of the analysis the detailed study of the isomeric
composition of topological isomers (chains, branched chains, loops, and so on) for a number
of associates was carried out.
The quantitative data on the concentration dependencies of the isomeric composition
and structural and energy characteristics of molecular nanostructures in liquid solutions,
ethanol-methanol, ethanol-water and others on the temperature and solution composition were
obtained.
References
1. A.M. Tolmachev, G.O. Khondar, K.M. Anuchin, A.V. Kucherov, T.V. Bogdan, Colloid. J.,
V. 71, N 6, P. 861–868 (2009)
2. James C. Phillips, Rosemary Braun, Wei Wang, James Gumbart, Emad Tajkhorshid,
Elizabeth Villa, Christophe Chipot, Robert D. Skeel, Laxmikant Kalé, Klaus Schulten, J.
Comp. Chem., 26(16), 1781–1802 (2005)
PHYSICO-CHEMICAL BASIS OF AZEOTROPIC MIXTURES SEPARATION

IN THE PRESENCE OF ADDITIONAL SUBSTANCES
Frolkova A.K.
e-mail: frolkova@mitht.ru
A large group of special methods of complex multicomponent mixes separation includes
the processes occurring in the presence of additional substances of varying volatility. It
includes, first of all, extractive (autoextractive) and its symmetric process – reextractive
rectification. It is possible to use practically non-volatile separating agents (SA), including
salts and ionic liquids, semi-volatile SA, as well as mixtures of SA with the synergetic effect
of increasing the agent selectivity. In some cases the chemically active SA and substance,
forming heteroazeotropes, are used, although these features in classical literature are
considered to be rather a disadvantages of such processes, than an advantages. The main
requirement to the SA – the increasing of the relative volatility (α) of separating components –
remaines unchanged for more than 70 years. But the study of general regularities of the α-
manifolds diagram formation in the derived concentration simplex for a variety of SA is still
actual, that creates the theoretical basis of the development and upgrading of the effectiveness
of the discussed separation processes.
Recent research, carried out at the Department of Chemistry and Technology of Basic
Organic Synthesis in MITHT, expanded significantly the concept about the impact of
additional substances to the structure α-manifolds diagrams of ternary mono - and
biazeptropic systems. The diagrams with the internal special points are revealed with the use
of computational experiment, which testifies to the extreme nature of the influence of the SA
flow on its selectivity. The engagement of diagrams of α-lines of all components pairs in the
derived system are suggested for separation results predictions.
The study of the behavior of the base (the original) system in the cross-sections with a
constant concentration of high boiling temperature SA allowed to explain the existence of the
extremes of the temperature on the extractive rectification trajectory by the mismatching of
the fold on the boiling temperatures surface and a single α-line, that is the consequence of
process dynamic system changes when multilevel feeding of the initial mixture and SA takes
place. The classes are allocated and an atlas of phase diagrams, favorable for the separation of
mixtures with the use of the mentioned processes, was made.
The diagrams of single α-surfaces course, which break the concentration tetrahedron into
regions with different ratio of components relative volatilities, are received for 13 quaternary
systems with mono - and biazeotropic homogeneous and splitting components: benzene – toluene
– cyclohexane – dimethyl formamid (DMSO); hexane – acetone – ethanol – dimethyl formamid
(DMSO); chloroform – acetone – methanol – dimethyl formamid (DMSO, water); chloroform –
acetone – ethanol – water; acetone – chloroform (toluene) – butanol – dimethyl formamid; methyl
t-butyl ether – methanol – tert.butanol – water; benzene – perfluorobenzene – methyl propionate
(tertiary amyl alcohol) - DMSO. The observed phenomenon of volatilities inversion allows to
change the order of components selection and manage the quality of product flows in the
complexes of extractive rectification. The regularities of relative volatility change in ternary
components, which are the signs of third dimension α-manifolds in the concentration pentatop are
studied for three five-component systems: methyl t-butyl ether – methanol – tert.butanol – water –
ethylene glycol (DMSO, dimethyl formamid).
project № 11-03-00295-a).
THERMODYNAMICS OF NICKEL(II) ION COMPLEXATION WITH NICOTINAMIDE

IN AQUEOUS ORGANIC SOLVENTS
Gamov G.A., Gavrilova M.A., Dushina S.V., Sharnin V.A.
Research Institute of Thermodynamics and Kinetics of Chemical Processes
of Ivanovo State University of Chemistry and Technology, Ivanovo
e-mail: kax504@isuct.ru
In the present work the complexation enthalpies of nickel(II) ion with nicotinamide in
two aqueous organic solvents were obtained using direct calorimetrical method (Table).
In aqueous ethanol the ΔHr dependence on the solvent composition has minimum at
XEtOH = 0.3 m.f. In aqueous dimethyl sulfoxide the change character of complex formation
heat is complicated.
Table
Х2, m. f.
solvent
0.0 0.1 0.3 0.5 0.7 0.85
aqueous ethanol, -ΔHr ± 0.60, kJ/mol 16.73 13.64 9.77 11.16 17.20 19.03
aqueous DMSO, -ΔHr ± 0.60, kJ/mol 16.73 12.97 16.37 15.40 13.75 14.46
In aqueous ethanol the complex is significantly enthalpy destabilized at XEtOH = 0.1

(Fig. a). When 0.3 ≤ XEtOH ≤ 0.5, the contribution of ionic constituent into enthalpy change of
reaction dominates. There is a strong linear correlation between ΔtrHNi and ΔtrHNiL.
20 ∆trH°, кДж/моль 10
∆trH°, кДж/моль
18 r
16 0
14
12 -10 L
10
8 -20
6
4 -30
2 L
0 -40
-2
-4 r -50
-6 2+
-8 NiL -60 Ni2+
-10
-12 Ni2+ -70 NiL2+
-14
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
XEtOH XDMSO
a b
Figure. The transfer enthalpies of the reactions and reagents of nickel(II) complexation
with nicotinamide towards an aqueous ethanol (a) and aqueous dimethyl sulfoxide (b)
At any dimethyl sulfoxide content the complex formation process is less exothermic
than in aqueous solution (Fig. b). The transfer of complex ion and Ni2+ is energetically
beneficial at XDMSO > 0.1. The ligand contribution dominates only when XDMSO = 0.5,
however, ΔtrHL correlates strongly with ΔtrHr in the solvent composition interval 0.3 ≤ XDMSO
≤ 0.7. The enthalpies of complex ion and Ni2+ transfer are also in significant interdependence.
THE THERMODYNAMIC STUDY OF SOLUTIONS OF DIALKYLSULFOXIDES

WITH ALCOHOLS
Ghazoyan H.H., Markarian S.A.
Yerevan State University, Yerevan, Armenia
e-mail: heghine@ysu.am
The study of volumetric properties and liquid-vapor phase equilibrium for binary
systems such as dialkylsulfoxide (DASO)-alcohol mixture has been fundamental and practical
interests. Fundamental importance is caused by the fact that the components of this system
are capable both to self-association, and to interact with each other. Obviously, that the
presence of such competing interactions considerably influences on the thermodynamic
properties of these solutions [1]. Moreover, sulfoxides, particularly dimethylsulfoxide
(DMSO) and diethylsulfoxide (DESO) have a wide application both in biology, and in
medicine [2,3].
The densities of binary DASO (DMSO and DESO)-alcohol (methanol, ethanol, 1-
propanol, 1-butanol) mixtures have been measured on a DMA 4500 vibrating-tube densimeter
over the 293.15–323.15 K temperature range at the atmospheric pressure. Excess molar
volumes were calculated and described by the Redlich–Kister equation.
Saturated vapor pressures of solutions were measured by means of the Clausius–
Clapeyron apparatus. Partial pressures of components were calculated by integrating the
Gibbs–Duhem equation. Excess molar Gibbs energies were described by the Redlich–Kister
equation, and correlation parameters were calculated as well.
It was found that molar excess volumes and Gibbs energies in all cases are negative. The
maximal negative deviation from ideality corresponds to the composition X DASO ≈ 0.4 ÷ 0.7 ,
which testifies that in this concentration range the formation of DASO–alcohol
heteroassociates prevails.
It was also found that molar excess values decrease as temperature increases. It suggests
that, as temperature increases, the destruction of homoassociates increases and
heteroassociates are mainly formed.
To explain the results obtained, the role of length of the hydrocarbon chain of
components has been considered.
References
1. E.A. Kazoyan, A.S. Khachatryan, Russian Journal of Applied Chemistry, 2012, v. 85, p.
1335.
2. S.W. Jacob, R. Herschler, Cryobiology, 1986, v. 24, p. 4.
3. S.A. Markarian, A.A. Poladian, G.R. Kirakosyan, A.A. Trchounian, K.A. Bagramyan, Lett.
Appl. Microbiol., 2002 , v. 34, p. 417.
THERMODYNAMIC AND KINETIC REGULARITIESCRYSTALLIZATION

OF PROTOTYPES OF BIOLOGICAL LIQUIDS
Golovanova O. A.
F.M. Dostoevsky Omsk State University, Omsk
e-mail: golovanoa2000@mail.ru
Methods of modeling allow to reveal features of processes of emergence of new growths
in a human body and action of the systems regulating their growth. At the same time studying
of formation of a number of minerals in not to peculiar environment for them with accurately
regulated conditions of a human body different (sometimes very significantly) from conditions
of the abiogenous environment, expands idea of genesis of minerals and promotes
development of the general theory of mineralogenesis.
Methods of thermodynamic modeling received broad distribution in geochemical
researches for the description of processes of mineralogenesis with participation of mainly
diluted solutions. The solution of a task includes use of the corresponding criterion answering
to a condition of stable equilibrium of system, and thermodynamic a reasonable choice of
association of minerals which can potentially be in balance with environment for this limited
area of conditions. Change of standard energy of Gibbs at formation of a deposit is connected
with work of solubility of slightly soluble connection by the equation:
∆G 0 − RT ln
=
1
= RT ln K s
0 (1) where – ∆G(0М Х q ),Т
Gibbs's standard energy,
( М р Х q ),Т Ks
0 р
kJ/mol; R – universal gas constant (J / моль∙К); T – temperature, K.

One of ways of graphic representation of balance the sediment ↔ rastvor in system in
which formation of almost insoluble connection from water solution proceeds, is construction
of "stability fields". The principle of creation of similar charts consists in establishment of
functional dependence of the minimum concentration of the cation which is a part of a deposit
which needs to be created for receiving supersaturation on this phase, from рН solution and
concentration of anion: pCM q + = f ( pC X p − , pH )
During the carried-out thermodynamic calculations conditions and possibility of
formation of almost insoluble connections in hypothetical solution of sediment-forming ions
are revealed. On the basis of the constructed charts of stability for a series of phosphates of
calcium and magnesium, and also calcium oxalate, areas at which formation of these phases
from solutions most thermodynamic is probable are defined.
Thermodynamic calculation reflects possibility of formation of phases only proceeding
from data on their thermodynamic stability in a standard condition and doesn't consider, in
particular, the kinetic factors having impact on process of formation of a solid phase in actual
practice.
When carrying out model experiments analogs of phosphatic minerals were received,
and also distinctions in the conditions of their education are revealed. The analysis of the
obtained data showed that size рН solution has the most essential impact on structure of a
being formed solid phase. Thus the variation of initial concentration of components of
solution, in the range of values, characteristic for biological liquid, brings in the basic to
quantitative, instead of to high-quality changes of structure of a deposit.
This work was partially supported by the Russian Foundation for Basic Research (№
12-03-98011-r_sibir_a).
THERMODYNAMICS OF MOLECULAR RECOGNITION BY SOLIDS CALIXARENES

Gorbatchuk V.V., Luchai K.V., Galyaltdinov S.F., Ziganshin M.A.
A.M. Butlerov Institute of Chemistry, Kazan Federal University, Kazan
e-mail: valery.gorbatchuk@ksu.ru
A search of principally new experimental approaches giving molecular recognition of
small neutral molecules is of major importance for a number of applications including
medical diagnostics and odor detection. A usual key-to-lock recognition scheme requires the
presence in a substrate (guest) of at least two specifically oriented functional groups capable
for strong enough H-bonding or donor-acceptor interaction with receptor (host). This
approach gives poor results for relatively inert compounds without such groups or with only
one H-bonding group.
The present work provides a solution of this problem using a specific property of
calixarenes. This is an ability of some calixarenes to remember previously bound guest after
the clathrate decomposition with formation of loose metastable polymorphic phase having
significant free volume up to 6 vol.% [1]. This memory is very selective and can be read in
DSC experiment as an exothermic effect of host collapse to dense phase. The memory
parameters (enthalpy and temperature of host transition) strongly depend on the guest
structure. Some hosts are able to remember only one guest in a large series of compounds with
similar structure including close homologues [2].
A true test for molecular recognition is the selectivity of host for guest mixture. Once
found for a host-guest pair, the memory effect persists also for guest mixtures with
unremembered compounds. Thus, qualitative and quantitative determination of a mixture
component can be made using only one receptor. For example, benzene and
tetrachloromethane can be discriminated from their mixtures with cyclohexane and
chloroform, respectively, using tert-butylcalix[6]arene polymorphism [3]. This is a genuine
molecular recognition competing by selectivity with chromatographic separation.
Another approach giving true molecular recognition is in using a two-step formation of
clathrate, which is observed for tert-butylthiacalix[4]arene derivative both on vapor sorption
isotherm and in kinetic response of mass-sensitive sensor. This approach is also extremely
selective being capable to discriminate, for example, benzene from its close homologues even
in mixtures [4].
References
1. A.V.Yakimov, M.A.Ziganshin, A.T.Gubaidullin, V.V.Gorbatchuk, Org. Biomol. Chem.
2008, 6, 982–985.
2. S.F.Galyaltdinov, M.A.Ziganshin, A.B.Drapailo, V.V.Gorbatchuk, J. Phys. Chem. B 2012,
116, 11379−11385.
3. G.D.Safina, M.A.Ziganshin, A.T.Gubaidullin, V.V.Gorbatchuk, Org. Biomol. Chem. 2013,
DOI:10.1039/C2OB27164H.
4. G.D.Safina, L.R.Validova, M.A.Ziganshin, I.I.Stoikov, I.S.Antipin, V.V.Gorbatchuk,
Sensors and Actuators B. 2010, 148, 264–268.
THE ENTHALPIES OF TRANSFER OF REACTANTS AND REACTIONS

OF COMPLEXATION BETWEEN IRON (III) AND NICOTINAMIDE
OR NICOTINIC ACID FROM WATER TO AQUEOUS ETHANOL
Grazhdan K.V., Kuranova N.N., Dushina S.V., Sharnin V.A.,
Aralkina N.V., Ekimovskaya A.A.
of Thermodynamics and Kinetics of Chemical Processes, Ivanovo
e-mail: konst84@land.ru
The heat effects of iron(III) perchlorate transfer from water to water-ethanol mixtures
were determined by the calorimetric method at 25,00 ± 0,01 ºC. The enthalpies of Fe3+ ion
transfer were calculated.
The heat effects of iron(III) perchlorate solutions dilution were determined as the
difference between the heat effect of the primary experiment and the heat effect of the blank
experiment. The primary experiment represented the breaking of the ampoules containing
aqueous Fe(ClO4)3 and HClO4, into a cell containing a water-ethanol solution of HClO4. The
blank experiment represented the breaking of the ampoules containing an aqueous solution of
HClO4, the cell containing the water-ethanol solution of HClO4. The contribution of
Fe(ClO4)3 dilution from concentrated to dilute solution was determined through a similar
primary and blank experiments for aqueous solutions.
The enthalpies of Fe3+ complexation with nicotinic acid and its amide were obtained
calorimetrically by the procedure described in [1, 2]. The organization of the experiments to
determine the heat effects of nicotinamide and nicotinic acid transfer from water to water-
ethanol solvent is presented in [3, 4].
The data obtained are represented in the table.
XEtOH, mol. f. 0,1 0,3 0,5 0,75
ΔtrH(Fe(ClO4)3) –0,1±0,4 4,7±0,6 5,6±0,9 1,6±1,1
ΔtrH(ClO4 ) [5]
-
–0,7 –2,6 –4,4 –5,0
ΔtrH(Fe3+) 2,0 12,5 18,8 16,6
ΔtrH(NicOH) [4] 9,24 11,28 6,57 10,71
ΔtrHr(NicOH+Fe ) [1]
3+
-14,33 3,79 11,45 10,84
ΔtrH(NicNH2) [3] 6,81 -0,06 -1,73 -1,12
ΔtrHr(NicNH2+Fe ) [2]
3+
-4,85 11,56 15,79 16,03
The results discussion was carried in scopes of the solvation-thermodynamic approach,
founded on the thermodynamic characteristics of the complexation reactants solvation.
The study was supported by The Ministry of Education and Science of Russian
Federation, project 14.B37.21.0801.
References
1. Kuranova N.N., Dushina S.V., Sharnin V.A. // Russian Journal of Inorganic Chemistry,
2008, v. 53, № 12, p. 1943-1947.
2. K.V. Grazhdan, S.V. Dushina, V.A. Sharnin // Russian Journal of Physical Chemistry A,
2009, v. 83, № 10, p. 1734-1736.
3. Kurysheva A.S., Sharnin V.A., Ledenkov S.F. // Zhurnal Fizicheskoi Khimii, 2004, v. 78,
№ 2, p. 229-233.
4. Kuranova N.N., Dushina S.V., Sharnin V.A.// Russian Journal of Physical Chemistry A,
2010, v. 84, № 5, p. 792-795.
5. Nevskyi A.V. et al. // Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol., 1984, v. 27, № 6,
p. 730-733.
THERMODYNAMIC QUANTITIES OF FORMATION REACTIONS

FOR BINARY AND TERNARY COMPLEXES OF SOME AMINO ACIDS
WITH COBALT(II), NICKEL(II) AND COPPER(II) IONS
Gridchin S.N.1, Pyreu D.F.2
1
2
Ivanovo State University, Ivanovo
e-mail: sergei_gridchin@mail.ru
Amino acids play a dominant role in the creation of peptide molecules, nitrogen
metabolism and other important biochemical processes. Study of coordination equilibria
between these vital ligands and 3d-metal ions is of particular interest to explain structural
features of various ferment active centers. It offers ample scope for progress in simulation of
their behaviour.
This work presents results of potentiometric, spectrophotometric and calorimetric
investigation of complex formation processes for Co2+, Ni2+, Cu2+ ions and some amino
carbonic acids. Among the main objects of this investigation are L-homoserine, L-serine, D,L-
alanine, L-lysine, L-ornithine, L-glutamine, L-asparagine and L-aspartic acid.
Thermodynamic quantities (log K, ∆G, ∆Н, ∆S) of protolytic and coordination equilibria
in systems metal + amino acid have been determined at 298.15K and ionic strength values
from 0.1 to 1.5 mole/l. The influence of “background” electrolyte character and concentration
on the relevant equilibria was under consideration. The data obtained were extrapolated to the
zero ionic strength. The corresponding thermodynamic quantity values have been calculated
for the standard solution.
Thermodynamic parameters for addition reactions of some amino acids to cobalt(II),
nickel(II) and copper(II) nitrilotriacetates have been evaluated. The log K, ∆G, ∆Н, ∆S values
for the mixed complex formation reactions were discussed together with the corresponding
thermodynamic parameters of similar formation reactions for the simple binary complexes.
The results obtained were compared with the corresponding data on related compounds
(amino acids, complexones, dipeptides and diamines) investigated earlier in this laboratory
under the same experimental conditions.
A plausible explanation of changes in the enthalpy and entropy values for the binary and
ternary complexes investigated has been suggested in view of the metal ion and ligand
structures (type of coordination, denticity, presence of hydrophobic and hydrophilic fragments,
solvation features of zwitter ions).
THERMODYNAMIC MODELLING OF Al – REM, Al (REM) – O SYSTEMS

Ilinykh N.I. 1, Sidorov V.E. 2
1
Ural Technical Institute of Telecommunications and Informatics, Ekaterinburg
e-mail: ninail@bk.ru
2
Ural State Pedagogical University, Ekaterinburg
e-mail: vesidor@mail.ru
Aluminum-REM alloys are widely used nowadays in different branches of industry due
to their unique mechanical, electrical and magnetic properties. Being chemically active these
alloys oxidize rather fast in the air. However, the information about the influence of oxygen on
physical and chemical properties of aluminum - REM alloys is lack or absent. Thus the main
aim of the work was to investigate the compositions of condensed and gas phases (taking into
account the evaporation of the melts) of aluminum alloys in different environments.
The thermodynamic modeling of Al-REM (REM = Ce, La, Y, Yb, Gd, Nd etc), Al-O
and REM-O alloys was performed using TERRA software (created in MSTU named after N.
Bauman) in the oxygen and argon atmospheres under total pressure of P = 105 Pa in the
temperature range of 300 – 3000 K.
The temperature and concentration dependences of the activities of components, the
partial and integral excess characteristics (enthalpy, entropy, Gibbs's energy), the equilibrium
composition of the condensed and gas phase were calculated.
The temperatures, enthalpies and entropies of “liquid - gas” transition were determined
and the phase diagrams of “liquid – liquid+gas - gas” type were constructed. The temperature
and concentration ranges for the components (phases) of the above mentioned systems in
condensed and gas states were determined.
For all the studied alloys, the composition of the condensed phases was found to be
dependent on temperature and initial chemical content. This information can be used for
prediction the composition-property dependences and modification of production regimes for
Al-REM alloys.
THERMODYNAMIC PROPERTIES OF NONSTOICHIOMETRIC PHASES

IN Tl2Te-PbTe-Bi2Te3 SYSTEM
Imamaliyeva S.Z., Huseynov F.N., Babanly M.B
Baku State University, Baku
e-mail: Babanly_mb@rambler.ru
Binary and complex tellurides of 6p-metals are promising high-performance for
thermoelectric materials [1].
Quasitenary system Tl2Te-PbTe-Bi2Te3 is characterized by the formation of a continuous
solid solutions with the Tl5Te3 crystal structure in section Tl4PbTe3-Tl9BiTe6 and a wide
composition area (up to 75 mol%) based on PbTe solid solutions in the system PbTe-TlBiTe2
[2].
In this work, we present the thermodynamic properties of solid solutions
(PbTe)x(TlBiTe2)1-x and (Tl4PbTe3)x(Tl9BiTe6)1-x which studied by electromotive force (EMF)
measurements.
For the measurements, the following concentration chains were constructed:
(-) Tl (s.) | liquid electrolyte, Tl+ | (Tl in the alloy) (s.) (+) (1)
In the chains of type (1), a glycerin solution of KCl with the addition of TlCl was used
as the electrolyte. EMF was measured by the compensation method in the temperature range
of 300-430K. The experimental procedure is described in [3].
From EMF measurements the partial molar thermodynamic functions of thallium
( ∆G, ∆H, ∆S ) in the alloys at 298 K were calculated. On the basis of obtained data the standard
thermodynamic functions of formation and the standard entropy of the solid solutions (PbTe)x
(TlBiTe2)1-x and (Tl4PbTe3)x(Tl9BiTe6)1-x were calculated.
For the calculations the thermodynamic parameters of the corresponding standard
integral thermodynamic functions of TlTe, PbTe, PbBi2Te4 and PbBi4Te7, as well as
elementary thallium and tellurium were taken from the literature. In all cases the estimated
standard deviations were calculated by accumulation of errors.
Table
− ∆ f G (298 K )
0
− ∆ f H (298 K )
0 0
S (298K )
Composition
кJ⋅mol-1 J⋅ К-1⋅mol-1
(PbTe)0,25(TlBiTe2)0,75 96,25±1,24 95,12±1,13 198±6
(PbTe)0,33(TlBiTe2)0,67 95,93±1,35 94,13±1,30 192±6
(PbTe)0,4(TlBiTe2)0,6 93,98±1,42 94,95±1,31 185±6
(PbTe)0,6(TlBiTe2)0,4 85,80±1,21 84,70±1,30 161±5
(PbTe)0,8(TlBiTe2)0,2 76,85±1,44 76,87±1,29 136±4
(PbTe)0,9(TlBiTe2)0,1 72,43±1,91 73,02±1,30 123±4
References
1. Shevelkov A.V., Chemical aspects of creation of thermoelectric materials // Russ. Chem.
Rev. 2008, v.77, pp.3-21.
2. Quseynov F.N., Babanlı M.B., Zlomanov V.P., Yusibov Yu.A. Phase equilibria in the system
Tl2Te-PbTe-Bi2Te3 //J.Inorg.Chem., 2012, №10, s.1473-1478
3. Babanly M.B., Yusibov Y.A. Electrochemical methods in thermodynamics of inorganic
systems. Baku, 2011, 306 p (ISBN 978-9952-453-17-1).
This work was supported by Science Development Foundation under the President of
the Republic of Azerbaijan - Grant № EIF-2011-1(3)-82/69/4-M-50.
INFLUENCE OF CONCENTRATION AND SOLVENT NATURE

ON THERMODYNAMIC CHARACTERISTICS OF THE CONDUCTIVITY
AND PROCES VISCOUS FLOW SOLUTION OF SALTS
Ivashkevich A.N.
Moscow Regional State Institute of Humanitits and Social Studies, Kolomna, Moscow region
e-mail: chimecol@mail.ru
The study of the thermodynamic characteristics of the process of electrical and viscous
flow of electrolyte solutions in a wide range of the composition of the solution, depending on
the nature of the solvent is one of the most important problems in the theory of solutions and
practical electrochemistry. Аlkylammonium salts and organic solvents with different
electrophysical and donor-acceptor properties as the objects of study are ideal for
implementation of this task.
The usage of alkylammonium salts allows us to study the systems not only in a wide
range but also in whole area of concentration, from dilute solutions to the molten salt, because
of their high solubility in diff erent solvents and relatively low melting point.
This paper discusses the results of the research of the dependence of conductivity and
dynamic viscosity of binary systems formed by tetra-n-butylammonium bromide (TBAB) with
benzene, chloroform, pyridine, acetonitrile, nitromethane, dimethyl sulfoxide and water from
temperature in the entire concentration range from dilute solutions to melt salt.
The temperature dependence (20 - 120 ° C) of electrical conductivity and dynamic
viscosity in all studied areas of the compound of solutions is adequately described by the
Vogel-Fulcher-Tamman equation.
Enthalpy of activation of conductivity (ΔH#æ), viscous flow (ΔH#η), conductivity,
corrected for viscosity (ΔH#æη), was calculated by the standard method for linear logarithmic
plots of the relevant properties of 1 / T. The values of ΔH#η more than ΔH#æ throughout the
concentration range for all studied systems, except for benzene, which is typical for
electrolyte solutions and molten salts.
Dependence of ΔH#æ and ΔH#η on the compound is S-shaped in the systems formed by
tetra-n-butylammonium bromide with pyridine, acetonitrile, nitromethane, which is typical
for systems with interacting components. TBAB - chloroform system's curves ΔH#æ and
ΔH#η concave to the axis of the compound. TBAB - benzene system's values of ΔH#æ are
higher than ΔH#η only at high salt concentrations from the melt to 75 mol.%. In case of lower
salt concentrations ΔH#η< ΔH#æ which is atypical for saline. We are aware of only one similar
case in the system TBAB-carbon tetrachloride. The feature of the system TBAB-benzene is
also a complex relationship ΔH#æ and ΔH#η passing through a minimum and maximum with
increasing salt concentration.
The observing features of changes in the quantities ΔH#æ, ΔH#η and ΔH#æη, the
temperature coefficients of conductivity, viscosity and electrical conductivity, corrected for
viscosity, and their dependence on the concentration and nature of the solvent are discussed
according to our developing physical-chemical model of the formation of ions in solution and
from the position of the Eyring transition state theory.
THE ASSOCIATION OF 1-1 ELECTROLYTES WITH THE FORMATION OF ION PAIRS

AND TRIPLES IN LOW DIELECTRIC CONSTANT MEDIA
Кalugin O.N., Panchenko V.G., V’ynnik I.N.
V.N. Karazin Kharkiv National University. Kharkiv. Ukraine
e-mail: valentinapvg@mail.ru
The results of the experimental conductometric study on 1-1 electrolytes (NaClO4,
LiClO4, LiNO3, NaI, Bu4NI, NaBPh4) in the solvents with low dielectric constant (ε < 15) are
presented. The following solvent media were investigated: neat ethyl acetate and
tetrahydrofuran, mixtures of tetrahydrofuran - dimethylformamide, acetone - chloroform,
acetone - dioxane, acetone - hexane, dioxane - methanol, butane-1-ol - octane, tetrahydrofuran
- ethylene glycol, tetrahydrofuran - water. The conductance data were analyzed using the
method proposed earlier [1, 2]. The equilibria of ion pairs (1) and ion triples (2, 3) formation
has been taken into account
[К+] s + [А-] s = [К+А-] s, КA, (1)
[К+А-] s + [К+] s = [К+А- К+] s, KT+ , (2)
[А-] s + [К+А-] s = [А- К+А-] s, KT− , (3)
assuming that the association constants of the cationic and anionic triples are the same
KT+ = KT− = KT .
The obtained association constants of ion triples are less than the association constants
of ion paring indicating the preferable formation of neutral species as compare with charged
ones. Since the lgKA dependence on the inverse value of dielectric constant is nonlinear, one
can conclude that the ion salvation plays a significant role in the ion association processes.
The KT values are almost insensitive to the variation of dielectric constant of a solvent and
temperature.
Using the obtained KT values, the structural parameters (a3) as the distance between the
centre of the ion and the dipole of the ion pair in the ion triple have been calculated by means
Delsignore [3] equation
KT =2 ⋅ 10 -3π N A a33Q b3 2 , (4)
where Q=∑ Y (
n-( 5 2 )) b
( n- 5 2 ) n! , b = µ e a32ε k B , Y = µ e ε k B r 2T .
n 2
The calculated a3 values indicate the formation of mainly solvent separated ion triple for
salts containing cation of alkali metals, and contact ion triples for the salts with
tetraalkylammonium cations.
References
1. Kalugin O.N., Panchenko V.G. Russian J. Phys. Chem. 2003. Vol. 77, No 8. P.1310-1314.
2. Kalugin O.N., Panchenko V.G., V’ynnik I.N. Russian J. Phys. Chem. 2005. Vol. 79, No 4. P.
734-739.
3. Delsignore M., Farber H., Petrucci S. J. Phys. Chem. 1985. V. 89, № 23. P.4968-4973.
MACROSCOPIC PROPERTIES AND MICROSCOPIC STRUCTURE OF THE BINARY

SYSTEMS OF ROOM TEMPERATURE IONIC LIQUIDS WITH MOLECULAR LIQUIDS
Kalugin O. N.1, Voroshylova Iu. V. 1, Marekha B. A.1,2, Chaban V. V.3,
Ryabchunova A. V.1, Lukinova O. V.1, Idrissi A.2
1
2
LASIR, Université des Sciences et Technologies de Lille, Villeneuve d'Ascq Cedex, France
3
MEMPHYS, University of Southern Denmark, Odense M. Denmark
e-mail: onkalugin@gmail.com
Room temperature ionic liquids (RTILs) have already found an impressive number of
applications due to the versatility of their properties which are determined by their
composition. In case of electrochemical application of the RTILs the diversity of credible
systems can also be expanded by combining RTILs with common electrochemical solvents
like acetonitrile (ACN). Many practically important properties of these mixtures (such as
conductivity, viscosity etc.) are modulated by phenomenon of ionic association to ion pairs or
to ionic aggregates of higher order. From the microscopic point of view, these properties of the
mixtures of RTILs with molecular solvents (which can be regarded as solutions of RTILs) are
defined by strong interionic interactions, especially by the structure motif of ion pairs.
Here we report the results of combined investigations of the sets of imidazolium- and
pyridinium-based RTILs and their mixture with ACN by using multitechnique approach.
On the basis of the conductometric measurements it was established that ionic
association in all RTIL-AN systems poorly correlates with the cation’s structure, although
strongly depends on the anion’s size and internal structure. Cation and anion of RTILs form
the ‘contact ion pairs’ (CIPs), where anion is coordinated by imidazole and pyridine rings.
Notably, all binary systems exhibit conductivity maximum between x(RTIL)=10 and 20%.
This maximum slightly shifts towards smaller x(RTIL), as counterion gets larger. Smaller
cations and anions lead to substantial conductivity growth. Our observations provide novel
insights into a complicated functional dependence of ionic conductivity versus ionic
concentration and temperature.
We have also studied solutions of two ionic liquids with common cation: 1-butyl-3-
methylimidazolium tetrafluoroborate, [Bmim][BF4], and 1-butyl-3-methylimidazolium
trifluoromethanesulfonate, [Bmim][TfO] in ACN by means of NMR-spectroscopy on 1H, 11B
and 19F nuclei. Concentration dependencies of chemical shifts (especially for 1H nuclei) reveal
different microscopic structure which can be interpreted in terms of weak F···H hydrogen
bonds between either aromatic or aliphatic hydrogen atoms of the [Bmim]+ - cation. The
experimental results are confirmed by ab initio calculations of the ion pairs. Bader's ‘quantum
theory of atoms in molecules’ (QTAIM) was used to quantify the abovementioned hydrogen
bonds as well as general features of electron density redistribution upon ion pairing in RTILs.
To elucidate an influence of microscopic structure and particle dynamics on
macroscopic transport properties of the imidazolium-based RTILs and their mixtures with
molecular liquids, the state-of-the-art atomistic-precision molecular dynamics simulations
have been performed on pure [Emim][BF4] and [Bmim][BF4] and their mixes with ACN by
applying a new methodology in the force field generation (PCCP 2011, 13, 7910). The
conductivity correlates with a composition of ion aggregates simplifying its predictability. The
maximum is found at x(RTIL), where the number of free (not clusterized) ions exceeds the
number of ion pairs. Large amounts of ACN stabilize ion pairs, although they ruin greater ion
aggregates.
PARTIAL MOLAR VOLUME COMPONENTS OF WATER + ALIPHATIC ALCOHOL

MIXTURES
Karabekova B.K., Bazaev A.R
Institute of Problems of Geotermy, Daghestan Scientific Center of the Russian Academy
of Sciences, Makhachkala, Republic of Daghestan
e-mail: badji @mail.ru
Partial molar volume of component of real gaseous mixtures (homogeneous liquid

mixtures) is determined by formula [1]:
,
(1)
where Vm– molar volume mixtures at Т and р; х– molar fraction of second component.
For calculation of using (1)
one needs values of Vm and its
dependences on composition x at
constant temperature T and pressure p
of mixture p. In this work for
calculation of partial molar volumes
we used results of p,Vm,T,x-
measurements of water+alcohol
mixtures (methanol, ethanol and 1-
propanol) with x=0.2, 0.5, 0.8 in the
range of temperatures 613.15 – 653.15
К and pressures 20 – 50 MPa [2].
Dependence of molar volume on
concentration Vm=f(x)p,T is described
Dependence of partial molar volume of by polynomial equation with relative
components on concentration of ethanol for deviation 0,5%.
water+ethanol mixtures at T=653,15 K and p=40 Characteristic feature for all of
MPa. three researched mixtures is that there
is insignificant growth of partial molar
volumes of water and decreasing of partial molar volumes of alcohols with increasing of
alcohol concentration. Water+hydrocarbon mixtures in critical state have similar character of
dependence of partial molar volume on concentration [3].
References
1. Karapetyanc M.H. Chemical thermodynamic, 3 edition, M.: Chemistry. 1975. 584 p.
2. Abdurashidova А.А. Dis. … candidate of technical scince. Makhachkala: Institute of
Problems of Geotermy, Daghestan scientific Center of the Russian Academy of Sciences.
2010. 200 p.
3. I.M.Abdulagatov, K.M.Magomedov, A.R.Bazaev, E.A. Bazaev. Journal of Physical
Chemistry. №2. V.75. P. 263-266.
CORRELATION OF STATIC DIELECTRIC PERMITTIVITY AND WATER ACTIVITY

OF ELECTROLYTE SOLUTIONS IN THE TEMPERATURE RANGE
Karataeva I.M., Lyaschenko A.K.
Kurnakov Institute of General and Inorganic Сhemistry RAS, Moscow
e-mail: aklyas@mail.ru
At present time the sufficient material on water activity of aqueous electrolyte solutions
is accumulated. The electrostatic hydration contribution plays an essential role in the
thermodynamic properties of solutions. It can be estimated by means of static dielectric
permittivity of solutions in wide area of concentrations. The experimental method of
microwave dielectric spectroscopy (7-25 or 7-120 GHz) is advanced for εs determination of
concentrated electrolyte solutions in the temperature range. Earlier [1, 2] linear character of
dependence of water activity (aw) on inverse value of static dielectric permittivity (1/εs) was
shown at 298 K (30 examples). The aqueous solutions of chlorides, sulphates and nitrates of
alkaline metals, and also solutions of nitrates of copper and yttrium in a wide range of
concentrations were investigated. It is established the concentration limit of the first structural
zone of solutions where this dependence is observed. The occurrence of deviation is
connected with the concentrations where ionic-water clusters and the transition from water-
electrolyte to electrolyte- water solvent are realized. The equation for calculation of water
activity according to static dielectric permittivity is offered: aw=1 + b (1/εs - 1/εH2O), где εH2O
- static dielectric permittivity of water, b – a coefficient different for each electrolyte.
At present work the dependence aw– 1/εs in the solutions is considered in the
temperature range 283- 323 K. For this purpose our own experimental data of static dielectric
permittivity of solutions and literature data of the water activity are used. Analysis is carried
out for the next electrolyte solutions: NaCl, KCl, KF, Cs2SO4, Na2SO4, Li2SO4, (NH4)2SO4,
LiNO3, NaNO3, NH4NO3, KOH, HCl. It is shown that the linear dependence aw – 1/εs is
maintained at temperatures range 283-323 K for the solutions of NaCl, KF, Cs2SO4, Li2SO4,
LiNO3. In the solutions of HCl, KCl, Na2SO4, (NH4)2SO4, NaNO3 the changes of value “b”
are observed. In the solutions of KOH, Na2SO4, KCl, HCl the concentration range where the
linear dependence aw– 1/εs exists is reduced.
Unfortunately the experimental data on static dielectric permittivity in the temperature
range is not sufficient for the more detail analysis. At the same time it is visible, that static
dielectric permittivity of electrolytes is the important factor that determine the thermodynamic
properties of the solutions in the temperature range.
Work is executed at support of the RFBR, the project № 12-03-00062а.
References
1. Lyashchenko A.K., Karataeva I.M.. Relation of water activity to the static dielectric
constant of concentrate electrolyte solutions//Doklady Phys. Chem.(Doklady Akademii
nauk). 2007. Vol. 414. P.120-122.
2. Lyashchenko A.K., Karataeva I.M. Activity of water and Permittivity of Aqueous Solutions
of Electrolytes // Russian Journal of Phys. Chem., 2010, Vol. 84, No. 2, P. 320–328.
THE COMPARISON OF THE RESULTS OF DNA CONDENSATION IN SOLUTION

INDUCED BY POLYCATIONS AND SMALL CHARGED COMPOUNDS
Kasyanenko N.A., Dribinsky B.A., Lysyakova L.A.
Department of Physics, St. Petersburg State University, St. Petersburg
e-mail: nkasyanenko@mail.ru
DNA condensation in vitro is the conformational transition from the swollen molecular
coil in solution to the nanoscale particles without the destruction of secondary structure of
macromolecules under the influence of various agentы. Double stranded DNA is a rigid and
high charged polymer. For the condensation it is necessary to overcome the great electrostatic
repulsion between negatively charged units (phosphate groups), leading to swelling of
polyelectrolyte DNA. The study of DNA condensation is important, for example, to select the
optimal conditions for the formation of gene vectors. Synthetic polycations are widely used as
coupling agents for the formation of non-viral gene vectors. The features of the formation of
DNA-polycation complexes in solution for the organization of small condensed particles are
regarded. The comparison of this process with the result of action of small condensed agent in
DNA solution is performed. The influence of chain length, charge density and structure of the
condensed agents on DNA condensation and size of nanoparticles is discussed. We use a
high-molecular linear calf thymus DNA and circular plasmid DNA, poly-L-lysine of various
molecular mass, oligopeptides, polyamines, synthetic polycations. Investigations were carried
out using Dynamic light scattering, Viscometry, Dynamic Birefringence, Spectrophotometry,
Gel electrophoresis, Atomic Force Microscopy. The influence of the degree of polymerization
of polycations and structure of small condensed agents (oligopeptides, polyamines, trivalent
metal ions, surfactants) on the conformational changes of DNA induced by their presence in
the solution and size of nanoparticles which appear at determined conditions is regarded. A
comparison of DNA complexation with oligopeptides, polyamines and metal ions to study the
role of charge localization in the condensation of DNA is carried out. Compared
conformational changes of DNA molecule prior to its condensation in solution with different
compounds give the rule for the dividing of condensed agents into two classes. The first
consists of small condensed compounds which cause the intermolecular reorganization of
DNA coil before the condensation. Polycations can’t produce such influence on DNA
conformation. One can see the analog of first-order phase transition in macroscopic systems.
Hydrodynamic radius of the condensed particles according to Dynamic Light Scattering data
is (65 ± 10) nm for polycations and (125 ± 25) nm for the oligomers, which is consistent with
the data of Atomic Force Microscopy. The condensation of DNA induced by polycations of
considerable length is not observed the formation of any intermediate structures. But Atomic
Force Microscopy detects the formation of "condensation nuclei" in the form of dense
structures surrounded by parts of noncondenced macromolecule when use the oligopeptides
for DNA condensation. The phase diagrams for the systems under study were built. The AFM
images of different structures realized during DNA condensation and come before this
phenomenon in a solution will be presented.
THE ACOUSTIC AND THERMODYNAMIC PROPERTIES

OF BINARY LIQUID MIXTURE OF N-OCTANE + N-DODECANE
Khasanshin Т., Holubeva N., Poddubskij O., Samuilov V., Shchamialiou A.
Mogilev State University of Foodstuffs, Mogilev, Republic of Belarus
e-mail: Khasanshin@tut.by
In this work the results of measurements of the speed sound in a binary liquid mixture of
n-octane + n-dodecane and calculation of thermodynamic properties at temperatures of 298
and 433 K and pressures till 0.1 and 100 MPa are presented.
The research measured the transit time of acoustic pulses in the binary mixture, and the
speed sound in the liquid mixture of octane + dodecane at the temperatures of 298 and 433 K
and pressures of 0.1 and 100 MPa over the whole range of composition. The cargo piston
manometers are applied measure of pressure. Temperature was taken by the platinum
thermometer of resistance. The uncertainty of the temperature measurement was estimated to
be 0.02 K, pressures of 0.05%. The structure of binary mixture was prepared in a weight way.
Hromatografic analysis was carried out before and after measurements. N-alkanes were
purchased from Aldrich firm with mass fraction more than 99%.
The uncertainty of experimental data does not exceed 0.1%.
Authentic speed of sound measurements at atmospheric and elevated pressure and
literary data on density and an isobaric thermal capacity at atmospheric pressure were used as
input data in calculating thermodynamic properties. Missing values of density and isobaric
thermal capacity were found with the use of correlation dependence of the molar volume and
the molar isobaric thermal capacity, pure alkanes and their binary mixtures in line alkanes
from hexane to hexadecane from their molar weight.
The algorithm, and the program of calculation of properties of the liquid mixture of
octane + dodecane in high pressures are made. The calculation procedure is based on the
known ratios connecting thermodynamic and acoustic values. The table containing values of
the speed of sound, density, isobaric and isochoric thermal capacity, adiabatic and isothermal
compressibility in the whole range of parameters is received. Values of the excess molar
volumes, excess molar isobaric thermal capacities, excess adiabatic and isothermal
compressibility, and also deviations of speed of a sound from ideality for the studied mixture
are calculated. It is shown that value of excess molar volumes are negative. Dependence of
thermodynamic properties on temperature, pressure and structure are discussed.
THERMODYNAMIC PROPERTIES OF TERNARY LIQUID MIXTURES

OF N-OCTANE + N-DODECANE + N-HEXADECANE
Khasanshin Т., Holubeva N., Poddubskij O., Samuilov V., Shchamialiou A.
Mogilev State University of Foodstuffs, Mogilev, Republic of Belarus
e-mail: Khasanshin@tut.by
An analysis of current experimental studies and theoretical calculations of
thermodynamic properties of ternary mixtures of n-alkane was done in the present paper. The
overview showed that experimental data were scarce and unsystematic. It seems not to have
been subjected to overall analysis. The measurements were undertaken only for some types of
mixtures and compounds. The Acoustic Method for determining thermodynamic properties of
mixtures was used.
The object of the investigation was a ternary mixture of n-octane, n-dodecane and n-
hexadecane, i.e. homologs with a big difference in the length of the carbon chain. The
research measured the transit time of acoustic pulses in the ternary mixture, and measured the
speed of sound in the liquid mixture of n-octane, n-dodecane and n-hexadecane at the
temperatures of 298 and 433 K and pressures of 0.1 and 100.1 MPa with an uncertainty no
exceeding 0.1%.
Authentic speed of sound measurements at atmospheric and elevated pressure were used
as input data in calculating thermodynamic properties. The values of density and isobaric
thermal capacity at atmospheric pressure were calculated by means of establishing a
correlation between the defined properties of the atomic mass number of carbon in the alkane
molecule and an average atomic mass number of carbon in all mixture components.
Calculation of densities, isochronous and isobar thermal capacity, the isothermal liquefiability
coefficient, and the excess molar volume were done. Some empirical equations for the
calculation of the excess molar value for the ternary mixture were reviewed on the basis of the
relevant data for binary mixtures. Interdependencies of thermodynamic and redundant
properties relative to temperature, pressure and composition were discussed.
The obtained calculations and evaluations proved the employed method to be valid in
providing correct and reliable data.
СOHERENCНY OF CHEMICAL REACTIONS OF THE NANODIMENSIONAL

METALCOMPLEX CATALYST
Kibalnikova O.V.
Saratov State Technical University, Saratov
e-mail:okib@inbox.ru
In the chromatograhpy column applicable for research of sorption of organic gases use
the geterogenizirovanny nanodimensional metallocomplex catalyst (3-nitrilpropanamin on
colorchrom), a representing thin-film heteroconversion. Boundary of heterostructures situation
are located so close , that in this interval the defining role is played by dimensional effects.
Over heteroboundary “the hard proton conductor -hydrogenated metal“ is carried out
reversible and direct, i.e. with catalyst participation, an exchange of protons. Introduction in
the thin-film catalyst of the groups inclined to reversible redox to transition allows to use a
sorbent with “switching” reactionary ability. One of features of these reactions is the
coherence, i.a. emergence of oscillatory modes. In this case is a quantum coherence in the
form of electronic-spin quantum beat.
At electronic -spin coherence realization the ostsillyation of spin pair between a singlet
and a triplet. Being formed connection find magnetic bistability-ability to exist in low-spin
(diamagnetic) and high-spin (paramagnetic) conditions, so-called effect of a crossover. On
drawing 1,2 adducing dependences of free energy of association G and U (rmin.) at education
and self-organization an ion-conductivity ordered structures from column temperature for
toluene and pyridine.
-7
0
0 50 100 150 200
-8 100 150 200
-1
U(r min)105, Дж/моль
-9
G 104 J/mol
-2
-10
-11 -3
-12 -4
-13
-5
-14
-6
Т,о С
Т, oС
Fig.1. Dependence G education an ion-conductivity Fig.2. Dependence U (rmin.) formation ion-

the regulate structures from column temperature conductivity the regulate structures from column
at toluene sorption (c=44,6 M/m3) temperature at pyridine sorption (c=44,6 M/m3)
References
1. A.G. Stromberg, D.P. Semchenco. Physical chemistry. M: Hig.School. 2001. 527 p.
2.Yu.M. Baikov // Electrochemistry. 2009. №4.P.388.
3. T.V. Magdasieva, K.P. Butin // Successes of chemistry. 71 (3) 2002 P.255.
4. V.V. Volhin. Coherentnost in chemical reactions. SPb:Publising house “Fallow deer”,
2008,-448p.
5. Zh. I. Alfyorov // U.F.N. 2002 T.172. № 9. P. 1072
LIQUID-LIQUID EQUILIBRIA IN SYSTEMS CONTAINING BIOFUEL COMPONENTS

AND 1,3-DIOXOLANE DERIVATIVES AS ADDITIVES:
EXPERIMENTAL DATA AND RESULTS OF MODELING
Kilina A.A., Kuranov G.L., Prikhodko I.V., Pukinsky I.B., Smirnova N.A.
Saint Petersburg State University, Department of Chemistry, St. Petersburg
e-mail: igor1964@mail.ru
Cyclic ketals (in particular, 1,3-dioxolane derivatives) are perspective additives to
biofuels capable of increasing their octane number and phase stability [1]. We focus on the
phase behavior of systems containing 2,2-dimethyl-1,3-dioxolane-4-methanol (DMDM) and
2,2-dimethyl-1,3-dioxolane (DMD), the effects produced by these additives being compared.
The results of the liquid-liquid equilibria (LLE) study are presented for binary, ternary and
quaternary systems containing dioxolane, a saturated or aromatic hydrocarbon (n-heptane and
toluene, respectively), ethanol and water. LLE data (binodal curves and tie lines) published
previously [2] and our new experimental results are discussed. The measurements were
performed using polythermal and isothermal methods; refractometry, gas-liquid
chromatography and the Karl Fischer titration being applied for the analysis of the liquid
phases.
The studies for binary mixtures of DMDM and DMD with water, ethanol, heptane and
toluene over the temperature range 243-313 K have shown that DMDM - heptane and DMD -
water solutions exhibit the miscibility gap. The liquid-liquid phase boundaries and connodes
for ternary and quaternary systems were determined at 293.15K. The data for quaternary
hydrocarbon – ethanol – water - DMDM system demonstrate the extension of the
homogeneous region and the changes in the topology of the phase diagram in the case when
heptane is replaced by toluene. The addition of DMDM or DMD results in diminishing of the
immiscibility area and in some increase of the solubility of water in hydrocarbon-ethanol
mixtures. Due to its OH-group DMDM has appeared a significantly more effective additive
than DMD.
The group contribution UNIFAC model was applied to calculate LLE in the systems
formed by the dioxolane derivative (DMDM, DMD), water, ethanol and hydrocarbon
(heptane, toluene). Interaction parameters for the cyclic ether “CH2O” group were revised
using our experimental data. The results of the data correlation and the accuracy of the
prediction of the equilibrium phase diagrams are discussed.
The experimental data obtained and the results of thermodynamic modeling can be
helpful in the search of additives increasing the phase stability of biofuels.
References
1. Varfolomeev S. D. et al. // Patent. RU 2365617. Agent for increasing the octane number of
a gasoline automobile fuel. 2008.
2. Yakovleva M. A., Prikhodko I. V., Pukinsky I. B., Smirnova N. A. // Vestnik Saint-
Petersburg Univ. Ser. Physics & Chemistry. 2011. Iss.2. P.117-128.
Financial support from the RFBR (grant #10-03-00419) and St.Petersburg State
University research grant is gratefully acknowledged.
THERMODYNAMIC PROPERTIES OF SOLID SOLUTION

OF MAGNETITE AND HERCYNITE
Kimyashov A.A., Lykasov A.A.
Chelyabinsk State University, Chelyabinsk
e-mail: kimyashov@mail.ru
Analysis literature`s data have been indicated, the thermodynamic properties of spinel
solution in the Fe – Al – O system have been poorly studied at temperatures below 1000oC.
The purpose of this work is to investigate thermodynamic properties of spinel solution at
temperatures of 1100 – 1300 K by measuring EMF.
The samples for analysis were obtained by solid-phase reaction that occurs when iron,
magnetite and aluminum hydroxide powders are mixed. Synthesis was performed in a vacuum
at a temperature 1300 K.
The EMF was measured in a cell with a solid oxygen conduction electrolyte:
−Pt, Fe, FeO │ ZrO2+ Y2O3│ Fe1-cAlcOy, Pt +. (1)
Standard electrode is equilibrium mixture iron and wustite. The experiments were performed
while raising and lowering the temperatures within the range of 1100 – 1300 K.
In accordance with experimental data, the activity of magnetite in the spinel solution
was calculated according to the formula
E
2F
=
ln aFe3O4
10 ⋅ RT
3 ∫ (4 − 3 y)dE ,
0
(2)
E
where Eo (mV) is the EMF equilibrium value of cell (1) for mix of wustite and magnetite.
The values of the activities for magnetite calculated in accordance with formula (2) are shown
in Fig.1.
The =ƒ( ) function was described
in terms of the theory of regular solutions,
according to which the energy of mixing (Q)
depends only on the temperature:
2
X FeAl2O4
⋅Q
a=
Fe3O4 X Fe3O4 ⋅ exp ( ) (3)
RT
The activities of magnetite calculate in accordance
with formula (3) are shown in Fig.1 with solid
lines. The model is apparently in good agreement
with the experimental data and can be used to
describe the thermodynamic characteristics of a
spinel solution. The activities of hercynite (the
dashed line in Fig.1) were calculated in accordance
Fig. 1. Dependences of the activities with a formula analogous to Eq.3. From the
of magnetite (solid line) and dependence it follows that magnetite and hercynite
hercynite (dashed line) on the molar are partially soluble in each other at temperatures
fraction of magnetite below 1123 K. Using the theory of regular solution
at temperatures of: made it possible to estimate temperature of
1 – 1273, 2 – 1173, 3 – 1073, decomposition of spinel solution. The critical
4 – 973 К temperature of layering of spinel solution is 1084 K.
THERMODYNAMIC AND STRUCTURAL PROPERTIIES OF AQUEOUS SOLUTIONS

OF GLYCOSAMINOGLYCANS IN THE SELF-CONSISTENT FIELD
Kolesnikov A.L. 1, Nogovitsin E.A. 1, Budkov Yu. A.2
1
Ivanovo State University
2
Institute of Solution Chemistry, Russian Academy of Science, Ivanovo
e-mail: bancocker@mail.ru
Glycosaminoglycans are linear and long unbranched polysaccharides consisting of a
repeating disaccharide unit. Hyaluronic acid is a non sulphate glycosaminoglycan. It is a part
of connective, epithelial, and neural tissues. Hyaluronan is one of the major component of
extracellular matrix, it found in many body fluids (saliva, synovial fluid, etc.). Heparin is
synthesized in mast cells, clusters of which there are in the bodies of animals, especially in the
liver and lungs. It is used for prevention and treatment of thromboembolic diseases in
operations on the heart and blood vessels, to maintain the liquid state of the blood in
cardiopulmonary bypass and hemodialysis, as well as to prevent blood clotting in laboratory.
Chondroitin sulfate is a sulfonated glycosaminoglycans, which is a specific component of
cartilage and a part of the synovial fluid. As part of aggrecan, chondroitin sulfate is a major
component of cartilage. The tightly packed and highly charged sulfate groups of chondroitin
sulfate generate electrostatic repulsion that provides much of the resistance of cartilage to
compression. Loss of chondroitin sulfate from the cartilage is a major cause of osteoarthritis.
This paper presents the results of the calculation of the thermodynamic and structural
properties of aqueous solutions of hyaluronic acid, heparin and chondroitin sulfate with added
salts NaCl and CaCl2. We use a theoretical approach which is based on the Gaussian
equivalent representation for the partition and distribution functions in the form of functional
integrals [1-3]. An equation of state for the semi-flexible polymer chains in solution was
received. The equation of state describes the experimental data of the osmotic pressure [4-6].
We calculated such properties of polyelectrolytes as persistence length, radius of gyration,
compressibility, entropy, and degree of dissociation. Radius of gyrations which was calculated
for the polymer chains of chondroitin sulfate and hyaluronic acid decreases with increasing
ionic strength. Our results are consistent with the available research data [7]. Dependence of
the radius of gyration of heparin on concentration of monomers has a maximum at the lowest
supplements of NaCl. In the solution of chondroitin sulfate degree of dissociation decreases
with increasing concentration of polymers, and in solutions of hyaluronic acid and heparin it
increases with increasing concentration of polymers. The mean force potential which was
calculated for the monomers in solution has a minimum. It corresponds with the presence of
attraction between disaccharides on the different polymer chains.
References
1. E.A. Nogovitsin, Yu. A. Budkov, Russian Journal of Physical Chemistry A, 2011, 85 , p.
1363–1368.
2. E.A. Nogovitsin, Yu. A. Budkov, Physica A, 2012, 391, 2507.
3. S. A. Baeurle, E. A. Nogovitsin, Polymer, 2007, 48, 4883-4899.
4. F. Horkay, P. J. Basser, D. J. Londono et al, J. Chem. Phys.,2009, 131, 184902.
5. N.O. Chahine, F.H. Chen et al, Biophysical Journal, 2005, 89, 1543-1550.
6. R.M. Peitzch, W.F. Reed, Biopolymers,1992,Vol.32,219-238
7. M. Bathe et al, Biophys. J. 2005, 88, 3870- 3887.
THE VISCOELASTIC PROPERTIES OF MAGNETIC LIQUIDS AND THEIR

DEPENDENCE ON THERMODYNAMIC STATE VARIABLES
Komilov К, Zaripov A.K.
Tajik National University, Dushanbe, Tajikistan
e-mail:k.komilov@mail.ru
From temperature, density, concentration, saturation magnetisations of a material of
magnetic particles and intensity of an exterior magnetic field the contribution of separate
mechanisms of a viscous dissipation to an interior friction of a magnetic liquid allows to
estimate examinations of dependences of coefficients of viscosity and elastic moduli. The
existing literary data shows that the question on dependence of coefficients of viscosity from
various thermodynamic state variables of a magnetic liquid is yet enough explored, as these
theories have either static, or phenomenological character [1]. For more detailed analysis of an
explored question build-up of the microscopic theory on the basis of molecular-kinetic
representation which remains till now unclosed is necessary.
The purpose of the present conferring is numerical examination of dependences of
coefficients of volume η v (ω ) and shear η s (ω ) viscosity, and also volume K r (ω ) and shear
µ (ω ) elastic moduli of magnetic liquids from various thermodynamic state variables under
the influence of an exterior nonuniform magnetic field. For carrying out of numerical
calculations we will use expressions of these quantities which have been gained earlier in
operation [2]. Numerical calculations are spent for the magnetic liquids prepared on the basis
of kerosene, and also water and firm particles of magnetite Fe3O4. According to effects of
numerical calculations with growth of density and concentration of explored magnetic liquids
of value of coefficients of viscosity and elastic moduli non-linearly increase, and with
temperature magnification slowly decrease. These effects are in the satisfactory consent with
the existing literary data [3,4]. Reduction of coefficients of viscosity with temperature
increase, most likely, is related to expansion of a liquid and impairment of interpartial
interactions.
The carried out analysis shows that character of dependence of coefficients of viscosity
and elastic moduli in both explored magnetic liquids from concentration and density is
identical. It is caused by that with growth of density and concentration in magnetic liquids the
medial distance both between liquid-carrier molecules, and between magnetic particles
essentially decreases and, as consequence, all views of interaction between structural unities
of a magnetic liquid essentially increase.
References
1. Berkovsky B.М., Medvedev V.F., Krakov M.C. Magnitnie jidkosti. М: Khimiya, 1989. –
239 s.
2. Odinaev S., Komilov K., Zarifov A. On the molecular theory of relaxation processes and
the viscoelastic properties of magnetic liquids // Rus. Journ. of Phys. Chem. – 2006. – V.
80. – № 5. – P. 751–757.
3. Rah K., Eu B.Ch. Density and temperature dependence of the bulk viscosity of molecular
liquids: Carbon dioxide and nitrogen // J. Chem. Phys. – 2001. – V. 114. – № 23. – P.
10436–10447.
4. Matusevich N.P., Orlov L.P., Samoilov i dr. Poluchenie i svoystva magnitnikh jidkostey /
Preprint ITMO im. A.V. Likova AN BSSR. – Minsk: 1985. – № 12. – 52 s.
EFFECT OF TEMPERATURE ON THE STRUCTURAL CHARACTERISTICS

OF WATER-SPAN80/TWEEN80-DEСANE SYSTEMS
Koneva A.S., Chernyshev Y.S., Safonova E.A., Lezov A.A.
e-mail: Alisha987@gmail.com
In this study, the effect of temperature on the structural characteristics of water-in-decane
Winsor IV microemulsions stabilized with a mixture of non-ionic surfactants Span80 (sorbitane
monooleate) and Tween80 (polyoxyethylene sorbitan monooleate) was investigated. The systems
at different surfactant ratios were studied by changing of water and surfactants concentrations. By
use of the mixture of Span80 (HLB 4.9) and Tween80 (HLB 15.0) the hydrophile–lipophile
balance (HLB) of amphiphilic additive is varied that can improve stabilization of the
microemulsions.
The self-diffusion coefficients, sizes, densities and viscosities of microemulsions were
determined in the temperature range 298.15 - 333.15 K at water content up to 10 wt.%.
The hydrodynamic radii of aggregates were determined by photon correlation spectroscopy
(PCS).
To measure the self-diffusion coefficients the spin-echo 1H NMR was used in the presence
of a regulated stationary magnetic field gradient. The self-diffusion coefficient D is directly
related to the decay of the amplitude of the spin echo signal according to the following equation:
where A(G0) and A(0) are the signal intensity in presence and absence of field gradient, γ is the
proton–gyromagnetic ratio, G0 is the magnetic field gradient and τ is the time gap between the
pulses. Three contributions to the general dependence of A(G0) can be distinguished. These
components with different values of D correspond to the diffusions of decane, surfactant
monomers and reverse micelles or microemulsion droplets.
An increase in temperature leads to monotonic increase in D values of reverse micelles of
Tween80 + Span80 in decane at 35 wt.% of the total surfactant content. The D values of
microemulsion droplets forming by the water addition reduce in comparison with D of the reverse
micelles. The effect of temperature on the self-diffusion coefficients of microemulsion droplets
for С10H22(62.7 wt.%)-Span80/Tween80[49/51] (33.3 wt.%)-H20(4.0 wt.%) system is shown in
fig. 1. At a certain temperature the dependencies obtained change for all three components. This
is probably the result of the new phase formation. According to the PCS data the droplets sizes
increase in the temperature range studied.
pure
C10H22
1E-5
C10H22
D, cm2s-1
surfactant
monomers
1E-6
microemulsion
droplets
1E-7
2,85 2,90 2,95 3,00 3,05 3,10 3,15 3,20 3,25 3,30 3,35 3,40
1000/T, K-1
Fig. 1. The self-diffusion coefficients of components in dependence on inverse temperature.

The work was financially supported by the St. Petersburg State University (projects
11.37.141.2011 and 12.38.76.2012).
THERMODYNAMIC AND KINETIC LAWS OF CALCIUM OXALATE

MONOHYDRATE CRYSTALLIZATION
Korolkov V.V.1, Golovanova O.A.1, Punin Yu.O.2
1
F.M. Dostoevsky Omsk State University, Omsk
e-mail: korolkov-92@mail.ru
2
Study of crystallization of compounds that enter into the composition of physiogenic
and pathogenic organic-mineral aggregates (OMA) is important and actual field of modern
researches. One of the main components of OMA is calcium oxalate which has a large
significance in its formation.
As is generally known, formation of solid phase in crystallization process takes place on
existing surfaces or on the surface of nuclei. Gibbs energy of nucleation is made up of
volumetric, surface and constituent due to the elastic deformation energy of the structural
change in solids. For liquid phase the Gibbs energy of nuclei formation can be restrict the first
two constituents:
V
∆G = ∆GV + ∆GS = ⋅ ( µ s − µl ) + σ s.
VM
The energy of nucleation and the value of critical radius of nucleus depend on the
supersaturation: the higher the supersaturation, the smaller the Gibbs energy of nucleation and
the smaller size of the nuclei.
We have shown that the formation of compounds that enter into the composition of the
pathogenic organic-mineral aggregates occurs in non-equilibrium conditions, besides kinetic
factors play a certain part in it.
To study the kinetics of the crystallization process saturation ratio was chosen
γ = C0 Cs = 5, 7, 10 produced by a chemical reaction: Ca 2+ + C2 O 4 2− → CaC2 O 4 .
Determination of kinetic parameters of crystallization – the rate constants and the orders of
crystallization – is based on time dependence of the degree of reaction
α =− (C0 Cτ ) (C0 − Cs ) obtained from conductometric analysis (Table).
Table. Kinetic characteristics of the crystallization of calcium oxalate monohydrate

Characteristic γ =5 γ =7 γ = 10
n 7,9 10,1 12,0
lg k 26,5 33,1 38,6
The orders of crystallization n in functions lg k = f (γ) are significantly greater than two,
which is not consistent with the dislocation mechanism of crystal growth. In addition, for a
given system exponents increase with the growth of initial supersaturation. In our opinion,
these orders are the result of the approximation of exponential law, which describes the two-
dimensional nucleation mechanism.
As a result of research of the kinetics of monohydrate calcium oxalate formation the
values of the rate constants and orders of crystallization are obtained, and found that the
growth of crystals of calcium oxalate monohydrate occurs by two-dimensional mechanism.
This work was partially supported by the Russian Foundation for Basic Research
(№ 12-03-98011-r_sibir_a).
THERMODYNAMIC PROPERTIES AND PHASE EQUILIBRIA

IN THE WATER – BUTANOL (1, 2, ISO-) – 18-CROWN-6
AND THE WATER – PROPANOL (1, 2-) – 18-CROWN-6 SYSTEMS
Kovalenko N.A., Uspenskaya I.A.
e-mail: nik-kovalenko@yandex.ru
Due to the unusual structure the crown ethers form stable complexes with some metal
ions. These complexes are widely used in extraction processes, analytical and organic
chemistry. Special properties of the crown ethers are revealed more fully in the nonaqueous or
mixed medium of chemical reactions. For a prior estimation of these reactions it is necessary
to have information about stability constants and interaction parameters of solution
components. The purpose of this work is a modeling of the water – alcohol – 18-crown-6
systems, which is based on excess Gibbs energy functions of binary systems with opportunity
to include the higher order interaction parameters.
The binary water (alcohol) – 18-crown-6 subsystems were not experimentally studied
enough, unlike the water – alcohol solutions. Therefore the static vapor pressure apparatus
was built for obtaining activities of a solvent in binary solutions of crown ether. The pressure
gauge was calibrated with a vapor pressure of pure water in a temperature range of 291.15 to
304.15 K. The vapor pressure of water in the water – sodium chloride system at 298.15 K was
measured to check the reliability and accuracy of the whole measuring system after
calibration. As a result the vapor pressures in the solutions of 18-crown-6 in water, (1-, 2-,
iso-) butanol, (1-, 2-) propanol were measured in a wide concentration range at 293.15 and
298.15 K.
The general local composition model was used for the description of thermodynamic
properties of ternary solutions. According to this model the excess Gibbs energy with account
of ternary interaction parameters can be written as:
G ex 3
Φi z 3 θi 3  3 
= ∑ x i ln + ∑ q x
i i ln + ∑ x
Φi i 1 =
i ln  ∑ x j ρ ji  −
=RT i 1 x=
i 2i1 = j1 
 3   3   3 
−q1 x1 ln  ∑ θiτ i1 + θ 2θ3τ 231  − q2 x2 ln  ∑ θiτ i 2 + θ1θ3τ 132  − q3 x3 ln  ∑ θiτ i 3 + θ1θ 2τ 123 
=  i 1=   i 1=  i1 
This equation reduces to well-known local composition models UNIQUAC (when ρij = 1, τijk =
0), Wilson (when qi = 1, ri = 1, ρij = 1, τijk = 0) and Tsuboka – Katayama (when qi = 1, ri = 1,
τijk = 0).
Parameters of the model were fitted using experimental data of the water – alcohol
systems (vapor-liquid and liquid-liquid equilibria, mixing enthalpies), the water – 18-crown-6
system (activities of the solvent, solubility of crown ether, dilution enthalpies) and the alcohol
– 18-crown-6 system (activities of the solvent, solubility of crown ether). Obtained earlier
miscibility gaps in the water – alcohol – 18-crown-6 systems were used for testing the results
of calculation and for the modification of thermodynamic model by ternary interaction
parameters’ introduction.
The work is performed at User Facilities Center of M.V.Lomonosov Moscow State
University under support of Ministry of Education and Science of Russia (Contract
N16.552.11.7081) and RFBR grants number 11-03-00499-a and 12-03-31069-mol.
ACID-BASE AND COMPLEX FORMATION PROPERTIES OF GLYCYLGLYCINE

IN THE WATER-DIMETHYLSULFOXIDE SOLUTION
Kovaleva J.A., Naumov V.V., Isaeva V.A., Sharnin V.A.
e-mail: oxt703@isuct.ru
Dissociation constants of reactions of glycylglycine-ion (pk1), glycylglycine (pk2) and
constant of complex formation of nickel(II) with glycylglycine (lgkst) were measured by
potentiometric method at T=298K and I=0.1M(NaClO4) in the solvent H2O-DMSO composition.
Pk1 increases with the growth of mole fraction of DMSO in solution is established.
Dependence of pk2=f(XDMSO) has extreme character with a minor peak at 0.2-0.3 mole fraction
DMSO.
It is known in most cases the complex stability monotonically increases in complexes of d-
metal with ligand carbocsil type due to increasing concentration of organic component in the
solution. It is detected for complex formation of glycylglycine with Ni(II) in water-acetone [1]
and water-ethanol [2] solution. Hardening of complex [NiGG]+ is observed at small additives
DMSO in H2O-DMSO solution then stability has little decreases.
The ΔG° transfer of glycylglycyn-ion from water in H2O-DMSO solution (fig.2) were
determined for the analysis of reagents solvent contributions in ΔG° reaction of [NiGG]+ change.
The ΔG° reaction of formation [NiGG]+ were measured by interphase distribution method. The
analysis of reagents solvent contributions to ΔG° reaction formation of [NiGG]+ change shown
that increase of complex stability is determined by the change of ligand ΔG° destabilization
(contribution II) exceeds the differences in [NiGG]+-ion and Ni2+ ion resolvation (contribution I)
at low concentration of DMSO in H2O-DMSO solvent:
ΔtGor= ΔtGo ([NiGG]+)- ΔtGo(Ni2+)- ΔtGo(GG-).
I II
9 pK2 9
10
GG-
8 8
[NiGG]+- Ni2+
∆trG°, kJ/mole
7 7
pK1 5
lgK1
pKi
6 6
5
lgK1 0 X(DMSO), mol. tr.
5
0,0 0,2 0,4 0,6
4 4
1
3 X(DMSO), mol. fr. 3
-5
0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
Fig. 1. The dissociation constants of glycyl- Fig. 2. Solvent composition of H2O-DMSO

glycine-ion pK1, glycylglycine pK2 and influence on the ΔG° reaction formation of Ni2+
constants of stability [NiGG]+ (lgKst) in the with glycylglycine-ion (1) and ΔGo resolvation
solvent H2O-DMSO composition. reagents.
The difference between the contributions of I and II contributions begin to decrease
resulting in the decrease of ΔtG0 reaction negative value at high concentrations of DMSO.
References
1. V.A.Isaeva, V.V.Naumov, V.A.Sharnin//Koordin. chimiy.–2009.–T.35.–№11.–S.878-880.
2. V.V.Naumov, V.A.Isaeva, V.A.Sharnin //Jurn. Neorg. Chimiy.–2011.–T.56.№7.S.1208-121.
The investigation is performed with the support of Russian Federation Ministry of
Education and Science, agreement № 14.В37.21.0801.
THERMODYNAMIC MODELING OF LIQUID CRYSTAL – NON-MESOGEN SYSTEMS

Kowalski R.1, Pestov S.M.2
1
Technische Universität Hamburg-Harburg
2
Liquid crystals (LC) have found a wide application in display technologies. Systems
containing thermotropic LC are the most interesting and difficult objects for physico-chemical
analysis [1]. Phase diagrams of LC – non-mesogen systems are important both for the solvent
selection for purification of mesogens and for choice of components (dichroic dyes, low
viscosity additives) for LC mixtures.
Solubility curves of LC that belongs to different homologues series (cyanobiphenyls,
phenylbenzoates, benzoic acids) are investigated. The possibility to reveal the solid state
polymorphism of mesogens by investigation of LC - non-mesogen systems is demonstrated.
The type of molecular interactions in LC – non-mesogen systems plays the main role in the
choice of a solvent for crystallization. Usage of the thermodynamic methods to predict the
phase diagram type, to calculate the solubility curves and invariant point position seems to be
very interesting. Excess thermodynamic functions for melting are calculated. The models
based on the solubility parameter (usage of Hildebrand and Hansen solubility parameters, the
Flory-Huggins equation) are applied for the demixing prognosis. Applicability of the group-
contribution methods to estimate activity coefficients of components (UNIFAC models) is
checked on the solubility curves calculation. Data on thermodynamic and physical properties
for mesogens are taken from [2] or calculated using the group-contribution methods.
Restrictions and advantages of the considered thermodynamic methods are discussed.
Correlations between alkyl chain length of LC and their solubility in solvents of different
polarity are determined. A correlation of the invariant points position on the components
properties is revealed. A dependence of the phase diagram type on the excess thermodynamic
functions is discussed.
References
[1] Molochko V.A., Pestov S.M. Phase equilibria and thermodynamics of systems containing
liquid crystals. Print. Center MITHT, Moscow, 2003. 242 p. (in Russ.)
[2] Pestov S.M. Physical properties of liquid crystals. / Landolt-Boernstein. N.S. VIII/5A.
Springer, Berlin, 2003. 492 p.
STABILILTY FUNCTIONS OF THE MELTS IN T1-T2-M

(T1, T2 – TRANSITION METALS, M – SIMPLE METAL)
Kuznetsov V.N., Kabanova E.G.
Chemical Department, Lomonosov Moscow State University, Moscow
e-mail: vnk@general.chem.msu.ru
Fictive (not found experimentally) miscibility gaps often arise during predictions of
thermodynamics of ternary disordered phases (f.e., melts of primary solid solutions) based on
extrapolation of bounding binaries. In particular, those were found when the calculations of
some ternaries like Cu–Pd–Sn, Au–Pd–Sn, Al–Co–Cu and others were attempted using
common methodics like Kohler, Toop, and Muggianu. Moreover, such fictive miscibility gaps
were detected in published descriptions of experimental thermodynamic data when those were
treated with insufficient care.
To clarify that situation Lupis stability function Ψ was calculated in the frame of the
model which combines Muggianu extrapolation with ternary interactions assumed to have
linear concentration dependence:
G (x1, x2, x3) = ΣXsGij(xi, xj) + x1x2x3(L0x1 + L1x2 + L2x3)
Xs (123)
Here i, j, k = 1, 2, 3 are indices of components, sum is taken over binaries, i.e. pairs (i,j)
with i < j.
That model is implemented in the Thermo-Calc software and is widely accepted for
CALPHAD calculations of phase equilibria for systems with 3 and more components.
The resulting expression for Lupis Ψ function may be expressed as sum of Ψ function
values for bounding binaries, calculated at x1, x2, x3 in the ternary, plus accounts from
parameters of ternary interactions as well as from squares and pair products of all the
interaction parameters (both binary and ternary ones). The result obtained generalize well-
knows formulae of Meiering (1950) which were obtained in the frame of regular solution
model.
Published thermodynamic data for the Cu–Au–Sn, Ag–Au–Sn and Ag–Pd–Sn ternaries
were used to gain an impression of typical behavior of Ψ function in disordered phases in the
systems formed by two transition and simple metals. There are fairly detailed data both for
enthalpies of formation in wide composition regions and for tin activity.
The approximation possibilities of the model were investigated. It was found that
combined effect of parameters of ternary interactions on the Ψ function is counter-intuitive, as
negative values of those not uncommonly give rise to de-stabilizing (in the sense of Ψ
function) effect.
The results obtained were used for prediction of thermodynamic properties of liquid and
fcc solid solutions in the Au-Pd–Sn and Cu–Pd–Sn ternaries. Some recommendations for the
search of the proper values of parameters of ternary interactions were formulated to preclude
the appearance of fictive miscibility gaps in a course of extrapolational predictions of
thermodynamic properties of the ternaries of this kind, including non-investigated and poorly
investigated ones.
All the calculations were performed using computer algebra system (CAS) maxima,
which is distributed under GPL.
THERMODYNAMIC PARAMETERS OF VISCOSITY FLOW PROCESSES

OF THE SYSTEM OF CETYLPYRIDINIUM BROMIDE–NICOTINIC ACID–WATER
Lachinyan M.L., Harutyunyan L.R., Harutyunyan R.S.
e-mail: romik@ysu.am
The viscosity study of the system cetylpyridinium bromide (CPBr)-nicotinic acid
(NicA)-water has both theoretical and practical significance. It is important to note the
components of this system are used for medical-pharmaceutical aims.
The values of relative viscosity of the system CPBr-NicA-water was obtained and bases
on Jones-Dole equation the values of B -coefficients were determined. The B -coefficient is
dependence on from the properties of solvent and solute and means the interaction of solute
ions with solvent [1]. The values of B -coefficients of the system CPBr-NicA-water at
different concentrations of NicA and at different temperatures are given in Table 1.
Table 1. The values of B -coefficient of the system CPBr-NicA-water for premicellar

concentrations of CPBr
[NicA].102, B , dm3/mol
mol/l 298 К 303 К 313 К 318 К
0.0 3.27 5.94 7.21 8.50
0.5 -4.21 -3.90 -3.02 -2.49
0.7 -3.54 -2.81 -2.75 -1.07
1.0 -2.53 -2.40 -2.23 -0.81
The negative values of B -coefficient show that in the presence of NicA the structure
breaking component of viscosity is dominant [1]. On the bases of values of B -coefficient,
( )
according with transition-state theory, the values of energy of activation ∆µ 20 ≠ , enthalpy of
(
activation ∆Η 0≠
2 ) and entropy of activation (T∆S ) of viscoflow process were determined
0≠
2
[2].
Table 2. The values of thermodynamic parameters of activation of viscoflow process of the

system CPBr-NicA-water for premicellar concentration of CPBr
[NicA].102, mol/l ∆µ 2o ≠ , kJ/mol ∆H 2o ≠ , kJ/mol T ∆S2o ≠ , kJ/mol
0.0 1985.2 3516.7 1011.3
0.5 2497.2 3982.1 1098.7
0.7 3148.7 4027.1 1381.3
1.0 3902.2 4293.2 1493.8
The positive values of T∆S 2 and ∆H 2 indicate that transition-state is associated
0≠ 0≠
with bond breaking [2].
References
1. T. Erdey-Gruz. Transport phenomena in aqueous solutions. Academiai Kiado, Budapest,
1974.
2. D. Feakins, D.J. Freementle and K.G. Lawrence, J. Chem. Soc., Faraday Trans., 170,
1974, 795.
SOLVENT SUBLATION IN SOLUTIONS OF RARE-EARTH ELEMENTS

Lobacheva O.L.
The National Mineral Resources University «Mining», Saint-Petersburg
e-mail: olga-59@yandex.ru
Extensive experimental material accumulated in the world on methods of adsorption of
surface separation, allowed to solve many serious environmental problems of the present time.
In particular, the task of extraction of trace amounts of toxic substances, heavy metals,
of rare-earth elements can be solved also with the help of processes of surface separation
(solvent sublation).
Solvent Sublation (S. S.) is a combination of ion flotation and the liquid-liquid
extraction. Unlike conventional liquid-liquid extraction, in S. S. mass transmission from the
aqueous phase to the organic happens with the participation of gas bubbles (as in the case of
foam separation). Method is relatively little studied.
For the first time the term "Solvent Sublation" (in English solvent sublation" was introduced
by F.Sebba in 1962.
In contrast to the froth separation in S.S. (solvent sublation from the Latin sublatio -
rise) sublat, adsorbed bubbles, and submitted them to the surface of the water solution, is
stored in a thin (5-10 mm) layer blending with water and organic liquids. In S.S. mass
transmission from the aqueous phase to the organic happens with the participation of the gas
bubbles. This eliminates a number of problems, connected with through emulsification. In
addition, the volume of the organic phase is relatively small, as it is determined by the
capacity in regard to sublet and cross-sectional area of the machine, but is not connected (as in
a normal liquid-liquid extraction) with the value of the specific surface area of between
organic and water phases.
The above mechanism can be implemented only in a small gas - 3-5 cm3 per 1 cm2 area
of the layer of the organic phase. These effects are typically not taken into account, however,
they may be of considerable importance.
In the work of the used S.S. column height of 70 cm and 5 cm in diameter. The studied
solutions contained 10-4моль/kg Ce+3, Eu+3, Sm+3 and sodium dodecylsulfate as a transport
agent. As the organic phase was used 2-octanol. The process of S.S. spent more than 2 hours.
Thus, from the obtained experimental data on the extraction of rare-earth metals with
the help of the solvent sublation method, it can be concluded that the method is highly
effective compared (in particular, the process of extraction). Removing the reaches of 99.0%.
References
1. Adsorptive bubble separation techniques / Ed. by R.Lemlich. N.Y. 1972. 342 p.
2. Lobacheva O.L., Chirkst D.E., Dzhevaga N.V. Solvent sublation ions of yttrium of diluted
aqueous solutions with the use of sodium dodecylsulfate //Russian Journal of Applied
Chemistry. 2012. V. 85. № 8. P. 1208-1212.
The work has been performed according to the Federal program AVCP № 2.1.1/973
and GK № 0622 from October 05.10.2010.
MOLECULAR-BASED PREDICTIVE MODELS APPLIED TO HIGH ADDED VALUE

OXYGEN-BEARING MOLECULES AND THEIR MIXTURES
Lugo R.1, Paricaud P.2, Coquelet C.3, Passarello J.P. 4, de Hemptinne J.C.1
1
IFP Energies nouvelles, Rueil-Malmaison, France
e-mail: rafael.lugo@ifpen.fr
2
ENSTA ParisTech, Paris, France
3
Mines ParisTech, CEP/TEP, Fontainebleau, France
4
Laboratoire des Sciences des Procédés et des Matériaux, LSPM,
CNRS-UPR 3407 Université Paris
Due to the rarefaction of fossil ressources, green chemistry, and in particular the chemistry
of plant-based products, is now a real alternative to petrochemicals, the latter being less
compatible with the concept of sustainable development. Lignocellulosic biomass (LCB) appears
particularly as an interesting raw material providing a wide variety of families of high added
value molecules that can be used in the production of chemicals. The design of green and
innovative processes for the valorisation of biomass (biorefinery) requires the understanding of
the thermodynamic behaviour of species associated to LCB loads. These systems are particularly
complex due to the wide variety of oxygenated compounds and their intra- and intermolecular
interactions that make these mixtures highly thermodynamically non-ideal. The Equations of
State (EoS) used for hydrocarbons (models typically found in most process simulators) fail to
reproduce these non idealities and the challenge for the design and optimization of biorefinery
units is to have appropriate tools that can adequately characterize the loads, in the same way as
fossil loads are described in current industrial applications.
Due to the large variety of molecular families and structures that need to be taken into
account, the development of predictive models is of high importance. To ensure their
predictability, these models must have a strong theoretical basis so that they can be extrapolated
beyond the pressure, temperature, composition and molecular families spectra used for their
evaluation and adjustment. In this work, we have applied the Group Contribution (GC) PPC-
SAFT EoS [1] to different oxygen bearing molecules and their mixtures with different solvents
(water, hydrocarbons, alcohols...). Top-of-the-list molecules (alcohols, acids, ketones, aldehydes
...) have been treated in previous works, of which a synthesis will be provided here. The present
work will be specifically focused on the thermodynamic modelling of multifunctional molecules
having an aromatic ring and at leas an oxygen-bearing function: m-cresol, anisol, catechol,
guaiacol, furfural, syringol, vanilline, eugenol and quinone. We have also compared our
predictions with those obtained using the quantum COSMO-based approaches [2,3] and, when
necessary, we performed original phase equilibrium measurements. In particular, we discuss the
effects of self- and cross-association phenomena and how these phenomena can me modelled
using the predictive approaches previously mentioned.
References
1. D. Nguyen-Huynh, JC. de Hemptinne, R. Lugo, JP Passarello, and P. Tobaly , Industrial &
Engineering Chemistry Research 50 (12), 7467–7483 (2011)
2. J. Li , P. Paricaud, Energy & Fuels 26 (6), 3756–3768(2012)
[3] M. Nala, E. Auger, I. Gedik, N. Ferrando, M. Dicko, P. Paricaud, F. Volle, JP Passarello, JC. de
Hemptinne, P. Tobaly, P. Stringari, C. Coquelet, D. Ramjugernath, P. Naidoo, R. Lugo, Fluid
Phase Equilibria 337, 234-245 (2013).
Financial support from the French National Research Agency, through project MEMOBIOL
(ANR-09-CP2D-10-01), is gratefully acknowledged.
MICROSTRUCTURE OF IONIC ASSOCIATES IN ACETONITRILE SOLUTIONS

OF TETRAALKYLAMMONIUM SALTS AND IMIDAZOLIUM IONIC LIQUIDS
FROM NMR EXPERIMENT
Lukinova O.V.1, Marekha B.A.1,2, Idrissi A.1, Kalugin O.N.1

1
V. N. Karazin Kharkiv National University, Kharkiv, Ukraine
2
Universite Lille 1 - Sciences et Technologies, Villeneuve d'Ascq, France
e-mail: elena.v.lukinova@gmail.com
Solutions of tetraalkylammonium (TAA) salts in aprotic solvents are currently one of the
most widespread electrolyte components for supercapacitors (electric double-layer capacitors).
Ionic liquids (ILs) and their mixtures with molecular solvents are considered as promising
alternative electrolytes for such systems. One of the important working parameter of
supercapacitors defined by an electrolyte is electrical conductivity which is primarily
determined by ionic association for the solutions in polar aprotic solvents (like acetonitrile,
AN) with moderate value of dielectric constant.
Here we present the results of proton NMR study of solutions of TAA salts (Et4NBr,
Et4NBF4, Bu4NBr, Bu4NBF4) and 1-butyl-3-methlyimidazolium based ILs (BmimBF4,
BmimPF6) in AN in the concentration range of 0.02 – 1 mol/dm3 at 298 К.
The concentration dependencies of cations R4N+ and Bmim+ proton signals revealed
that the most sensitive to the ion pairing are the α-methylene hydrogens of the TAA cations
and imidazolium hydrogen atoms of ILs. Structures of the ion pairs formed by the studied
electrolytes were analyzed by means of quantum chemical modeling. Some examples of the
optimal configurations of the ion pairs are shown in figure 1.
Figure 1. Optimal geometrical configurations for ion pair of TAA salt Bu4NBF4 and
of imidazolium IL BmimBF4.
It was shown that in case of TAA salts anion occupies empty space between alkyl groups
of a cation forming contact ion pairs of penetrated type, while imidazolium ILs are
characterized by contact ion pairs where anion is located around an aromatic ring (fig. 1).
SPACE MODEL MOUNTING FOR CONSTITUTIONAL DIAGRAM

OF MULTICOMPONENT SYSTEM
Lutsyk V.I.
Institute of Physical Materials Science SB RAS, Ulan-Ude
e-mail: vluts@pres.ipms.ru
Thermodynamic calculation sometimes produce the phase diagrams (PD) with the
problems, when phase regions are lost and some phases are not taken in consideration as a lack of
thermodynamic data. Idea to assemble a space model of PD from its geometrical elements
produced an effective instrument for specialists in materials science and technology. Original
technique for PD engineering has been offered: 1) a space scheme of 3-phase regions is to be
elaborated; 2) contours of the surfaces of unruled nature are to be closed and data of
thermodynamic assessment are used on this stage; 3) surfaces should be approximated as the
minimal ones (with the minimal area); 4) all geometrical elements are designated, and their
“names” contain the meaning (reason) of these designations. After the computer assembling the
PD space model helps to solve different fundamental and applied tasks.
By means of these models [1–2]: 1) all 3-phase regions are divided into the fragments with
the reactions of eutectic or peritectic types; 2) concentration fields of invariant reactions permit to
design microstructure of heterogeneous material, when competition of crystals with different
dispersity produces alloys and ceramics which differ by microconstituents of phases assemblages;
3) any experimental or simulated section of phase diagram (isotherm and isopleth) may be
corrected and verified; 4) new schemes are offered to optimize experimental techniques for
invariant composition determination.
If 3D model of T-x-y diagram is formed as a set of surfaces, it may be used only to check
the geometrical features of PD. If 3D model consists of phase regions, it permits to analyze the
mass balances and to design the microstructures. Some peculiarities of micro- and nanostructure
forming may be explained by the fragmentation of 3-phase regions according to the different
reactions. Earlier it was known only about the change of reaction L→Ir+R3 for L+R3→Ir in Ti-Ir-
Ru system (R1=TiIr & R2=TiRu form solution R, R3=TiIr3, R4=Ti3Ir). Thanks to the PD
computer model for this system two more 3-phase regions with melt and three subsolidus regions
were determined with the transformations: region Ir+Ru+R3 is divided into 4 parts, region
Ru+R+R3 has three “2-wing” surfaces of 2-phase reactions ∆mC=0, ∆mR=0 & ∆mR3=0, but they
divide it into 6 fragments in such way, when there are 3 reactions of eutectoid type with 3
reactions of peritectoid type between them. One more reason for the microstructures variety is the
competition of crystals with different dispersity, when a field of invariant reaction is divided into
the fragments with the tiny eutectical crystals, with more large primary crystals and with the both
type of these crystals. This competition can be observed on the diagrams of vertical and
horizontal mass balances.
Computer model of PD gives the possibility to analyze the crystallization stages for any
composition and to find the concentration fields both with individual set of microstructure
elements and the fields at which the crystallization scheme and microconstituents of phases
assemblage coincide with those in the adjoining fields. It is used as an important tool to
investigate multicomponent system, to correct its constitutional diagram, to design the
miscrostructures of heterogeneous material and to decipher its genotype [3–4].
References
1. V. Lutsyk, V. Vorob'eva // Perspectivnye materialy, 2011, no 13, p. 191-197 (in Russian).
2. V. Lutsyk, A. Zelenaya // Solid State Science, 2012, Vol. 14, no 11-12, p. 1604-1608.
3. V.I. Lutsyk, A.E. Zelenaya, V.V. Savinov // Crystallogr. Rep. 2012, Vol. 76, no 7, p. 71-74.
4. V.I. Lutsyk // Bulletin of Buryat Scientific Centre (Russian Academy of Sciences, Siberian
Branch), 2012, no 1(5), p. 78-97. (in Russian).
CONSTRUCTION OF 4D-MODEL OF THE PHASE DIAGRAM OF Fe-Ni-Cu-S SYSTEM

ON THE BASIS OF EXPERIMENTAL RESULTS
Lutsyk V.I., Vorob’eva V.P., Zyrianov A.M., Starykh R.V.1, Sinyova S.I.1
Physical Problem Department, Buryat Scientific Centre of SB RAS, Ulan-Ude
1
Saint Petersburg State Polytechnical University
e-mail: kafedra-cm@yandex.ru
Diagrams of phase equilibrium are fundamental products, used by researchers in a wide
field of applications. In particular, phase diagram of Fe-Ni-Cu-S system represents the basis
for majority compositions of sulfur-metal products and semi-products in pyrometallurgical
processing of copper and nickel. Information about phase transformation in the volume of
this system will allow predicting crystallization processes of metallurgical liquids in a wide
range of compositions, optimizing parameters of heat performance of metallurgical
equipment, carrying out material balance calculations of coexisting phases at any temperature.
In spite of high importance of discussed system in the pyrometallurgy of copper and
nickel, available and confident information about phase diagram of Fe-Ni-Cu-S system is
absent. Probably, it is connected with some methodical difficulties of experimental research
and very complicated graphic interpretation of received results.
Present work has combined experimental researches of phase transformation in 3D-
volume of concentration triangle with using of modern analytical methods (DTA, TGA, SEM,
and EPMA) and computer modeling of phase limits with following construction of 4D-model
of quaternary Fe-Ni-Cu-S system.
Initial data for computer modeling are temperatures and compositions of nonvariant and
monovariant transitions, as well as liquidus and solidus temperatures in a wide field of
compositions of Fe-Ni-Cu-S system. Indicated parameters are obtained with using of complex
of modern experimental physicochemical methods: differential thermal analysis,
thermogravimetry, scanning electron microscopy and electron probe microanalysis.
Construction of computer model of quaternary Fe-Ni-Cu-S system, as well as boundary
ternary subsystems is carried out with using of reference book named “Computer models of
volume phase diagrams of main topological types”, issuing by authors of present work.
STRUCTURAL DYNAMICS, DIELECTRIC SPECTRA AND THERMODYNAMIC

PROPERTIES OF AQUEOUS ELECTROLYTE SOLUTIONS
Lyashchenko A.K.
Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow
e-mail: aklyas@mail.ru
A new approach was suggested, that allow establishing the correspondence between
short scale dynamics (elementary motion) of water molecules to long scale (dielectric
relaxation) and macroscopic thermodynamic hydration properties (osmotic coefficient,
chemical potential and activity of water) of electrolyte solutions in a wide range of
concentrations. Broadband dielectric spectroscopy can examine this matter because of low
frequency limit of dielectric spectra is the static dielectric permittivity. On the other hand
linear character of dependence (aw) of 1/εs was shown (30 examples).
The static dielectric permittivity (εs) is thermodynamic characteristic of electrolyte
solutions which is directly used in macroscopic solvation (hydration) theories. In the
concentrated solutions of salts εs is not equal to dielectric permittivity of pure water which
enters into many theoretical equations for calculation of activity coefficients, constants of
equilibrium and other thermodynamic parameters (Debye-Hukkel, Pitzer, Fuoss equations
etc.). It determines the presence of empirical parameters in such equations. Direct
measurements εs in electrolyte solutions are impossible because of their high conductivity.
However, there is a possibility of εs determination by the use of the microwave dielectric
measurements, computer simulation and geometrical models of hydration spheres.
The experimental method of dielectric spectroscopy (7-25 or 7-120 GHz) was advanced
for εs determination of concentrated electrolyte solutions in a temperature range 288-308K.
On the basis of these data the static dielectric constants were calculated. It was found out
experimentally significant differences of values and dependences εs in various concentration
ranges (in the concentrated solutions εs = 20-30) and practical absence of εs changes in high
concentrated solutions. There are simple relation between spectral features of complex
formation and static dielectric permittivity of electrolyte solution.
The mechanism of water elementary and collective dynamics in electrolyte solutions is
considered on the basis of confined rotator theoretical model (with different types of
elementary motions), experimental dielectric (in the range 7-120 GHz) and absorption (up to
800 cm-1) data. The spectra of complex dielectric permittivity and absorption in all orientation
frequency range are described using the theoretical scheme. The common structure–kinetic
model of ion hydration shells is suggested. It includes the fraction of molecules in good
tetrahedral configurations, the fraction of molecules in distorted configurations and molecules
with partly frozen degree of orientation freedom. The new scheme of aqueous dielectric
polarization is proposed where unchanged bulk water with εs = 80 and partly “frozen”
molecules in the first coordination sphere are present. For 1:1 electrolytes the dielectric
saturation and electrostriction in the hydration shells of ions are absent. The common
principles of the structure-kinetic and thermodynamic theory of hydration are established at
the level of the molecular orientation processes.
Work is executed at support RFBR, the project. № 12-03-00062.
THERMODYNAMIC MODELING OF THE In-Sn-Zn SYSTEM

Lysenko V.A., Vassiliev V.P.
Lomonosov Moscow State University, Chemistry Department, Moscow
e-mail: vallys2@yandex.ru
Lead-tin solder alloys are widely used in modern electronics. However, owing to
increased environmental concerns on lead usage as well as legislative restrictions,
development of lead-free solders is highly demanded. In-Sn-Zn alloys are very perspective for
the drop-in replacement of Pb-Sn solders, therefore thermodynamic description of the In-Sn-
Zn system and calculations of phase equilibria in this system are of great interest.
In this study, analytical expression for the Gibbs energy of liquid phase in the In-Sn-Zn
ternary system was found using the available in literature themodynamic descriptions of the
binary subsystems as well as experimental data on the liquidus of the system and
thermodynamic properties of the ternary liquid. The obtained expression was used to calculate
phase equilibria by minimizing the Gibbs energy of the In-Sn-Zn system.
The liquidus surface projection and coordinates of the invariant equilibria of the system
were determined. Three vertical sections of the In-Pb-Zn phase diagram with the molar ratios
of In/Sn=1, In/Zn=1 and Sn/Zn=1 were calculated. The results of the calculations agree well
with the available experimental data.
(project no. 11-08-01154).
THERMODYNAMIC CHARACTERISTICS OF COMPLEX FORMATION

OF THE ETYLENDIAMINDISUCCINIC ACID WITH A NUMBER OF 3d-ELEMENTS
Lytkin A.I., Chernyavskaya N.V., Chernov А.S.
Ivanovo State University of Chemical Technology, Ivanovo
e-mail: ail@isuct.ru
Poliaminopolicarbonic acids such as etilendiamindisuccinic (EDDS) acid containing
one type of electron donor substituents, to recommend to the dawn of the good itself in many
areas of science and technology, by the universality of their complexing properties, biological
activity, not toxicity. The practical use these chelating and complexones, their influence on
biochemical processes require a comprehensive study of the thermodynamic characteristics of
reactions of these compounds in solution.
We have carried out the thermodynamic researching of complexing properties and
energy of processes complexation of etilendiamindisuccinic acid with a number of practically
important metals: Cu (II), Ni (II), Cd (II), Co (II), Pb (II), Zn (II). It was found that the
exothermic processes of complex Cu (II), Ni (II), Cd (II), Co (II), Pb (II), Zn (II) with EDDS
decreases in the series:
∆H CuА
0
2− = -50,02±0,10 kJ/mol > ∆H
0
NiА 2−
= -27,19±0,21 kJ/mol > ∆H CdA = -16,51±1,08
0
2−
kJ/mol > ∆H CoA 2 − = -14,75±0,80 kJ/mol > ∆H PbA2− = -14,61±0,27 kJ/mol >
0 0
∆H ZnA
0
2− =
-14,05±0,65 kJ/mol.
Similar associations were observed in the stability of these complexes:
lg β CuA2− = 18,35±0,10 > lg β NiA2− = 16,01±0,04 > lg β CoA2− = 13,54±0,10 >
lg β ZnA2− = 12,77±0,06 > lg β СdA2− = 12,07±0,06 > lg b PbA2− = 11,65±0,09.

The lower the enthalpy of formation of complexes, the more the process is controlled by
the entropy factor, that is, observes a dependence on the electronic structure of the central ion.
∆SCuA
0
2− = 150 J/mol⋅К > ∆S
0
CdA2− = 176 J/mol⋅К >
∆S PbA
0
2− = 201 J/mol⋅К > ∆S CoA
0
2− = 204
J/mol⋅К > ∆S ZnA

0
2− = 236 J/mol⋅К > ∆S
0
NiA 2− = 252 J/mol⋅К
A similar regularity is observed for complexes with ethylenediaminetetraacetic acid
(H4Edta), the immediate analogue of etilendiamindisuccinic acid, which agrees well with the
single-type structure hexadentatny complexones found in structural studies.
ENTHALPY AND SOLUBILITY DATA OF H2S IN AQUEUS SALT SOLUTIONS

AT CONDITIONS OF INTEREST FOR GEOLOGICAL SEQUESTRATION
Majer V., Koschel D., Coxam J.-Y.
Institute of Chemistry of Clermont-Ferrand,
CNRS-Blaise Pascal University 63177 Aubière, France
e-mail: vladimir.mayer@univ-bpclermont.fr
Describing the dissolution of acid and greenhouse effect gases in aqueous electrolyte
solutions under high pressures and at moderately elevated temperatures is of great interest in
connection with their geological storage in deep saline aquifers. The dissolution of hydrogen
sulphide in NaCl(aq) and CaCl2(aq) was studied by direct calorimetric measurements of the
heat of mixing ∆Hmix at condition where H2S is gaseous, liquid or supercritical. The
measurements were carried out using a customized mixing unit developed for an isothermal
differential heat flux calorimeter Setaram BT 2.15D. The experimental technique was
specifically adapted for operating with H2S taking into consideration its high toxicity. The
heats of mixing were obtained with the 1 and 3 mol.kg-1 NaCl(aq) at target temperatures of
323, 353 and 393 K, and at pressures up to 13, 31 and 20 MPa, respectively. Analogous
measurements and were performed with 0.33 and 1 mol.kg-1 CaCl2(aq) at the medium
temperature and pressures up to 31 MPa in order to investigate the effect of the cation
valence. The experiments were always carried out in the regions where the solution is
unsaturated and saturated by H2S. The obtained concentration dependence of ∆Hmix allowed
deriving simultaneously both the limiting enthalpy of solution ∆Hsol of H2S and its solubility
limit. Comparison with the earlier published data for H2S in pure water at identical conditions
(Koschel et al. Ind.Eng.Chem.Res. 2007, 46, 1421-1430) gives the information on the salting
out effect and its dependence on temperature, pressure, as well as on the concentration and
nature of the salt. The newly obtained data are also compared with those resulting from the
measurements with supercritical CO2 at analogous conditions (Koschel et al. Fluid Phase
Equilibria 2006, 247, 107-120).
PROCESSES OF SALT PRECIPITATION IN THE FLOW WATER-SALT SYSTEMS

Makaev S.V., Valyashko V.M.
e-mail: makaev@gmail.com
Supercritical water oxidation (SCWO) is the method that is used for disposal of organic
wastes by decomposition and oxidation them in supercritical water under temperatures about 450-
550°C and pressures about 200-300 atmospheres. Inorganic acids are produced with
decomposition of organic compounds and they should be neutralized because of their high
corrosion activity, especially in hydrothermal condition. Solubility of resulting salts of type 2
(such as sulphates, carbonates and phosphates of alkali metals) is extremely low. The same is with
similar salts which are already present in wastes. Crystallization of such salts leads to plugging of
flow SCWO systems and it is a main obstacle for wide use of this perspective supercritical
technology of waste removal. There are expensive methods to bypass plugging of flow facilities
such as using high flow velocity or reactor with cooled parietal volume [1].
We proposed [2, 3] a method to prevent crystallization of salts of type 2 by adding to initial
solution a quantity of salts of type 1 which are high soluble in water at elevated temperatures and
their water solutions are hydrothermal solvent for type 2 salts. Research was conducted in
custom-made laboratory flow reactor at different flow rates (5 and 2.5 ml/min), temperatures up
to 450-500°C and pressures up to 300 atmospheres. Systems K2SO4–KCl–H2O, K2SO4–K2CO3–
H2O, Na2SO4–NaCl–H2O were used as a model. Maximum concentration of type 2 salts that
doesn't plug flow facility is equal to 0.10-0.15 n/n% in most cases (depends on nature of salts).
When adding about 1 n/n% of type 1 salts occurs we don't see plugging for solution with
concentration of type 2 salts (or mixture of type 2 salts) up to 0.30 n/n% (values vary for different
salts). That means it is necessary to have about 3-4 excess in type 1 salts concentration to free
flow path. With decreasing flow rate to 2.5 ml/min it is necessary to have excess of type 1 salts
concentration in 7-10 times to eliminate the plugging. Precise values depend on nature of salts,
for example, 0.13 n/n% of Na2SO4 requires 1.11-1.21 n/n% of NaCl to liquidate the blockage of
reactor at flow rate of 2.5 ml/min.
The influence of organic wastes on plugging of facility was studied by the example of
Na2SO4–NaCl–H2O system. Ethanol and ethyleneglycol (up to 5 n/n%) were used as model
substances. It was shown that with addition of organic compounds it is necessary to have higher
concentration of type 1 salts for free flow streaming. For both substances it was required to
increase NaCl concentration to 1.28 n/n% with the same concentration of Na2SO4. Organic
additions decompose at this conditions and we performed the analysis of obtained gases.
The experiments with addition of H2O2 as oxidizing agent for organic impurities were
performed using the same model system. Measurements were complicated because of the strong
and fast corrosion of the reactor and also by the fact that decomposition and oxidation in this case
proceeds much faster and were accompanied by rapid gas production resulting in pressure and
temperature jumps. Data about concentration strongly vary but it is possible to notice that assured
removal of plugging requires about 8 times excess of NaCl concentration.
References
1. Marrone P.A., Hodes V., Smith K.A., Tester J.W. J. Supercrit. Fluids. 2004. V. 29. P.289.
2. Valyashko V.M. Proceedings of the 13th International Conference on the Properties of Water
and Steam. Ottawa: NRC Research Press, 2000. P. 727.
3. Makaev S.V., Bitohov T.M., Kravchuk K.G., Urusova M.A., Valyashko V.M. SCF-TP. 2010. V.
5. №4. P. 75.
SOLVATION THERMODYNAMICS OF HARD-CORE PARTICLES

IN POLYMER MATRIX: A MODEL DESCRIPTION
Malakhov A.O.
Topchiev Institute of Petrochemical Synthesis,
e-mail: malakhov@ips.ac.ru
Solvation thermodynamics of gases and vapors in condensed matter is a classical field
of physical chemistry. The large collection of the accumulated experimental facts requires the
theoretical comprehension, for which the phenomenological approaches are clearly
insufficient.
A common trend today is computer simulation (e.g., molecular dynamics). However,
this way of describing the system gas/solvent is too labor-consuming, especially if in the role
of solvent polymer acts and it is necessary to receive thermodynamic functions over a wide
range of temperatures and pressure.
The alternative, in our view, is the development of approximate statistical
thermodynamic models that take into account the main structural features of the solvent and
solute and enabling it is enough simply to calculate both thermodynamic functions, and
distribution of free volume of polymer on size of microcavities.
The model offered in work is development of the scaled particle theory known in
physics of simple liquids. In this model, the polymer molecules are represented as a sequence
of units, hard spheres. Effective (depending on temperature) diameter units are chosen so that
the model reproduced the isothermal compressibility of the real polymer. The proposed model
has been tested by comparison with the available data of computer experiments.
Within this approach analytical expression for partition coefficient of the solute in the
solvent and the appropriate thermodynamic functions is received. The task about the
dissolution of hard sphere (the most hydrophobic molecule!) in the real polymers
(polydimethylsiloxane, polystyrene) is considered. Hard particle acts as a molecular probe:
variation of its size allows finding distribution of available free volume of polymer. Note that
the distribution of free volume is one of the most important characteristics (along with
partition coefficient) determining permeability of polymer membranes.
The work also addresses the following issues: how the solubility of a gas depends on the
chain length of the polymer molecules, as changes entropy of dissolution depending on the
condition for process – isochoric or isobaric, does differ qualitatively solubility in the
polymeric liquids and glass and others.
The obtained results are useful from a methodological point of view and are the basis
for examining the solvation thermodynamics of real ("soft") molecules in polymers.
PHASE EQUILIBRIUMS IN THE Ag-Tl(Pb, Bi)-I SYSTEMS AND

THERMODYNAMIC PROPERTIES OF INTERMEDIATE PHASES
Mashadiyeva L.F., Aliyev Z.S., Shevelkov A.V.1, Babanly M.B.
Baku State University
e-mail: leylafarm@rambler.ru
1
Complex silver iodides are a vast family of compounds having different crystal
structures and properties. Many of them are superionic conductors, possessing high Ag+
conductivity. Many of these compounds are used as ion-selective electrodes, solid-state
electrolytes in the different kind of electric batteries, sensors, displays, etc.
Interaction of AgI with iodides of 6p-elements was earlier investigated. It was shown,
that in these systems a number of ternary compounds are formed.
The result of complex investigation of phase equilibriums and thermodynamic
properties of the Ag-Tl(Pb, Bi)-I systems are shown in this activity.
For investigations initial binary compounds were synthesized from the elements of high
purity grade in evacuated (~10-2 Pa) silica ampoules. Alloys of investigated systems were
prepared from binary and elemental components in various quantities in vacuum with
subsequent longtime thermal annealing.
Investigations were performed by X-ray powder diffraction (Bruker D8 ADVANCE
diffractometer with Cu-Kα1 radiation) and differential thermal analysis (NTR-72 device
equipped with two chromel–alumel thermocouples), as well as by measuring of EMF of
chains
(-) AgI (s) | Ag4RbI5(s) | (Ag in alloys) (s) (+) (1)
at 300-360 К temperature range.
Results of EMF measurements confirm the correctness of all drawn solid-state
equilibriums of investigated systems in AgI-TlI-I2, AgI-PbI2-I2 and AgI-BiI3-I2 composition
area, constructed by using of DTA and RFA methods. It was established that silver-lead
iodides were decomposed at 410 K on solid-state reactions.
Partial molar functions of AgI and silver in various phase areas of investigated systems
were calculated from EMF measurements. Based on solid-state equilibriums diagrams the
potential-forming reactions are determined. The lasts are used for calculation of standard
thermodynamic functions of formations and standard entropies of ternary compounds of the
Ag-Tl(Bi)-I systems (table).
Table
Compound − ∆ f G (298 K )
0
− ∆ f H (298K )
0 0
S (298K )
кJ⋅mole -1
J⋅К-1⋅mole-1
AgTl3I5 492.52±2.52 463.4±9.7 623.1±24.5
AgTlI2 212.29±1.03 198.8±4.6 268.3±12.1
AgTl2I3 348.63±1.55 328.4±5.9 413.1±14.8
AgBi2I7 378.8±16.2 379.4±14.5 559.3±17.8
Ag2Bi3I11 608.1±24.5 607.0±21.8 895.9±29.0
Ag2BiI5 307.0±8.5 303.8±9.7 334.5.4±17.1
THERMOCHEMICAL CHARACTERISTICS OF BARIUM CERATE

DOPED BY INDIUM AND NEODIMIUM OXIDES
Matskevich M.Yu.1, Matskevich N.I.1, Wolf Th.2, Bryzgalova A.N.1, Chupakhina T.I.3,
Anyfrieva O.I.1, Vyazovkin I.V.1
1
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy
of Sciences, Novosibirsk
e-mail: calorimetry@yandex.ru
2
Karlsruhe Institute of Technology, Institute of Solid State Physics, Karlsruhe
3
Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences
The compound MCe1-xRxO3-d (M = Ba or Sr, R = rare earth elements, x = 0−0.2) has
been the subject of intense investigation in recent years because of the potential application in
fuel cell, sensor, and ceramic membrane technologies. It is necessary to note that the dopant
solubility limit is less than 20% of the available B sites, and therefore, the possibility of
introducing protonic defects into the matrix is limited. It is important to increase the dopant
solubility for further practical applications. All attempts to increase the dopant solubility limit
were unsuccessful. Another problem is stability of doped BaCeO3 perovskites. The stabilities
of these phases, particularly, thermodynamic stability, are important. The paper is devoted to
determination of formation enthalpy of BaCe0.7Nd0.2In0.1O3-d phase and thermodynamic
stability in respect to decomposition to binary oxides.
We synthesized the BaCe0.7Nd0.2In0.1O2.85 sample for the first time. In the sample the
field of solubility was increased by involving of indium. Polycrystalline samples of
BaCe0.7Nd0.2In0.1O2.85 were prepared by solid-state reaction: BaCO3 + 0.1Nd2O3 + 0.05In2O3 +
0.7CeO2 = BaCe0.7Nd0.2In0.1O2.85 + CO2. The temperature of synthesis was 1400 ºC. The
phase purity was analyzed with X-ray diffractometer (STADI-P, Stoe diffractometer,
Germany, Cu Kα1 radiation). The samples were shown to be phase-pure ceramics with an
orthorhombic structure (space group is Pmcn).
The derivation of the enthalpy of formation of BaCe0.7Nd0.2In0.1O2.85 was done using the
principal scheme based on the dissolution of barium cerate doped by neodymium oxide and
indium oxide as well as the mixture of barium chloride, cerium chloride, indium chloride and
neodymium chloride in hydrochloric acid [HCl (sol)] with KI.
The measured enthalpies of dissolution were used for calculating the standard formation
enthalpy of barium cerate doped by neodymium and indium oxides (BaCe0.7Nd0.2In0.1O2.85).
Literature data for formation enthalpies of BaO, CeO2, Nd2O3 and In2O3 were used to
calculate the enthalpies of formation of BaCe0.7 In0.1Nd0.2O2.85 from binary oxides as
following: BaO(s) + 0.7CeO2(s) + 0.1Nd2O3(s) + 0.05 In2O3(s) = BaCe0.7Nd0.2In0.1O2.85 (s).
∆oxHo (BaCe0.7In0.1Nd0.2O2.85, s, 298.15 K) = −69.8 ± 10.1 kJ/mol. Using these data and data
on entropies we established that above-mentioned mixed oxide (BaCe0.7Nd0.2In0.1O2.85) is
thermodynamically stable with respect to their decomposition into binary oxides at room
temperatures. We compared our data with data on ∆oxHo for BaCe0.8Nd0.2O2.9 and noted that
the stability is increasing with adding of indium oxide in sample.
This work is supported by Karlsruhe Institute of Technology (Germany), Russian Fund

of Basic Research (Project № 12-08-31556 for young scientists) and Program of
Fundamental Investigation of Siberian Branch of the Russian Academy of Sciences.
SELF-ACCEMBLY OF LOW MOLECULAR WEIGHT AND POLYMERIC

SURFACTANTS IN SOLUTION OF DIFFERENT POLARITY
Mel,nikov A.B.1, Bogdanov D.V.1, Kudryashova Z.A.2,
Makarov I.A.1, Suchanova T.A.1, Zorin I.M.1, Rumzev E.I.
1
St. Peterburg State University, St. Peterburg
e-mail: mab-phys-spbu@yandex.ru
2
Polymerized (PMs) and nonpolymerized micelles surfactants of N-acryloyl-11-
aminoundecanoic acid (PAAU) and 2-acrylamid-2-metilpropansulfo acid are investigated by
methods of molecular hydrodynamics (PAMPS-DDA).
It was calculated hydrodynamic sizes, molecular weights and degree of aggregation in
these systems.
A comparison of the PAAU size in acid and salt form in DMF and water showed the
significant difference of diameters (PMs) 5 times. This is due to different polarity solvents.
Increase of hydrodynamics size was found for PAMPS-DDA in a series of alcohol –
dimethylformamide – chloroform solvent for system. Model of self-organizing aggregates in
different environments has been proposed.
ISOCHORIC HEAT CAPACITY AND PVT PROPERTIES

OF BINARY AZEOTROPIC SYSTEM N-HEPTANE–WATER
Mirskaya V.А., Nazarevich D.А., Ibavov N.V..
Institute of Physics of Dagestan Scientific Center of RAS, Makhachkala
e-mail: veronika_mir@mail.ru
Investigated system n-heptane - water [(1-x) C7H16 + x H2O] (x denotes polar
component content) is a representative of complex hydrocarbon – water systems consisting of
components which differ substantially in molecular structure and properties.
The study of such systems is interesting from the standpoint of basic research: further
development of the theory of solutions for complex systems consisting of substances of
different molecular nature, and also a determination of the effect of polar component
impurities on the phase diagrams configuration of hydrocarbon compounds.
The results of the study azeotropy phenomena in complex systems are of interest at the
design of technology for the extraction, azeotropic distillation and obtaining from oil the
chemicals of high purity. Isolation of high-boiling fractions from hydrocarbons is achived by
an azeotropic distillation using a steam. Alkanes are the main components of oil and gas
condensate systems.
There are a number of studies on the thermal properties of these systems. For the first
time the authors began an experimental study of the complex thermal properties (isochoric
heat capacity, Cv, density, ρ, x, pressure P) hydrocarbon – water systems.
The components of the system n-heptane and water do not have a mutual solubility
under normal conditions. In consequence of which their mixture is a heterogeneous three-
phase system a liquid-liquid-vapor with internal interfaces.
Investigations were carried out on an automated PC-based pilot plant that is based on
the well-known technique of high-temperature adiabatic calorimetry, piezometer, described in
detail previously, having a GSSSD techniques status.
The temperature and volume dependences of thermodynamic properties of the system
[(1-x) C7H16 + x H2O] were studied for several constant compositions x = const with different
content of the polar component (water) in the intervals from the normal boiling temperature of
components up to 670 K.
The studied systems are characterized by a very low energy interactions between
molecules of hydrocarbon and polar water molecules. The behavior of the properties of such
systems in a particularly significantly different from those of single-component liquids and
mixtures whose components are mutually-soluble.
As a result of researches on the temperature and volume dependences of the isochoric
heat capacity and pressure are found the peculiarities in behavior of thermophysical properties
of dual exfoliating system n-heptane - water, allowed to identify areas of mutual solubility of
components, the dependence of composition displacement of the system azeotrope state on the
temperature and pressure.
Work was supported by the Russian Foundation for Basic Research (grant № 10-08-
00322-a).
THE CALCULATE OF THE COORDINATES EUTECTIC POINT

IN THE SYSTEM MnS – SrS
Monina L.N., Minikaeva G.F.
Tyumen State University, Tyumen
e-mail: monina83@yandex.ru
Construction of phase diagrams - a long and difficult process, bonded with a large
expenditure of time to reach equilibriums, especially in systems formed solids. The scientists
attempts to use calculated methods to predict the type and construction of the phase
diagram.The system MnS - SrS is a eutectic. Methods of microstructural, microhardness and
X-ray analysis for the 15 samples of different chemical compositions and conditions of
received (samples annealed at 1470 K and crystallized from a melt). The difference of the
ionic radii of Mn2+ and Sr2+ more than 35 %, that does not allowed to suppose about extended
regions of solid solutions on the basis of initial sulfide MnS and SrS. Quantities of the eutectic
crystals in samples containing 2, 95 mol. % SrS, as well as the not changed of the unit cell
parameter and microhardness grain for samples are similar in composition to the original
simple sulfides MnS (2-20 mol. % SrS) and SrS (70-95 mol.% SrS) allows suggests that there
is no area of solid solutions [1]. According to the experiment, the composition of the eutectic
of 33.3 mol. % SrS, the melting point of eutectic crystals 1520 K.
The calculated coordinates of the eutectic point at use of the following equations:
Schroeder's, Efimov-Vozdvizhensky's, Cordes's, Vasilyev's and by equation changes ot the
properties of the system proposed in [2]. An important condition for the adequate application
of this equation - the minimum areas of solid solutions, the ions form a solid solutions must
be isomorphic, or lack of solid solutions. The equation in [2] allows calculating the
coordinates of the eutectic point without first conducting the experiment, only based on the
melting point of the initial components MnS and SrS. The equation Schroeder's is a
thermodynamic equation that includes important parameter - the heat of melting of the
components system. According to equation [2] the coordinates of the eutectic point - 22 mol.
% SrS, T = 1520 K. For the application of the Efimov-Vozdvizhensky's, Cordes's, Vasilyev's
need to know one of the coordinates of the eutectic point - the temperature or composition.
The temperature of melting of the eutectic crystals that calculated by Efimov-
Vozdvizhensky's, Cordes's, Vasilyev's is 1534 K, 1487 K, 1510 K, 1637 K, respectively.
References
1. Monina L.N., Potapov A.G., Chelnokova O.A., Yurkova O.S. Phase equilibria in the MnS -
SrS, MnS - BaS / / Proceedings of the VI Russian Conference "Physical and chemical
processes in condensed state and at interfaces", Voronezh. 15-19 October. 2012. P.345-346.
2. Ganeev A.A., Khalikov A.R, Kabirov R.R. Development of the method of calculation of the
eutectic concentration and temperature diagrams / Bull. USATU. Ufa - 2008. - T. 11. - № 2
(29). - P.116-122.
THERMODYNAMICS OF INTERCALATION INTERACTION

OF DOUBLE-STRANDED DNA WITH ACTINOCINE DERIVATIVES
Moroshkina E.B.
Saint-Petersburg State University, St-Petersburg
e-mail: evmorosh@mail.ru
A number of different organic compounds are able to form the equilibrium complexes
with double-stranded DNA. A change in DNA structure under interaction results in breaking
of its biologic functions, this being a base of bioactivity of such compounds. One of the
modes of DNA binding with organic compounds including a flat heterocyclic chromophore is
intercalation. Intercalation model of binding involves insertion of a flat heterocyclic
chromophore in double-helix DNA between to neighboring pairs of nitrogen bases, effecting
the inherent changes in its macromolecular parameters, those as a contour length and
thermodynamic rigidity. The thermodynamic parameters of this interaction are determined by
many techniques. As a presence of heterocyclic chromophore gives rise to longwave
absorption band of the compound which does not overlap with similar band of DNA, the most
widely used are the spectral ones.
This paper presents the results of studies concerning the DNA interaction with various
actinocine derivatives involved in actinomycine antibiotics.
The compounds were synthesed at a department of organic chemistry of St-Petersburg

State Institute of Technology. For all the compounds, with viscometry and dynamic
birefringence techniques , can be determined the intercalation mode of binding these
compounds with DNA. The thermodynamic parameters of binding of these compounds with
DNA were determined by spectrophotometry and spectropolarimetric titration methods.
The dependence of parameters of intercalation binding of compounds on substitute
origin, ion strength of a medium, ligand ionic state was analysed. It was shown that
protonizing of chromophore substitute gives rise to ligand affinity to DNA, but, even with no
charge on ligand surface, ion strength of a medium affect the value of binding constant. At a
presence of additional binding centers of ligand with DNA, at positions 1 and 9, their effect on
intercalation binding of chromophore depends on a distance between chromophore and those
centers of binding.
EFFECT OF AQUA-ALCOHOL MIXED SOLVENTS

ON THE STABILITY OF 18-CROWN-6 SODIUM ION COMPLEXES
Motornova M.N., Maximov A.I., Mamontov M.N., Uspenskaya I.A.
e-mail: ira@td.chem.msu.ru
The stability of the crown ester complexes with ions depends among other things upon
nature and composition of solvent. It was earlier determined that constants of the complex
formation of 18-crown-6 (18C6) with sodium, potassium and thallium ions in the mixed
solvents are proportionally to alcohol content [1]. Some experimental results [2] contradict to
this correlation, so the purpose of present work was to make additional measurements of
equilibrium constants for the reaction
→[Na (C12 H 24 O 6 )]
+
Na + + C12 H 24 O 6 ← (1)
in aqua – n-propanol mixtures. The values of stability constant for the 18-crown-6 – sodium
ion complex at 298.15 K were calculated with the results of electrochemical cell
measurements:
Cl--ISE|NaCl(m)+TBAH(I-m)+H2O(100-wAlc)+Alc (wAlc) (+ 18C6) | Na+-ISE, (2)
where wAlc is the weight percentage of alcohol in the solvent, TBAH is a solution of tetra-n-
butylammonium hydroxide. The equilibrium constant for the complex formation (eq.1) was
expressed in terms of the initial ( mi0 ) and equilibrium ( mi ) molal concentrations:
+ − m
m[Na (C H O )]+ 0
m Na Na +  F∆E 
K (1) = = , m Na + = m Na + exp − ,
( )
12 24 6 0
m Na + mC12 H 24O6 m Na + mC12 H 24O6 − m Na + + m Na +

0 0
 RT 
where ∆Е is a difference of EMF cell (2) in the presence and without of 18-crown-6. Values
of the logarithm of the [Na(C12H24O6)]+ formation constants versus molar fraction of alcohol
in mixed solvents are presented at Figure. As can be seen, linear dependence between lgК(1)
and composition of mixed solvent really exists, so it is possible to estimate the complex
formation constants at 298.15 K in any water−alcohol solvent without additional experiments.
Figure. Plot of the logarithm of the

complex formation constants of 18-
crown-6 with sodium ions vs. the alcohol
content xAlc in the mixed solvent at 298.15
K; ♦ - present work, ◊ - literature data
References
1. Igumnov S.N., Mamontov M.N., Uspenskaya I.A. // J.Chem.Eng.Data, 2012, 57(2), 456.
2. Didi Yu., Tsurko Е.N., Bondarev N.V. // Russ. J. Gen. Chem., 1997, 67(6), 885.
ENTALPHIES OF COMPLEX FORMATION OF NICKEL(II) WITH

GLYCYLGLYCINATE-ION IN WATER-DIMETHYLSULPHOXIDE MIXTURE
Naumov V.V., Kovaleva Yu.A., Isaeva V.A., Sharnin V.A.
The Research Institute of Thermodynamics and Kinetics of Chemical Processes, Ivanovo
e-mail: nvv_1985@mail.ru
The report presents the results of calorimetric investigation of nickel(II) complex
formation reactions with glycylglycinate-ion in water-dimethylsulphoxide solvent in the
composition range 0.00÷0.60 mol. of DMSO. Nickel(II) with glycylglycinate-ion forms
mono-, bis- and triscomplexes according to equations:
Ni2+ + GG- ↔ [NiGG]+, ∆H1 (1)
[NiGG] + GG ↔ [Ni(GG)2],
+ -
∆H2 (2)
[Ni(GG)2] + GG- ↔ [Ni(GG)3]-, ∆H3 (3)
As the content of DMSO in the solution, an increase exothermic reactions of mono- and
biscomplexes. Joining third anion ligand to bisligandnoy particle accompanied by a decrease
with increasing concentration of exothermicity nonaqueous component (Fig. 1).
Fig. 1. Enthalpy characteristics
-
100 [Ni(GG)3] of reactions formation mono-,
80 bis- and trisglycylglycinate
GG- complexes of nickel(II) and
60
reagents solvation in water-
dimethylsulphoxide mixtures.
∆trH°, kJ/mol
40
20 [Ni(GG)2]
Addition of each subsequent
0
0,1 0,2 0,3 0,4 0,5 0,6
ligand increases the differences
-20 [NiGG]+ in resolvation enthalpy of
X(DMSO), mol. fr.
r1 complex species (fig. 1). In the
-40
Ni2+ case of the complex compounds
-60 formation on the third stage of
coordination the differences in
solvation of tris- and
biscomplexes are much higher than the change of ligand solvation enthalpy and, thus,
determine the decrease in the exothermicity of complexation on the third stage. Probably large
exothermicity of complexation reactions of nickel(II) with gliycylglycinate-ion due to the
metal-ligand coordination through the amine nitrogen atom of glycylglycine. The interaction
of ion-complexing with the peptide oxygen atom is played a secondary role.
On the basis of thermochemical data found that the formation of complexes nickel with
glycylglycine in water and aqueous solutions of DMSO at its low concentrations (till 0.2÷0.4
mol. fr.) is determined by the enthalpy and entropy components, but at higher concentration of
DMSO main contribution to the formation of the mono- and biscomplexes makes the enthalpy
factor, while for the triscomplexes the entropic component becomes determinant.

OPTIMIZATION OF THERMODYNAMIC MODEL OF SPENT FUEL EXTRACTION

Nechaevskiy S.Yu., Ochkin A.V.
D.I. Mendeleev University of Chemical Technology of Russia, Moscow
e-mail: ochkin@rctu.ru
The modern fuel reprocessing is based on the system H2O-HNO3-UO2(NO3)-TBP-
diluent. The thermodynamic model of this system includes a division of the main system into
subsystems and the investigation of their thermodynamic properties.
The analysis of subsystems has been based on the next principles:
1. Molar fractions xi are used as a concentration scale. Rational activity coefficients fi (fi
= ai/xi where ai is a thermodynamic activity) are applied during some calculations.
2. Gibbs-Duhem equation is used to calculate an activity or a coefficient activity of a
component “i” on concentrations of other components
xidlnai +∑ xjdlnaj = 0 (1)
xidlnfi +∑ xjdlnfj = 0 (2)
A cross differentiation relation has been used to calculate effect of water concentration
on activity coefficients of other components
(∂lnai/∂mj)mi.mk = (∂lnaj/∂mi)mj.mk (3)
Where mi is a molality of component i in (3) and derivative is calculated at first on mi and mk
but then on mj and mk.
3. There are three groups of interaction that should be taken into account during the
calculations of activity coefficients. The interaction of components 1 and 2 can be taken into
account as
lnf1 = b1 φ2n or f1 = exp(b1φ2n) (4)
where φ2 is a volume fraction of second component. 2.0<n≤2.2.
At first the interaction of H2O with TBP was described with the equation
xw = Kt·φt ·aw·exp(b1·φ tn) + k2·[Kt·φ t·aw·exp(b1φ tn)]2 + Kd·φ d·aw (5)
where the indexes “t” and “d” are related to TBP and the diluents respectively. An interaction
between water and TBP is taken into account in equation (5) in accordance with equation (4)
and the linear additively of the water solubility is presumed.
The mass action law has been used to calculate the formation of solvates
xds = Kex∙ aUN·xt2∙ft2/fds (6)
xij = Kij·aai·atj/fij (7)
where indexes «ds», «UN», «t» and «a» are related to disolvate, uranyl nitrate, TBP and acid,
Kex is an extraction constant of uranium, Kij is a constant of formation of solvate formation
from i acid molecules and j TBP molecules, ft , fds and fij are rational activity coefficients of
TBP, a disolvate and a solvate from i acid molecules and j TBP molecules.
The equilibrium in three three-component systems H2O-TBP-diluent, H2O-HNO3-TBP
and H2O-UO2(NO3)-TBP and one four-component system H2O-HNO3-TBP-dodecane has
been calculated. The calculation results are presented in various publications and summed in
the report at the conference ATALANTA-2012 [1].
The problems of the optimization of the elaborated model are the main aim of this
report. The homogeneity of relative errors of experimental concentrations are assumed during
calculations. However errors of molar fractions used in equations (5)-(7) are not homogeneous
usually. Then the problem of errors of calculated constants is arisen.
Reference
1. Ochkin A., Gladilov D., Nechaevsky S. Procedia Chemistry, 2012, v. 7, p. 315.
THERMODYNAMICS OF Na2O-Al2O3-SiO2-H2O SYSTEM

Nekhoroshev E.E., Lebedev L.G, Voskov A.L., Kovalenko N.A.
e-mail: nekhoroshev-chem@mail.ru
Despite the fact that Bayer process for alumina production is used for above one
hundred years, its exergy coefficient is low. Such situation is the reason of search of efficient
methods for an active alkali and aluminum return to the cycle and for an utilization of
ecotoxic red mud. One of the main red mud constituents are the hydroalumosilicate phases.
For an efficient solution of the task of existing manufactures optimization and to decrease the
produced waste amounts it is necessary to have a physico-chemical model of Bayer process.
The aim of this work is the optimization of parameters of thermodynamic model of
liquid phase of the Na2O-Al2O3-SiO2-H2O system and condensed phases equilibria assessment
using the obtained model.
Pitzer model was used for liquid phase properties description in the Na2O-Al2O3-H2O
and Na2O-SiO2-H2O subsystems. Interaction parameters for NaOH solutions were taken from
literature [1]; values of interparticle interaction parameters in the sodium aluminate solution
were calculated from the experimental data about osmotic coefficients and gibbsite solubility
in the temperature interval 30-70°C. Na+, OH- and Al(OH)4- were considered as main ions. It
was shown that obtained parameters satisfactory describe not only gibbsite-solution
equilibrium in the wide ranges of temperature and concentration, but also an existing data
about boehmite-solution equilibrium in the temperature range 80-160°C (see Fig. 1) not used
in the optimization process. This fact confirms the prediction ability of the proposed model.
After taking into account the ion pair association in the extremely concentrated solutions the
sodium aluminate Na2O∙Al2O3∙2.5H2O solubility was described for the first time.
(a) (b)
Fig. 1. Description of data about phase solubility in the alkaline aluminate solution: (a) gibbsite, (b) boehmite.
During the modeling of liquid phase properties in the Na2O-SiO2-H2O system a taking
into account of H2SiO42- and H3SiO4- forms allowed us to adequately describe osmotic
coefficient data at 25°C.
For independent correctness verification of proposed liquid phase model of Na2O-
Al2O3-SiO2-H2O system an experimental investigation of vapour pressure (and water
activities) were carries out for the quaternary solutions.
Reference:
1. Pabalan R.T.,Pitzer K.S. Thermodynamics of NaOH(aq) in hydrothermal solutions. //
Geochimica et Cosmochimica Acta.1987. V. 51. P. 829-837.
The investigations were financially supported by RFBR (Projects No. 13-03-00328 and
12-03-31069-mol_a).
MICRO-INHOMOGENEITIES IN THE HOMOGENEOUS FLUID

OF SMEARED CHARGES
Nikolaeva A.L., Vlasov A.Yu.
Saint-Petersburg State University, Department of Chemistry, Saint-Petesburg
e-mail: alexandra.l.nikolaeva@gmail.com
Some conceivable applications of systems composed of big charged particles immersed
in a neutralizing sea of smaller particles of a solvent relate to possible development of phases
having charge waves. This type systems are exemplified by aqueous colloidal suspensions,
water solutions of polymers and polyelectrolytes. Charge waves are procured by clusters or
strips which preferably consist of particles with the same sign of charges. At times these are
observed in the aforesaid systems. Theoretical analysis of structure in fluids with sphere-
symmetry potentials is based on the investigation into the asymptotic decay of the total pair
correlation functions (TPCF), particularly, in the domains of the state space where the latter
change the mode of decay from monotonous to exponentially damped oscillations. A change
of the behavior signals a presence of a crossover point on a phase diagram. Varying state
points for a given system gives rise to a crossover line. This line heralds instability with
respect to a transition to a modulated phase. There are two types of such instability. The first
one represents an appearance of clusters. Then, a value of a TPCF oscillation period is
considerably greater than the size of particles and clusters are composed of some tens or even
hundreds of particles. In this case, the crossover line is termed a Kirkwood line. If the period
of oscillations equals a particle diameter, then instability with respect to a crystalline lattice
arises. Its boundary in the state phase is designated as a Fisher-Widom line.
We considered one-, two- and three-component fluids where particles interact via a
l  r 
modified Coulomb potential (qi q j ) ⋅ B erf   (qi – charge of species i, lB – Bjerrum length,
r  2σ 
σ - diameter of a particle, erf(x) – error function, r – inter-particle separation) with addition of
a term corresponding to their soft quadratic repulsion within a cut-off radius. For calculation
of the pair correlation functions and thermodynamic properties we used the hyper-netted chain
closure of the Ornstein-Zernike equation. But the pivotal focus of our study was an
ascertainment of the crossover and identification of its nature. The point is that the nature of
the crossover is established in two ways, viz., 1) by phenomenological relations between the
TPCF oscillation period and temperature and 2) analysis of poles of the TPCF Fourier image.
After testing these methods over a wide range of thermodynamic conditions in such systems
we have established that in a given systems instability conforms to a Kirkwood type what
means formation of cluster-type in-homogeneities. Both methods provide perfect coincidence
of instability boundaries in the state space. It is worth a note that the system is
thermodynamically stable at investigated domain of the phase diagram. This fact is confirmed
by calculating of principal co-factors of iso-dynamic matrix of Helmholtz energy.
DIAGRAMS OF CHEMICAL AND ELECTROCHEMICAL STABILITY

OF Sc – Si SYSTEM
Nikolaychuk P. A.
Chelyabinsk State University, Chelyabinsk, e-mail: npa@csu.ru
This study is devoted to thermodynamic description of Sc – Si – O and Sc – Si – H2O
systems at T = 298 K and p = 1 bar.
According to Sc – Si system phase diagram [1], two scandium silicides – Sc5Si3 and
ScSi – exist is system at standard conditions. The third silicide, Sc2Si3, exists only at elevated
temperatures. All silicides are stoichiometric compounds, without any noticeable homogeneity
ranges. There are no data on solid solubility of Si in (hexagonal-Sc) and Sc in (diamond-Si), it
is vanishingly small, and the components can be treated as insoluble in each other.
The standard Gibbs energies of formation of scandium silicides are calculated from
data on their standard enthalpies of formation [2, 3] and entropies at 298 K [4].
Both scandium and silicon can form only one oxide; there are Sc2O3 and SiO2,
respectively. Some intermediate phases exist between two these oxides [5], but only
thorvertite, Sc2Si2O7, has reliable thermodynamic information [6]. Thermodynamic properties
of oxidation reactions in Sc – Si – O system at 298 K are calculated and the state diagram of
Sc – Si – O system is plotted. It seems that chemical affinity of scandium to oxygen is greater,
than that of silicon, and it oxidizes more easily. The oxidation of Sc – Si system in air
environments ends with formation of Sc2O3 and Sc2Si2O7 in scandium-rich region and of
Sc2Si2O7 and SiO2 in silicon-rich region.
In water environments, scandium can form only Sc3+ cations [6], and silicon can exist
in many isopolyacids, the simplest of which are H2SiO3 and H4SiO4 [7]. However, only two
H+ can dissociate from the acids, therefore, the presence of anions like HSiO3− , SiO32− ,
H 3SiO−4 and H 2SiO24− in solution is to be considered. And finally, the electrochemical
formation of scandium hydride (ScH2) [8] and silicon hydrides (SiH4, Si2H6) [9] is possible.
The potential – pH diagram of Sc – Si – H2O system is plotted at temperature of 298
K, air pressure of 1 bar and activities of ions in solutions, equal to 1 mol l–1, with
consideration of different forms of silicon acids and anions. Basic chemical and
electrochemical equilibria in system are summarized. The domains of thermodynamic stability
of various phases are depicted. Thermodynamic stability of Sc – Si system in air and water
environments is determined by the composition of the system.
References
1. V. N. Eremenko, K. A. Meleshevich, Yu. I. Buyanov and P. S. Martsenyuk, Poroshk.
Metall., 12 (1988), 52.
2. Yu. M. Golutvin, E. G. Maslennikova and L. G. Titov, Izv. Akad. Nauk SSSR, Met.,
6 (1984), 47.
3. L. Topor and O. J. Kleppa, Metal. Trans. B, 20 (1989), 879.
4. N. I. Sichev, P. V. Geld and G. I. Kalishevich, Zh. Fiz. Khim., 54 (1) (1980), 224.
5. Zhiliang Hong et al. J. Am. Ceram. Soc., 92 (2009), 193.
6. J. G. Travers, I. Dellien and L. G. Hepler. Thermochim. Acta, 15 (1976), 89.
7. J. V. Walther. Essentials of Geochemistry. Second Edition. Jones & Bartlett Learning, 2005.
704 p.
8. T. Kobayashi and H. Takei. J. Less Comm. Metals, 70 (1980), 243.
9. F. Cotton and G. Wilkinson. Advanced Inorganic Chemistry. New York – London – Sydney
– Toronto: John Wiley & Sons, 1972. 1147 p.
THERMODYNAMICAL PROPERTIES OF CALCIUM AND CADMIUM NITRATES

IN N-METHYLPYRROLIDONE AT 298.15 K
Novikov A.N., Rassokhina L.Yu., Vasilyov V.A.
Mendeleev University of Chemical Technology of Russia,
Institute in Novomoskovsk
e-mail: lara.2204@mail.ru
The actuality of investigation of non-aqueous solutions was caused by their wide
utilization in industry, science and engineering. The solvent methylpyrrolidone chosen as the
object of investigation is widely used in practice. However the data of its properties are
limited.
Heat capacity Cp and density ρ of solutions of calcium and cadmium nitrates in N-
methylpyrrolidone (MP) at 298,15 K were experimentally investigated. For measurement the
precision calorimetric and densimetric installation were used. The error of Cp and ρ
measurements wеre not more than ±1·10-3 J(g·K)-1 and ±2·10-5 g·cm3.
ФV of calcium and cadmium nitrates in MP were calculated. The standard partial molal heat
capacities C P02 and volumes V20 of Cа(NO3)2, Cd(NO3)2 in MP at 298,15 K being of interest
for the thermodynamics of solutions were determined by the extrapolation of concentrated
dependences of ФС and ФV to the state of infinity dilution. The separation of the C P02 and V20
values into ionic components was performed on the basis of the C Pi0 and Viо values for the
nitrate ions in MP [1, 2] and using the condition of the additivity of partial molar values.
The interaction of ions with solvents includes several effects, such as the electric
polarization of solvents, the formation of cavities of a certain size in solvents for the
accommodation of ions, changes in the structure of solvents, and universal and specific
interactions between ions and solvent molecules. Each of these effects is accompanied by
changes in thermodynamic properties. The standard partial molar heat capacity and volume of
an ion is also influenced by all these effects and can be presented as the sum of several
contributions: the intrinsic heat capacity (volume) of an ion in solution, the changes in heat
capacity caused by solvate formation (excluding specific solvation), the changes in volume
caused by electrostriction and the changes in heat capacity (volume) caused by reorganization
of the primary structure of a solvent and specific interactions between ions and solvent
molecules.
It is of interest to compare the properties of the Ca2 + , and Cd2 + ions having close
electrostatic characteristics but quite different natures. Complex formation is characteristic of
the cadmium ion and not characteristics of the calcium ion. For this reason, the interaction of
Cd2 + with MP molecules results in the formation of bonds covalent to a substantial extent,
whereas Ca2 + form predominantly electrostatic bonds. Since the Ca2 + and Cd2 + ions have
equal charges and almost equal sizes and, therefore, almost equal values all contributions,
excluding effect specific solvation. We can estimate the. values of specific solvation
contribution; the difference between the values C Pi0 and Viо for ions Ca2 + and Cd2 + is –19 J
(mole⋅K)-1 and 11 cm3⋅mole-1.
References
EFFECT OF THE NATURE OF THE BENZOIMIDAZOPHTHALAZINE

DERIVATIVES ON THE THERMODYNAMIC PARAMETERS
OF THEIR INTERACTIONS WITH DNA MOLECULE
Osinnikova D.N. 1, Moroshkina E.B. 1, Kuznetsov V.A. 2
1
St. Petersburg State University, St. Petersburg; 2Research Institute of Hygiene, Occupational
Pathology and Human Ecology, St. Petersburg
e-mail: osinnikovadasha@yandex.ru
Among the large number of chemical compounds possessing biological activity, the
compounds showing an antitumor activity as a result of their direct interaction with DNA
molecule and inhibiting the matrix function of the latter have received much attention. When
searching the new antitumor drugs, many new compounds have been synthesized and
investigated. These compounds can form the reversible complexes with DNA.
In this work the interaction of DNA with synthetic derivatives of
benzo[4,5]imidazo[2,1-a]phthalazine were studied by means of spectral and hydrodynamic
methods. These derivatives have different substitutes at the 9th position: piperazine,
morpholine, pirrolidine and piperidine. The compounds under investigation were synthesized
in the Research Institute of Hygiene, Occupational Pathology and Human Ecology by
Kuznetsov V.A. [1].
N 9 R1
5 N
R2
All compounds form complexes with DNA molecule in water solution. The binding
isotherms were obtained by spectrophotometric titration. Isotherms were analyzed based on
the model with excluded binding sites [2]. Thermodynamic binding constants and the number
of binding sites were determined.
Derivatives with piperazine at the 9th position have the highest affinity to DNA. An
increase in characteristic viscosity of DNA molecule upon binding with the piperazine
derivatives allows us to make an assumption about intercalation of these derivatives into the
DNA double helix.
A change in characteristic viscosity of DNA during the complex forming, hence, the
way of binding the macromolecule with derivatives containing the remainders of morpholine,
pirrolidine and piperidine in 9th position depends on the nature of substitutes at 5th position.
A huge aromatic substitute prevents the intercalation of the chromophore of these compounds
into DNA double helix.
References
1. Kuznetsov V.A., Shubin A.M. [et all] Tetrahedron, 62 (2006) 10018
2. Mc Ghee J.D., von Hippel P.H. J. Mol. Biol., 86 (1974) 469
THEORETICAL DESCRIPTION OF THE DEMIXING PROPERTIES OF AgI-NaCl

WITHIN MEAN SPHERICAL APPROXIMATION
Peshkina K.G, Tkachev N.K.
Institute of High-Temperature Electrochemistry RAS (Ural branch), Russian Federation
e-mail: kspeshkina@mail.ru
In the molten salt binary NaCl-AgI the miscibility gap in the range of temperature from
760 to 793 ° C in the range of concentration of 20-80 mol.% NaCl takes place [1]. There are
no published data on density of each phase of the system below the consolute point.
Knowledge of such an important value, as the density of the melt NaCl-AgI is necessary for
the evaluation of other physical and chemical characteristics and because the difference of
densities of coexisting phase is the order parameter for the liquid-liquid phase transitions and
it stands major role in industrial processes. Its change depending on the different parameters
of the immiscible melt is an important source of information about mean interparticle
distance, which in turn reflect the nature of the forces acting between the components.
In this work we use mean spherical approximation of the charged hard sphere model of
different diameters [2] for evaluation of the miscibility gap and associated densities of the
coexisting phases above and below the critical point of mixing for the system NaCl-AgI. It is
important that the calculation is not empirical, and does not contain adjustable parameters: in
this case it is necessary only the ionic radii of constituent species.
Comparison of the experimental and calculated data for the miscibility gap in the system
NaCl-AgI demonstrates satisfactory agreement for the consolute temperature. The difference
is of the order 10%. However, the configuration of the calculated gap is characterized by
rather much asymmetry. The experimental determination by direct visual observation of con-
solution shows that the position of the critical point on the axis of the composition is observed
at near-equimolar mixture of sodium chloride and silver iodide and temperature of 1067K.
Maximum of the miscibility gap calculated within MSA approximation corresponds to the
critical concentration of NaCl 0,594, and the temperature 134 degrees below the experimental
one [1].
It is shown that the statistical theory of charged hard spheres is a useful tool for the
analysis of demixing salt mixtures of silver halides with alkali metals. We will discuss
possible reasons of the discrepancies of the theory and experiment. Probably, there is another
contribution into the enthalpy of mixing concerning with polarisabilities of the embedded
ions. Perspectives of microscopical description of immiscible molten salt mixtures will be
discussed as well.
References
1. Flor G., Sinistri C. Z. Naturforsch., 1982. 18, N 37, P. 1067.
2. Tkachev N.K. Rasplavy, 1999. N 4, P.90.
This work was supported by RFBR (12-03-00346).
PHASE EQUILIBRIA AND THE SOLUTIONS BOUNDARY OF METASTABILITY

IN THE BENZOIC ACID – NAPHTHALENE SYSTEM
Pokintelitsa E. A., Postnikov V.A., Shchebetovskaya N.V.
Donbass National Akademy of Civil Engineering and Architecture,
Physics and Material Science Department, Makeevka, Ukraine
e-mail: postva@yandex.ru
The work is devoted to research of the eutectic mixtures crystallization regularities in
the system of benzoic acid - naphthalene depending on the concentration of component and
the liquid phase overheating above the liquidus temperature by the thermal analysis (DTA,
CTA) and optical microscopy methods. The mass of the alloy samples were from 100 to 200
mg. The lines of phase equilibria is defined and state diagram is built (Fig(a)). According to
experimental data, the eutectic point has the coordinates Те=66.9±0.5оС and хе=51±3%mol.
of naphthalene. The pre-crystallization liquidus and solidus melts supercoolings is defined.
The average values of a liquidus supercoolings ΔТL‾ is marked (□) on the state diagram and
thus the region of metastable states of melts is defined. It has been established the regularity of
melts overheating ΔТL+ influence on liquidus and solidus supercoolings ΔТL‾ and ΔТе‾
respectively (see Fig(b)). Between the two types of supercoolings is observed the back
correlation, as seen from Fig.(b) for the composition x=90%mol. naphthalene.
The analysis of phase equilibria in the studied system showed a considerable
discrepancy between the experimental values with the values of the liquidus line in the
approximation of ideal solutions of (line s-h-r). The excess thermodynamic function were
determined by the using of the experimental values of the liquidus themperature. The received
information formed the basis for the development of nucleation model in eutectic systems.
Fig(a). The state diagram in the benzoic acid – Fig(b). The melts overheating ΔТL+ on
naphthalene system (dotted line – the metastable liquidus ΔТL‾ and solidus ΔТе‾ influence
melts boundary, shr-line – ideal solutions model). (x=90%mol. naphthalene).
THERMODYNAMIC AND KINETIC BASES OF PHENOMONOLOGICAL

ESR-SPECTRA DYNAMIC MODULATION THEORY
FOR FLOUROALKYLATED AND OTHER RADICALS
Polenov E.A., Melnikov P.V., Chausov I.S.
e-mail: epolenov@mail.ru, melnikovsoft@mail.ru
Generally used interpretation of dynamical modulation (DM) effects in magnetic
resonance spectra is based on time-and-frequency approach within which the correlation time
τ, that is inversely to rate constant, and the circular frequency ω are the principal
characteristics. Function that directly affects the spectral profile form is the complex spectral
density:
J(ω) =g0(IC – i·IS)= j(ω) –i·k(ω), (1)
where Re(J) = j(ω) is spread, and Im(J) = k(ω) is shift of resonance line.
j(ω)=g0[τ /(1+ω2τ2)]; k(ω)=ωτj(ω), (2)
Temperature-dependent fluctuations of equivalent nuclei movable groups result in
transformation of relevant multiplet, but temperature is the tacit variable within the generally
used description method, and analysis of spectrum superfine structure parameters, which are
accessible to direct measure, is appreciably impeded. Often the other system of variables in
which time τ is changed to habitual temperature T is more preferable. That is where the
thermodynamic representation arise from.
Temperature variable should be modified for description of different radical structures
because its point zero is related to the structure of radical. Gibbs canonical distribution
modulus Θ=θ-1 (θ = T-1-T0-1, T0 – center of the transient regime (I) of DM) become the natural
variable. Spectrum is caused by the spin state of electron-nuclear collective undergoing
thermodynamically reversible transitions in the conditions of microwave energy absorption
within the equilibrium with thermostat. Describable effect resembles to the blackbody
behavior.
Fulfilling the analysis of the equilibrium spin ensemble by the methods of the classic
statistical thermodynamics one may succeed in creating the temperature function for the
constant in the multiplet and for the temperature-dependent shifts values. By carrying out the
modeling of two interconvertible multiplet forms using stationary two-way kinetic one will
also repeat this effects. Scheme based on the direct analysis of spectral density results into the
same outcomes. The elementary micromolecular form of Arrhenius equation τ=τ∞·exp(E·T-1)
lies at the core of the transformation. Resultant equations of both the components are as
follows:
J0(θ)=ch-1(E·θ); (3)
K(θ)=½(κ, I2), κ=〈1; th(E·θ)〉, I2=〈1, 1〉, (4)
Temperature function for splitting constant is given by:
aДМ(θ)= ½(A, κ), where A = 〈(aE +<a>), (aE –<a>)〉. (5)
Here aE and <a>≡ aR are asymptotic limits of the observable constants when outermost
multiplet forms are reached.
Deduced system of equations is effective in the most difficult field of the spectrum
images mathematic reconstruction – of the transient spectrum regime. The temperature
variable is worth changing for the concept of the DM phase for the quality interpretations
because its qualitative peculiarities do not depend on the radical structure. This theoretical
scheme is confirmed by the direct experiments with the series of flouroalkylated radical-
anions.
THERMOCALORIC FEATURES OF BINARY SOLUTION AMMONIA–WATER

Polikhronidi N.G., Batyrova R.G., Stepanov G.V.
Institute of Physics of the Dagestan Scientific Center of the Russian Academy of Sciences,
Makhachkala, Dagestan, Russia
e-mail: polikhronidi@rambler.ru
Thermal values P,ρ,T and isochoric heat capacity CV for binary solution water-
ammonium of 0,2607 mole fraction of NH3 are measured in a constant volume adiabatic
calorimeter [1] in the region of critical state at wide ranges of temperatures and pressures.
The measurements are carried out in the neighborhood of a boundary curve at two-phase and
single-phase states along 42 isochores [2, 3] within intervals of densities (120 ÷ 671) kg/m3,
temperatures (403÷630) K, and pressures up to 28 MPa.
The PS, ρS, TS .parameters and a thermal coefficient of the pressure (∂P/∂T)VS on the
boundary curve of two-phase and single-phase states and isochoric heat capacities C”VS and
C’VS are determined by the thermal barogramm method.
In retrograde condensation region, the features of isochoric heat capacity CV on the
boundary curve as maxima in the cricondenterm as well as in the critical and also the extrema
of pressure thermal coefficient ((∂P/∂T)VS) as minimum in the critical point and as maximum
in the cricondenterm are found for the first time for studied binary system.
Internal pressure (∂U/∂V)T, heat capacity CS, entropy S, and isobaric heat capacity CPS
on boiling and condensation curves are calculated using obtained experimental values of PS,
ρS, TS, (∂P/∂T)VS, CVS on the boundary curve and known thermodynamic correlations.
It is for the first time for studied binary system the isobaric heat capacity on the
boundary curve is received from a side of two-phase state C”PS.
All calculation properties (∂U/∂V)TS, CS, CPS, S on boundary curve are shown to have
characteristic features both in the cricondenterm an d in the critical point.
References
1. Kh. I.Amirkhanov, G.V. Stepanov, B.G.Alibekov. Isochoric Heat Capaciti of Water and
Steam. Makhachkala. 1964.
2. N.G. Polikhronidi, I.M.Abdulagatov, R.G. Batyrova, G.V.Stepanov..Int. J. Thermophysics,
30, (2009), 737-781
3. N.G. Polikhronidi, I.M.Abdulagatov, R.G. Batyrova, G.V.Stepanov. Int. J. Refrigeration ,
32 (2009), 1897-1913.
This work was supported by the Grant of RFBR 10-08-00599a.

THE SODIUM-CALCIUM EXCHANGE REACTION BETWEEN AQUEOUS

SOLUTIONS AND THE CRYSTALLINE ALUMINOSILICATES
Pozdeev A.N., Mamontov M.N., Uspenskaya I.A.
Faculty of Chemistry, Lomonosov Moscow State University, Moscow
e-mail: mmn@td.chem.msu.ru
The experimental investigations of the ion exchange processes between sodium
aluminosilicates and calcium salts aqueous solutions were carried out by the potentiomety
method with ion-selective electrodes for Na+, Ca2+. The synthetic zeolites NaY
(Na2O∙Al2O3∙5.2SiO2∙8H2O, “UOP”, USA), NaA (Na2O∙Al2O3∙2SiO2∙3.1H2O, ZAO
“Nizhegorodskye sorbenty”, RF) were used as test systems. The material studied was the
nature cancrinite from Khibino-Lovozersky locality with composition
Na7.83±0.39Са0.36±0.08[Al5.55±0.28Si6.45±0.27O24](CO3)1.2(OH)0.6·2.5H2О.
The purpose of this work was to determine the separation ( TNa Ca
= yCa mNa y Na mCa ) and
Ca
equilibrium coefficients ( N K Na = y ' Ca x' 2Na y ' 2Na x' Ca ) [1] of the ion exchange reaction
2∙Na+ ( zeolite ) + Ca2+ ( solution ) = 2∙Na+ (solution ) + Ca2+ ( zeolite ) (1)
and then to evaluate the maximum degree of sodium substitution by calcium in a cancrinite.
The sodium and calcium ions concentrations in the solution were determined by means of the
electromotive forces (EMF) measurements at the temperature 40оС in the electrochemical cell
without a liquid junction:
Cl--ISE | aluminosilicate, H2O + CaCl2 + NaCl | Na+-ISE, Ca2+–ISE ,
where ISE denotes ion-selective electrode for appropriate ion. The aluminosilicate
(zeolite and cancrinite) was a fine fraction with a particle size less than 63 μ. Usually the
equilibrium state in the zeolite system was attained during 0.1 hour, but it took more than 90
hours for cancrinite. The concentration dependencies of EMF for different ISE are represented
by formulas:
E (Na, Cl − ISE ) = E01 + s1 ln(mCl ((γ NaCl±
) 2 mNaCl + K Na,Ca (γ CaCl
± 1/ 2)
2
) 3 / 2 mCaCl2 ,
E (Ca, Cl − ISE ) = E02 + s 2 ln(mCl2 ((γ CaCl
±
2
) 3 mCaCl2 + K Ca, Na (γ NaCl
± 2
) 4 mNaCl ),
where K Na,Ca , K Ca, Na are the previously measured selectivity coefficients of the
electrodes with respect to interfering cation. The values of the standard potential and the slope
of the response ( E0i , si ) were determined by prior ISE calibration in the aqueous solution of
appropriate cation salt. The mean ionic activity coefficients of the salts were calculated using
the Pitzer model. The measured coefficients for (1) at 40оС are presented in the table.
Table. The separation and equilibrium coefficients for the ion exchange reaction (1).
tot Ca N Ca
Aluminosilicate mequiv (solution), TNa K Na
mol/кg **
Zeolite NaY (faujasite) 0.199 1.02 1.03
Zeolite NaA 0.1 1.31 1.34
Nature cancrinite 0.2002 5.4∙10-4* 2.0∙10-5*
tot
* - the estimated values , ** - mequiv ≡ m NaCl + 2mCaCl2
Reference:
1. Helfferich F., Ion-exchange resins, Inostr. Lit., Moscow, (1962), p. 490.
This work was supported by the Russian Foundation for Basic Research, project no. 13-
03-00328.
MODELING EQUILIBRIA INVOLVING OXIDE-FLUORIDE SYSTEM Na, Ca, Al / / O, F

Pratskova S.E., Tyurin A.G.
e-mail: se_pratskova@mail.ru
Considering the oxide-fluoride melts of Na, Ca, Al / / O, F as ionic solution within the
framework of the general theory of "regular" ionic solutions [1] conducted simulation of phase
equilibria.
The expressions for the activities of the components by the equation:
+ ν−
RT ln a st = RT ln xνs st ⋅ yt st +
k l l s −1
ν st+ ⋅ ξ ∑ ∑ xi y j ⋅ ∆G stij + ν st+ ⋅ ∑ y j ⋅ [ ∑ ( xi2 ⋅ Qis( j ,1) + 2 xi x s ⋅
i =1 j =1 j =1 i =1
k t −1
⋅ Qis( j , 2) + 2 xi2 ⋅ x s ⋅ Qis( j ,3) ) + 2 x m ⋅ Qim
( j , 2)
+ 3 xi x m ⋅ Qim
( j ,3)
)] + ν st− ⋅ ∑ xi ⋅ [ ∑ ( y 2j ⋅ Q(jti,1) +
i =1 j =1
l
+ 2 y j yt ⋅ Q(jti, 2) + + 2 y 2j yt ⋅ Q(jti,3) ) + ∑ (2 yt y n ⋅ Q(tni,1) + y n2 ⋅ Q(tni, 2) + 2 yt y n2 ⋅ Q(tni,3) ) −
n =t +1
l −1 l
− ∑ ∑ y j y n ⋅ (2 y j ⋅ Q(tni,1) + 2 y n ⋅ Q(jn
i , 2) + 3 y j y n ⋅ Q(i ,3) )] ,
jn
where st - shorthand
j =1n = j +1
component of the solution A ( s+) B (t−) , ν st+ and ν st− - the number of cations and anions in the
ν st ν st
oxide or fluoride molecule, α and α - valence ions. Ion fraction of the cations and anions
s+ s−
are calculated by the equations:
l k
+
∑ν sj ⋅ n sj −
∑ν it ⋅ nit
j =1 i =1
xs = k l
; yt = k l
,
+ −
∑ ∑ν ij ⋅ nij ∑ ∑ν ij ⋅ nij
i =1 j =1 i =1 j =1
where nij - number of moles of substance (ij) in the solution, k - the total number of
cations, l - the total number of anions. Parameter ξ - the ratio of total cations to total anions,
that is,
k l l
+ −
∑ ∑ ν ij ⋅ nij ∑ αj ⋅yj
i =1 j =1 j =1
ξ= = .
k l k
− +
∑ ∑ ν ij ⋅ nij ∑αi ⋅ xi
i =1 j =1 i =1
To model the equilibria involving oxide-fluoride melts of Na, Ca, Al / / O, F, were
calculated ∆G stij - the Gibbs energy of metabolic reactions, based on data on the
thermodynamic properties of the system components. Evaluated the energy parameters of the
( j ,k )
theory - Qim (T ) and Q(ji,,nk ) (T ) , by processing experimental data on phase diagrams with the
warmth and melting oxides and fluorides of Na, Ca, Al, and Gibbs energies of formation of
compounds.
Reference
1. Tyurin, A.G. By thermodynamics of molecular and ionic solutions // Metals. 1993. № 2.
P. 48-56.
SIMULATION PROBLEMS OF SCALAR PROPERTIES

IN LIQUID TERNARY MIXTURES
Raeva V.M.
e-mail: raeva@wwwcom.ru
Composition – the property diagrams of ternary mixtures are used in the studies of
liquid solutions structure and evaluation of intermolecular interactions nature. These data are
of independent importance in the physicochemical analysis. For separation processes in
technology of organic products are of interest volume and transport properties of liquid
mixtures, necessary for calculations of mass transfer as well as thermo-physical properties,
which, together with the phase equilibria data, are necessary for the correct calculation of
mass-exchange processes.
Composition - the property dependences of ternary mixtures are obtained experimentally
as well as by calculation. The most demonstrative form for their presentation are isolines
diagrams. For the calculations mainly empirical models or polynomials are used, values for
ternary mixtures are obtained according to the data of the binary solutions. When
experimental data for ternary mixtures are available, researchers compared the results of
correlations focusing on the quantitative description of the property.
While calculating the properties of a ternary mixture according to its binary solutions
using different models inconsistent results can be obtained: isolines diagrams which built on
the correlated results of different models have various topological structure. Obviously such
data are of little theoretical and practical value.
The absence of contentual models for the description of various scalar properties
significantly complicates the study of composition – the property dependencies of ternary
solutions and limits the possibilities of their use for calculations of chemical and technological
equipment in commercial software packages.
Only using of models for heterogeneous equilibrium based on the concept of local
composition for the calculation of temperatures and pressures in three-component systems to
have the data for binary constituents is sufficient. In this case the description adequacy of
vapor-liquid equilibria provides the thermodynamic consistency. When calculating scalar
properties (isotherm-isobars obtained), as in heterogeneous equilibrium intensive value (P, T)
is associated with a field of nod vectors diagram, and there is mutual reflection of a vector
nature properties field and scalar property, represented as a scalar field induced by the
gradient.
There is no such an obvious connection for other scalar properties, that is, researchers
do not have a verification tool, diagrams composition – property are obtained using calculated
data. Therefore, for today a sufficient number isolines diagrams of scalar properties which are
inaccurate or even topologically incorrect is published. Check for the diagrams topological
structures constructed using the experimental data in case of precise measurement and non-
trivial composition – property dependences is also necessary.
THERMODYNAMIC PROPERTIES OF COMPLEXATION REACTIONS

OF Fe (III) AND (II) IN AQUEOUS SOLUTIONS OF IMIDAZOLE AND DIBAZOLE
Rajabov U.P., Rahimova R.N., Sharipov I.H., Ermamadova S.G.
Tajik State Medical University named after Avicenna, Dushanbe, Tajikistan
Tajik National University, Dushanbe, Tajikistan
e-mail:umarali55@mail.ru
There is not much information of complex coordination compounds of Fe (III), Fe (II) in
aqueous solutions of imidazole and dibazole. They refer to the limited interval concentration
conditions. Especially few data are reported on polynuclear and heterovalent iron complexes,
though they are just the part of active centres of iron-containing enzymes and facilitate
implementation of multi-electron transferences in the electron transport chains at biological
oxidation that, from the point of view of thermodynamics, are more efficient, than one-
electron chains. Thus the investigation of the thermodynamic parameters reactions,
accompanied by formation of polynuclear and heterovalent complex coordination compounds
of Fe (III), Fe (II) in aqueous solutions of imidazole and dibazole, is very urgent.
The method of oxidation potential was used to investigate of formation processes of
complex coordination compounds of Fe (III), Fe (II) in aqueous solutions of imidazole and
dibazole in the temperature range 288÷318 K and at the ionic strength 1.0 mole per litre. Joint
analyses of experimentally obtained relationships between oxidation potential (ϕ) and pH,
concentration of oxidized and reduced forms of Fe, azole, as well as generation of
stoichiometric matrix (mathematical model) of existing equilibriums in solution, showed that
the complexes of the following compositions are formed in the system: FeL3+, FeL(OH)2+,
FeL(OH)2+, Fe2 L2(OH)22+, FeL2+, FeL22+, FeIIIFeIIL2(OH)4+. Composition and constants of
complex coordination compounds and their degree of accumulation were defined precisely
with Yusupov oxidizing function by the iteration method. Coincidence of experimental and
theoretical oxidizing functions confirmed the accuracy of the defined complex compositions,
as well the constant value authenticity of their formation.
Estimated values of the formation constants of specified complex coordination
compounds were used for determination of enthalpy change and isobaric potential of their
formation reactions by the temperature coefficient method. Entropy changes were estimated
by the certain values of enthalpy and free energy changes. The obtained endothermic effect in
the reactions of complexes formation of specified composition above indicates that
destruction of previous bonds requires more energy than the release of the energy in a process
of new bonds formation. Imidazole and dibazole are monodentate ligands, but much larger
than water molecules, so in a process of complexes formation one ligand in the hydrate shells
can cause transfer more than one water molecule. Thus in formation reactions of complex
coordination compounds, the positive entropy changes are related both to the displacement of
water molecule out of inner coordination sphere, and to the release of several molecules out of
hydrate shells of the complexing agent and the ligand. During complexation negative values
G0 are increasing with temperature rise, since the probability of the spontaneous formation of
complexes is increasing.
THERMODYNAMICAL PROPERTIES OF POTASSIUM AND CADMIUM

THIOCYANATES IN N-METHYLPYRROLIDONE AT 298.15 K
Rassokhina L.Yu., Novikov A.N.
Mendeleev University of Chemical Technology of Russia,
Institute in Novomoskovsk
e-mail: anngic@yandex.ru
This work continues systematic studies of solutions of electrolytes and nonelectrolytes
in the aprotic dipolar solvent N-methylpyrrolidone (MP) [1–3]. Studies of multicomponent
systems is of theoretical and practical interest, because the majority of chemical processes are
conducted in such systems.
Heat capacity Cp and density ρ of binary solutions of potassium and cadmium
thiocyanates in N-methylpyrrolidone (MP) and ternary system KSCN – Cd(SCN)2 – МP at
298,15 K were experimentally investigated. For measurement of Cp hermetic calorimeter with
isothermal shell and platinum thermometer resistence as a temperature transducer were used.
The error of Cp measurements wеre not more than ±1·10-3 J(g·K)-1 For measurement of ρ the
precision picnometric installation (error ±2·10-5 g·cm3) were used. MP was dried over freshly
cut calcium hydride and distilled twice at low pressure. Karl Fisher titration indicated that the
water content was not more than 0,01-0,02% by weight. The purity of MP was found to be
99,7% by weight, as determined by gas chromatograpy analisis. The salts were dried under
reduced pressure at 353-423K for 8-10 h. All solutions were prepared by weight in a dry box.
ФV of potassium and cadmium thiocyanates in MP were calculated. The standard partial molal
heat capacities C P02 and volumes V20 of potassium and cadmium thiocyanates in MP at
298,15 K being of interest for the thermodynamics of solutions were determined by the
extrapolation of concentrated dependences of ФС and ФV to the state of infinity dilution. The
separation of the C P02 and V20 values into ionic components was performed on the basis of the
C Pi0 and Viо values for the potassium and cadmium ions in MP [4, 5] and using the condition
of the additivity of partial molar values. Considering that, agreement between values obtained
from data on KSCN and Cd(SCN)2 is satisfactory. If we take into account the errors of C Pi0
and Viо , the recommended values of С p0, NCS - is 112 J (mole⋅K)-1 and V NCS
0
- is 30,4
cm3⋅mole-1.
On the base of the data about Cp and ρ of binary solutions KSCN – МP, Cd(SCN)2 – МP
and ternary system KSCN – Cd(SCN)2 – МP additivity coefficients δс and δv were calculated.
The values of δс and δv were used to analyze the influence of various effects on ion-solvent
interactions.
References
1. V.A. Vasilyov, A.N. Novikov. Zh. Fiz. Khimii. 1993, 67, 1387-1395.
2. A.N. Novikov, V.A. Vasilyov. Zh. Fiz. Khimii. 2006, 80, 598-601.
3. A.N. Novikov, V.A. Vasilyov, O.F. Lenina. Zh. Fiz. Khimii. 2007, 81, 1947-1952.
4.. A.N. Novikov. Zh. Fiz. Khimii. 2009, 83, 13-16.
THERMAL PROPERTIES AND CRITICAL LINES OF WATER–PENTANE SYSTEM

AT HIGH CONTENT OF WATER
Rasulov S.M.
Institute of Physics of Dagestan Scientific Center of RAS, Makhachkala
e-mail: suleimanr1@rambler.ru
This work presents the results of researche on phase equilibriums of binary immiscible
systems n-pentane-water under normal conditions based on the measurements of PVTx
properties in temperature intervals from 300 K to 680 K, pressures up to 60 MPa and in a
wide interval of densities in the constant volume piezometer. Measurements of PVTx
properties surround a wide range of state parameters including the regions of equilibriums
liquid-liquid and liquid-vapor. Thermal properties of n-pentane-water system are obtained for
nine values of the water concentrations: 0.862; 0.881; 0.903; 0.925; 0.942; 0.973 and 0.987
mole fractions. Each concentration is measured along 10-11 isochores covering a wide
interval of vapor and liquid isochores. In the beginning, at large concentrations of water the
hydrocarbon liquid transits into vapor and next the water liquid transits into vapor. Critical
pressure and temperature for transition hydrocarbon liquid into vapor are the same as for
upper critical end point right to large concentrations of water in the mixture though the critical
densities differ: Tc = 463.8 K and Pc = 4.57 MPa. On isopleths of phase transition water
liquid-vapor, a local temperature maximum and local temperature minimum are observed.
When increasing the concentration, the difference between extremums arises. In a high
pressure region, all isopleths reveal a sharp rise. Upper locus begins in the critical point of
water, passing through the temperature minimum, directs towards the high pressure region. A
point corresponding to the temperature minimum divides the two-phase region into two parts.
Right part corresponds to the liquid-gas equilibrium and is aligned with critical point, when
increasing the temperature. Left part corresponds to the gas-gas equilibrium of second type
and lasts over critical temperature of water. A point, where the gas-gas and liquid-vapor are
aligned with, is called a double critical point and corresponds to the concentration of 0.925
mole fractions. For the double critical point of n-pentane-water system are obtained the
parameters Tc=625.5 K, Pc=33.7 MPa. In P-T diagram, the region of gas-gas equilibrium is
limited by a curve coming from the double critical point towards the higher T and P and by
isotherm coming from the double critical point towards higher pressures. The calculations of
T – ρ phase diagrams for binary mixture n-pentane-water shows that a value of critical
exponent δ is close to 0.325 what is typical for 3D Ising systems. However, for concentrations
corresponding to the double critical point, the value δ is twice as large, what confirms a
suggestion about the doubling of critical exponents in the double critical point.
IONIC ASSOCIATION AND ELECTRIC CONDUCTIVITY IN BINARY MIXTURES

OF IONIC LIQUIDS WITH ACETONITRILE AND METHANOL
Riabchunova А.V., Voroshylova I.V., Smaga S.R., Kalugin О.N.
e-mail: ryabchunova.anastasia@gmail.com
Room temperature ionic liquids (RTILs) are the multi atomic salts with a melting point
below 100 ◦C. Due to unique properties RTILs are widely used in a different areas of
chemistry, such as analytical, preparation chemistry and electrochemistry [1-2]. Nowadays
solutions of RTILs in non-aqueous solvents are considered as an alternative to the
conventional electrolyte solutions for electrochemical application.
In the present work we report the results of conductometric investigation of
imidazolium-based RTILs solutions in acetonitrile (AN) and methanol (МеОН) in a wide
range of concentrations and temperatures (5, 15, 25, 35, 45 and 55 ºС).
The values of limiting molar conductivity, Λ0, association constant, Ка, and parameter of
the closest approach of ions, R, were evaluated by means of Lee–Wheaton equation from the
experimental conductometric data. It was identified that R parameter in AN is equal within the
errors to the sum of ion structural radii for all RTILs and almost does not depends on
temperature. As opposed to AN, in MeOH R parameter increases with temperature increase.
The association constants of RTILs in AN are small and slightly depend on temperature. The
size of cation does not effect the values of Ka, whereas the size and nature of anion influence
significantly. This means that RTILs in AN and MeOH solutions form a contact ion pairs with
the similar structure where the distance between ions depends mainly on anion size. A
contribution of limiting ion conductivity of ions into a general conductivity and the influence
of solvation effects on hydrodynamics of ions in AN and MeOH solutions of RTILs were also
analyzed.
From the results of conductometric investigation at high concentrations we found that
the specific conductivity of all the investigated mixtures has a maximum at ~0.1−0.2 mole
fraction of RTILs which is shifted to higher concentrations with temperature increase. It was
shown that cation size influences mainly on the position of maximum, while the value of
maximum of specific electrical conductivity is governed by anion size.
References
1. R.D. Rogers and K.R. Seddon. Ionic liquids as Green Solvents. Progress and Prospects.
2003, Americal Chemical Society: Washington DC.
2. P. Hallett, T. Welton. Chem. Rev., 111 (2011) 3508.
THERMODYNAMICS OF PHASE TRANSFORMATIONS IN SYSTEM Ag2-xS–EuS

Rusejkina A.V., Galenko E.О., Petrova M.D.
Tyumen State University, Tyumen, e-mail: adeschina@mail.ru
According to results of research of specimen by methods MSA, XRD, DSC, the phase
diagram of the system Ag2-xS-EuS eutectic type with the formation of limited areas of solid
solutions (SS) based on the initial components construct (Fig.).
Т, К 2520
2200
1770
1700 89%
l SS EuS
1105 l+SS EuS Fig. 1. A - A phase diagram of the system Ag1.99S-EuS:

o - DSC data. The state of the samples according to the
1200
γ + l 2.5%
results of XRD and MSA: □–single-phase, Δ–two-
1082 91%
1.5% phase. Specimens for research is reflected on the
SS γ−
Ag1.99S
SS γ−Ag1.99S+SS EuS composition axis. B - Differential thermal dependence
865 1.5%
789 92% for docimasia of system Ag2-xS-EuS. Shooting
SS β−
Ag1.99S1.2%
SS β−Ag1.99S+SSEuS conditions at the agregate Setsys Evolution 1750 (TG-
700
Ag1.99S 20 40 мол.% 60 80 EuS DSC 1600); ν heating = 5 K/min, νAr = 25 ml/min,
Vteagle = 100 mkl.
During thermal analysis of docimasia samples 1-50 mol. % EuS on the thermograms
was tound the decrease in the peak area of the eutectoid phase transformation: 3.26
(3%) → 3.01 (6%) → 2.46 (20%) → 1.75 (40%) → 1.65 (50%) J/g. The average temperature of
the eutectoid for eight samples is 789 ± 4 K. The mix containing 1.5 mol. % EuS was taken as
a point of eutectoid composition. The balance equation was done for eutectoid phase
transformation in SS based on Ag1.99S: 0.997SS β-Ag1.99S (0.012 EuS; 0.988 Ag1.99S) +
0.003SS EuS (0.92 EuS; 0.08 Ag1.99 S ) ↔ SS γ-Ag1.99S (0.015 EuS; 0.985 Ag1.99S); ΔH = 3.2
± 0.3 J/g.
At the thermograms of docimasia samples containing 2-90 mol. % EuS presents the
melting peak of the eutectic mixture of crystals, the average temperature of the onset melting
point for 11 samples with different compositions is 1082 ± 3 K. We observed the decrease in
the value of the peak area: 16.75 → 16.65 → 15.84 → 14.00 → 10.96 → 10.44 →
7.92 → 6.10 → 3.3 → 2.29 → 0.1 J/g. Eutectic composition according to MSA and DSC, data
constructing a Tammans triangle and extrapolation the branches of the liquidus line in the
eutectic horizontal is 2.5 mol. % EuS. There are balanced equation eutectic melting crystals
was done: 0.997SS β-Ag1.99S (0.012 EuS; 0.988 Ag1.99S) + 0.003SS EuS (0.92 EuS; 0.08
Ag1.99S) ↔ SS γ-Ag1.99S (0.015 EuS; 0.985 Ag1.99S); ΔH = 16.7 ± 1.7 J/ g.
On the basis of EuS the SS area appears which has a temperature dependence. According
to the dependence of the parameter from composition, the appearance of the second phase in the
samples, the extrapolation of triangle Tamman sides the position of solidus and solvus points
was defined 89.0 (1770 K), 91.0 (1082 K), 92.0 (789 K) mol. % EuS.
Research is carried out with financial support from the government through the Ministry
of Education and Science of the Russian Federation according to the agreement number
14.V37.21.1184.
EFFECT OF IONIC SURFACTANTS ON THE CLOUD POINT BEHAVIOR

OF NONIONIC SURFACTANT AQUEOUS SOLUTIONS
Safonova E.A., Mehling T., Storm S., Smirnova I.V.
Saint-Petersburg State University, Saint-Petersburg
Hamburg University of Technology Institute of Thermal Separation Processes, Hamburg
e-mail: safonova@nonel.pu.ru
Aqueous surfactant solutions split into two phases if the temperature is increased
beyond a certain temperature, the so called cloud point temperature (CPT). This phenomenon
has been used to perform single stage extraction (cloud point extraction, CPE) of hazardous
compounds or high valued products by various authors [1, 2].
Nonionic type of surfactants is commonly used in the CPE processes. The origin of the
clouding phenomena for nonionic surfactant is attributed to the diminished solubility of the
surfactant in water [3]. Above the CPT, the micellar solution separates into two phases, of
which one is a concentrated surfactant solution, the micellar-rich phase, and the other one is
the micellar-poor phase, which contains the surfactant at the concentration close to the critical
micelle concentration (cmc). This phenomenon is reversible and re-establishment of the initial
solution conditions drives to formation of a single isotropic phase again. However,
mechanism of the phase separation is still under discussion.
The mixtures of nonionic with ionic surfactants in the CPE are of high potential. Mixed
systems often show very different properties from those of single surfactant systems.
Synergetic effects may occur on addition of nonionic surfactants to aqueous solutions of ionic
surfactants. Such effects are reflected in the reduction of the cmc, the increase of viscosity,
micellar growth, specific features of phase boundaries, changing in solubilization capacity etc.
[4, 5]. It is known, that the presence of even small amounts of ionic surfactant or neutral salts
has a strong effect on the CPT of nonionic surfactant [6, 7]. Such effects are really important
for surfactant based separation processes particularly in a micellar extraction.
In the present work, we have studied the effect of ionic surfactants
(cetyltrimethylammonium bromide, CTAB, or sodium dodecyl sulfate, SDS) on CP behavior
of nonionic Triton X-114, (1,1,3,3-Tetramethylbutyl)phenyl-polyethylene glycol. The data on
the liquid-liquid equilibrium from CPTs up to 60°C are presented. The influence of sodium
chloride addition is discussed. The structure of the aggregates was obtained from the
molecular dynamic simulations.
The partition behavior of vanillin (as a model substance) in two phase mixed micellar
solutions was under investigation. We successfully used the Triton X-114 – CTAB – NaCl –
water system for micellar extraction of vanillin by the continuous countercurrent CPE [8] for
the first time.
This work was supported by St. Petersburg State University and German Academic
Exchange Service (Research Grant 12.23.498.2012).
References
1. P. Mukherjee et al. Adv.Colloid Interf. Sci. 2011, 162, 59.
2. S. Xie, et al. Journal of Chromatography A, 2010, 1217, 2306.
3. F.H. Quina, E.O. Alonso, J.P.S. Farah. J. Phys. Chem., 1995, 99, 11708.
4. N.A. Smirnova, et al. Langmuir, 2002, 18, 3446.
5. De Oliveira HPM, Gehlen MH. Langmuir, 2002, 18, 3792.
6. K. Panchal et al. J. Disprs. Sci. & Technology, 2006, 27, 33.
7. McCarroll et al. Langmuir, 1998, 14, 2965.
8. T. Ingram et al. Chemie Ingenieur Technik, 2012, 6, 840.
INTERMOLECULAR INTERACTION BETWEEN PHOSPHORIC ACID AND

POLY(METHYL METHACRYLATE) IN N,N-DIMETHYLFORMAMIDE
Safonova L.P.1,2, Nguyen Van Thuc2, Manin N.G.1,2, Shmukler L.E.1
1
e-mail: lps@isc-ras.ru
2
The aim of this work was to study the interaction of phosphoric acid with poly(methyl
methacrylate) (PMMA) in N,N-dimethylformamide (DMF) by calorimetry. Previously, it was
found that the conductivity of the proton-conducting gel electrolytes based on PMMA higher
conductivity of acids in DMF, which were used to obtain gels. Perhaps this is due to the fact
that the polymer matrix is not an inert component of the gel, and affects the process of proton
transfer. To test the assumption that the probability of interaction between the molecules of
acid and the polymer matrix, as well as methyl-tri-methyl-acetate (MTMA) - a compound
which models a single link of the polymer chain, was identified in the thermal effects of the
following processes at 25°C:
DMF + PМММ→ DMF + Н 3 РО4
DMF + МТМА → DMF + Н 3 РО4
In the calculation of the enthalpy of interaction between phosphoric acid and PMMA
(MTMA) thermal effects were taken into account:
dissolution process of acid in DMF
DMF → DMF + H 3 PO4
dissolution process of PMMA in DMF
DMF + PМММ→ DMF
For comparison, the obtained values for PMMA and MTMA, the enthalpy of interaction
between phosphoric acid and PMMA was attributed to a single link of the polymer with a
number average molar mass of the polymer, which was determined by gel - permeation
chromatography.
This work was financially supported by Russian Foundation for Basic Researches
(grants № 11-03-00311-а and 12-03-97534).
STUDY OF PHASE EQUILIBRIA IN THE Cu–Si–Ni SYSTEM

Samoylova O.V., Trofimov E.A., Mikhailov G.G., Sharlay E.V.
South Ural State University, Chelyabinsk
e-mail: samoylova_o@mail.ru
The study of phase equilibria in ternary system Cu–Si–Ni is a very important for
analyses of bronze production and copper fire refining technological processes. The task of
this work is finding a possibility of formation of nickel silicides in conditions of existence
metal melt on the basis of copper.
Liquidus line of Cu–Ni system has been calculated using ideal solution theory. Liquidus
lines of Cu–Si, Ni–Si systems have been calculated using subregular solution theory.
Calculated results for all systems coincide with literary data [1–3]. Energy parameters of the
subregular solution theory have been defined during the calculation. Equilibrium constants of
silicides transition from solid to liquid have been defined also. Activities in the Cu–Si, Ni–Si
systems have been calculated for 1350, 1850 and 2050 °С temperatures in order to verify the
modeled liquidus lines. Activities of copper and silicon have negative deviation from Raoult’s
law. These results are in accordance with literature experimental data [4]. Activity of nickel
has negative deviation from Raoult’s law too.
Thermodynamic modeling of isothermal sections of Cu–Si–Ni ternary phase diagram
was done using subregular solution theory and thermodynamic data of binary phase diagrams.
Thermodynamic modeling was done for temperatures ranging from 950 to 1200 °С. Obtained
results indicate preferable formation of nickel silicides rather than copper silicides in copper
melt.
This work was supported by the Russian Foundation for Basic Research (grant № 12-
08-31055mol_а).
References
1. M.E. Dritz. Binary and multicomponent phase diagrams for copper systems. Moskow,
Nauka, 1979 [in Russian].
2. N.P. Lyakishev. Binary phase diagram of metals. Vol. 2. Moskow, Mashinostroenie, 1997
[in Russian].
3. N.P. Lyakishev. Binary phase diagram of metals. Vol. 3. Moskow, Mashinostroenie, 1999
[in Russian].
4. Miki T. Activity measurement of silicon in molten Cu–Si binary alloy /T. Miki, N. Ogawa,
T. Nagasaka and M. Hino // ISIJ International, Vol. 42, № 10. – 2002. – P. 1071–1076.
SIMULATORS TO MASTER THE LANGUAGE OF PHASE DIAGRAMS

Savinov V.V.1, Lutsyk V.I.1,2, Parfenova M.D.2, Sakharova A.A.2, Tyuryukhanova A.P.2
1
Institute of Physical Materials Science SB RAS, Ulan-Ude, e-mail: vluts@pres.bscnet.ru
2
Buryat State University, Ulan-Ude
New approach for phase equilibria investigation are based on the idea of a training
software creation for the teaching of qualified experts in the multicomponent systems study
area. This kind of the trainings software allows to create the phase diagrams (PD) computer
models and then to construct vertical and horizontal sections with the decoding of intersected
surfaces and phase regions, to calculate the mass balances, to generate the spectra of thermal
and X-ray phase analyses for given compositions. A user assumes the phase diagram topology
(Fig. a-c) by means of the binary systems information, and then determines all geometrical
elements by means of minimal number of experiments.
Figure. T-x-y diagrams with component B allotropy (a), decomposing АmВn (b) & incongruently
melting АmВnСk (c) compounds. Mass balances for (a) on isopleth B-AC (d). DTA and electrical
conductivity spectra on the curve еВСU of (a) imitation (e).
Main destination of PD computer model – to solve practical problems, beginning from
correct and compact representation of the experimental information and finishing calculations
of formed in the system microconstituents of the phases assemblages. Diagrams of vertical
mass balances give a possibility to follow the changing of phases mass fractions for the given
alloy in calculated temperature intervals. Horizontal mass balances diagrams help to show
relative phase fractions in vertical sections MN at given temperatures (Fig. d). It is possible to
generate the thermogram prototype for given alloy (Fig. e). The peak height of the DTA signal
represents the phase with the maximal increase or decrease of mass portions in the
corresponding temperature interval. Not gear but rectangular peak corresponds to the invariant
regrouping of masses on the horizontal plane. The alloy presence is supported by the elevated
electro conductivity. For a generation of X-ray spectra the training software has been fitted by
the data base with characteristics of initial components A, B and C and corresponding binary
and ternary compounds (with their polymorphous modifications).
THE ANALYSIS OF ENTRAINERS ISOSELECTIVITIES

Sazonova A.Y., Raeva V.M., Frolkova A.K.
e-mail: amelyschafe@mail.ru
Heavy and light boiling entrainers selection for distillation of binary mixtures usually
goes through two important steps: set generation of potentially selective substances and
choosing the most efficient of them. The second step is commonly characterized by energy
costs for separation in functional distillation unit.
At the first step thermodynamical criterion was applied to establish quantitative
matching in volatilities of separating compounds (1, 2) in presence of selective entrainer α 12
(E)
and difference of excess Gibbs energy values in binary mixture component – entrainer [1].
The capabilities of modern databases of physicochemical properties and phase
equilibrium allow to find a large number of potentially effective agents. To reduce the volume
of simulation experiments a further discrimination of E is required.
To solve this problem isoselectivities analyzing of potential entrainers S = α 12 (E)
α 12
was proposed.
Theoretical analysis of selectivity isolines diagrams for ternary systems 1 – 2 – RA has
revealed structures in which entrainer was effective for separation restricted area of separating
compositions 1 – 2 and structures in which an increase of E quantity led to a reduction in
selectivity.
The simulation experiment have been carried out for binary azeotropic mixtures with
industrial significance (organic and petrochemical syntheses technologies, chemical and
pharmaceutical industry). Diagrams of volatility α 12 (E)
= const and selectivity S = const
isolines have been obtained.
Entrainer choice was performed on the base of analysis of diagrams each type, as well as
combining both types of diagrams. Simultaneous analysis of diagrams α 12 (E)
= const and
S = const showed that the efficiency prediction results may be different.
The best entrainer, i.e. providing lower energy costs, if choosing from several providing
similar α 12
(E)
is the one with higher selectivity. This is illustrated when separating systems
methyl ethyl ketone – methanol, ethanol – water, cyclohexane – benzene, acrylonitrile – water
and 1-pentanol – propionic acid. Extractive agents providing the same selectivity in the
acetone – chloroform mixture were identified.
Using isoselectivity diagrams for evaluating the possibility of binary mixtures separation
with different compositions and formation of double entrainers for distillation have also been
proposed in this study.
Reference
1. Raeva V.M., Sebyakin A.Y., Sazonova A.Y., Frolkova A.K. The choice of possible
entrainers for the extractive distillation of binary mixture benzene – cyclohexane // Vestnik
MITHT. 2011. V. 6. № 1. P. 43-53.
RELATIONSHIPS BETWEEN THE GIBBS ENERGY AND ENTHALPY

OF SOLVATION PROCESSES
Sedov I.A., Solomonov B.N.
Kazan Federal University, Kazan
e-mail: igor_sedov@inbox.ru
It is well known that for many physical and chemical processes the changes of enthalpy
and entropy are linearly correlated, if we consider a series of participating molecules with
different structures. Such correlations are called compensation or isoequilibrium relationships
[1].
This means that there is also a linear relationship between the Gibbs free energy and
enthalpy change values. The accuracy of the Gibbs free energy values is usually much higher
than that of entropies. On the basis of a large amount of experimental data, we have analyzed
the relation between the Gibbs free energy and enthalpy for the process of solvation of various
molecules from the gas phase into an infinitely diluted solution at 298 K. For many substances
that belong to different classes of organic compounds dissolved in various nonassociated
solvents, there exist a single linear correlation between these two quantities: ΔG = 0.63ΔH +
16 kJ·mol–1. Correlations with similar coefficients are also obtained if we consider a single
solute dissolved in a series of solvents or a series of solutes dissolved in a single
nonassociated solvent.
A completely different situation is observed in the case of associated solvents. For any
molecule dissolved in such solvents the data point in ΔG vs ΔH plot deviates from the above
line in the direction of higher Gibbs free energy values. This can be viewed as a manifestation
of the solvophobic effect, which decreases the solubility of substances. This effect has its
greatest strength in water, is somewhat weaker in formamide and polyhydric alcohols, and
even much weaker in monohydric alcohols. The contributions into the enthalpy and Gibbs free
energy of solvation arising from the influence of the solvophobic effects were determined for
various solutes and solvents. For these magnitudes, the relationships with the structures of
solute and solvent were considered.
At the same time, thermodynamic properties of many self-associated solvents other than
water and alkanols remain poorly studied. In order to expand our knowledge about the
solvophobic effects, we have determined experimentally the enthalpies and Gibbs free
energies of solution of various apolar molecules (hydrocarbons and their halogenated
derivatives) in propylene glycol at 298 K. The methods of titration calorimetry and gas
chromatographic headspace analysis were used. The contributions of the solvophobic effect
into the Gibbs energy of solvation determined using these experimental values show a linear
increase with increasing molecular volume of the solute, like in other self-associated solvents
we have studied. Unlike in such solvents as water and formamide, in propylene glycol the
solvophobic effect was found to have a little influence on the values of the enthalpies of
solvation.
Reference
1. Liu, L., Guo, Q., Chem. Rev., 2001, 101, 673 – 695.
THERMODYNAMIC FUNCTIONS OF DISSOLUTION IN METHYL CELLOSOLVE

Sedov I.A., Stolov M.A., Solomonov B.N.
e-mail: igor_sedov@inbox.ru
Methyl cellosolve is an important solvent used in dye and rubber industries. However,
the thermodynamic properties of solutions in this solvent are virtually not studied.
Using a titration calorimeter, we have determined the enthalpies of solution at infinite
dilution for a series of alkanes and aromatic hydrocarbons at T = 298 K. For the same
compounds, limiting activity coefficients have been measured by gas chromatographic
headspace analysis of the equilibrium vapor phase, and the values of the Gibbs energies of
solvation have been calculated. Solvent effect on the relationship between the values of the
Gibbs energy and enthalpy of solvation is considered.
The obtained data are of interest for parameterization of empirical models of associated
solutions, as well as for studying the structure-property relationships for solutions in methyl
cellosolve.
INFLUENCE OF NONIONIC SURFACTANT STRUCTURE

ON THE SELF-ASSEMBLING PROCESSES IN MULTICOMPONENT SYSTEMS
AND SOLUBILIZING ABILITY OF LUMINESCENT COMPLEXES
Selivanova N.М., Кuzovkova М.А, Маkarova D.V., Galyametdinov Yu.G.
Кazan National Research Technological University, Каzan
e-mail: natsel@mail.ru
Organized media based on surfactants have been actively investigated as nanoreactors
for the synthesis of quantum dots, transport systems for drug delivery and models of
biological membranes. A highly sensitivity bioassay is widely used fluorometric method based
on the measurement of the sensitized luminescence of lanthanide chelates. One of the factors
of increasing the fluorescence intensity of lanthanide complexes is solubilization of chelates
in surfactant micelles media. The aim of this work was to study the processes of nonionic
surfactants self-organization in water and water-decanol media in the presence of lanthanide
ions and their chelates.
The objects of the study were systems based on nonionic surfactants tetraethylene glycol
monododecyl ether C12H25O(CH2CH2O)4H (С12EO4) and decaethylene glycol monododecyl
ether C12H25O(CH2CH2O)10H (С12EO10) lanthanide nitrates Ln(NO3)36H2O Ln(III)-La, Tb, Eu
in water and water-decanol media.
According tensiometry data incorporation of decanol molecules in С12EO4/H2O and
С12EO10/H2O systems reduces the surface tension and extreme changes in CMC. The
minimum value of CMC is observed at a molar ratio of surfactant/decanol = 0.4. Analysis of
the adsorption layer parameters showed that the incorporation of decanol in a binary system
surfactant/water leads to an increase in the polar part of the molecule, which indicates the
formation of mixed micelles. Incorporation of Ln (III) ions in the C12EO4/H2O/C10H21OH and
C12EO10/H2O/C10H21OH systems at a molar ratio of surfactant/Ln(III) - 1:2 leads to a
significant reduction in CMC compared with the binary system. However, for
C12EO4/La(III)/C10H21OH system in the presence of decanol the synergism of surface-active
properties wasn’t found. In the case of С12EO10/Ln(III)/C10H21OH system serious synergic
effect was observed. Aggregation numbers were determined using steady-state fluorescence
method with pyrene as a probe. The significant decrease of aggregation numbers in the
presence of decanol in С12EOm/H2O system was observed. This effect indicated the
penetration decanol in the micelle and the surfactant molecules displacement. According DLS
data the size of the micelles in the presence decanol at molar ratio 0.2-1.5 does not significant
change. Thus, the decanol forming mixed micelles does not affect on the size of the solvation
shell and localized in the polar part of the surfactant.
Analysis of the luminescent properties of Tb(Phen) and Eu(Phen) complexes in mix
system showed that in the presence of decanol the luminescence efficiency slightly reduced
but the lifetime of the TbIII ion increased in 2 fold and EuIII ion in 1.5 fold. Found regularities
indicate potential control of lanthanide luminescent properties by varying the composition of
organized microheterogeneous media.
The work was supported by the RFBR grant 11-03-00679-а.

THE THERMODYNAMICS OF 2,2΄-DIPYRIDYL SOLVATION

IN METHANOL-DIMETHYLSULFOXIDE SOLUTION
Semenov I.M., Repkin G.I., Sharnin V.A.
e-mail.ru: oxt703@isuct.ru
The data on the complex formation processes thermodynamics characteristics of all
participants are required to describe the solvent composition influence on the stability of
complexes from the side of solvation approach. The data on the Gibbs energies of solvation
reagents for binary nonaqueous mixtures are sorely limited. In this report the Gibbs energies
of 2,2΄-dipyridyl transfer in methanol-dimethylsulfoxide solvent are presented, the entropy
change is calculated and analyses of binary solvent composition influence on the solvation
thermodynamics characteristics of investigated amine is carried out.
The Gibbs energies of 2,2΄-dipyridyl transfer from dimethylsulfoxide to methanol are
determined at 298K by the distribution of amine between two immiscible phases. The phase
which is not mixed with methanol, dimethylsulfoxide and their mixtures is hexane [1]. The
entropy change of 2,2΄-dipyridyl Gibbs energy of transfer is calculated involving the literature
data on the enthalpies of amine solvation [2].
It is established that the rise of 2,2΄-dipyridyl Gibbs energy of transfer is observed with
the increase of methanol concentration in mixed solvent. This rise of 2,2΄-dipyridyl ΔtG due
to the entropy contribution dominance of enthalpy one which promotes the increase of
solvated amine stability. The rise of 2,2΄-dipyridyl exotermicity with the increase of methanol
in mixed solvent explains by the amine solvation [2] and decrease of 2,2΄-dipyridyl solvation
entropy caused by relation of solution molecules interaction contributions between 2,2΄-
dipyridyl and each other.
The composition of acetonitrile-dimethylsulfoxide and methanol-dimethylsulfoxide
solutions influence on the 2,2΄-dipyridyl solvation shows that the transition from
dimethylsulfoxide to acetonitrile also leads to the increase of amine transfer Gibbs energy but
the reason of that is variation as entropy as well as enthalpy contributions.
References
1. Rastvoriteli v organicheskoy khimii. Raykhardt KH. L.: Khimiya. 1973. 152.
2. Bykova G.S., Kuzʹmina I.A., Shormanov V.A. Zhurn. fiz. khimii.1995. 69. 7. 1330-1331.
3. Semenov I.M., Repkin. G.I., Sharnin V.A. Zhurn. fiz. khimii. 2013. 87. 3. 464-468.
ENTHALPIES OF MIXING OF LAURYLMETHACRYLATE

WITH SOME ORGANIC SOLVENTS
Serheyev V.V., Коs Yu.V.
Lviv Polytechnic National University, Lviv, Ukraine
e-mail: vsergeev@polynet.lviv.ua
The enthalpies of mixing for binary systems laurylmethacrylate (LMA) with benzene,
hexane and 1,2-diclorethane was measured by calorimetric methods as 293 K and
atmospheric pressure.
The raw materials, for determination heat of mixing, were of the commercial grade and
were supplied by MERCK (Germany). The chemicals received were further purified through
repeated evaporation. The chemicals were then selected based on their unique densities as
well and the refractive index. The contamination was kept below 0.2wt%, as verified through
chromatography.
The enthalpies were measured by differential microcalorimeter MID-200 with the use of
ampoules methodology. For verification of reliability of the presented methodology conducted
the series of experiments on determination of enthalpies of mixing of equimolar solution
benzene and hexane.
The enthalpies of mixing for solutions ∆mixH293 and mole fraction Ns the first component
of solution, in this case - solvent are reported in Table.
Table.
The enthalpies of mixing (J/mol ) at 293K
Benzene - LМA
Np, mol % 11,12 15,46 31,38 49,85 70,23 80,47
∆mixH293 -72,5 -60,2 70,1 241,8 281,6 234,7
Hexane – LМA
Np, mol % 11,25 30,58 50,29 60,53 70,12 90,08
∆mixH293 -38,2 54,9 198,6 242,6 254,3 150,3
1,2-Diclorethane – LМA
Np, mol % 19,57 31,54 52,07 70,04 82,63
∆mixH293 -67,2 73,9 364,6 457,6 366,2
The excess volumes for the investigated systems are negative for solvent concentrations
below 25 mol% and positive above this concentration.
The magnitude of enthalpies of mixing for equimolar solutions of investigated system
values showed the following trend
Hexane < Benzene < 1,2-Diclorethane
PHYSICOCHEMICAL PROPERTIES OF IONIC NANOFLUIDS

Shevelyova M.P., Paulechka Y.U., Kabo G.J., Blokhin A.V.,
Levitskaya T.N.
Belarusian State University, Chemistry Faculty, Minsk, Republic of Belarus
e-mail: marina.shevelyova@gmail.com
A number of ionic nanofluids (INF) composed of stacked-cup multiwalled nanotubes

(MWCNT) and 1-butyl-3-methylimidazolium and 1-butyl-1-methylpyrrolidinium room-
temperature ionic liquids (ILs) was prepared in two different ways. According to the
conventional procedure, MWCNT were grinded in IL until the uniform black fluid was
obtained. With this procedure ILs did not penetrate into MWCNT. Another procedure applied
in this work included degassing of the initial components followed by grinding. In this case,
MWCNT were filled with ILs.
Heat capacity of ionic nanofluids (INF) was measured in an adiabatic calorimeter over
the temperature range of T = (80 to 370) K. It was found that heat capacity of the materials
outside the temperature ranges of phase transitions and glass transitions can be calculated by
weight-averaging of heat capacities of the components. Moreover, the triple-point and glass-
transition temperatures of INF agreed well with the corresponding values for pure ILs.
Multiple heating-cooling cycles did not produce observable changes in thermodynamic
properties of the materials.
Density of INF was measured in a glass cylinder with a flat top. The apparent density of
MWCNT in INF prepared according to the procedure proposed in this work was close the
density of bulk graphite, and if the conventional procedure was used, the density was
significantly lower. Based on the obtained data, the structural parameters of nanotubes were
estimated.
THERMODYNAMICAL-TOPOLOGICAL ANALYSIS OF BINODAL SURFACE

OF QUATERNARY SYSTEMS WITH ONE PAIR OF SPLITTING COMPONENTS
Sharonova Ye.A., Frolkova A.V., Frolkova A.K.
e-mail: frolkova_nastya@mail.ru
The border of splitting area in quaternary systems is binodal variety, the dimension
which is equal to two and which is characterized by the presence of its singular points (tops)
and its structure of ribs bond. Special points of the binodal variety are: the critical points; the
point of equilibrium liquid phases – the tops of the splitting simplex of azeotropes;
Analysis of bimodal surface of quaternary system (i-j-k-l (splitting binary component i-
j), was conducted under the following assumptions: the system consists of one pair of
components with limited mutual solubility (i-j), which always contains heteroazeotrope; if
there are ternary azeotropes in the system, they are also heterogeneous.
The analysis of all possible cases of singular points combination on the sweep of the
tetrahedron allowed to obtain a digraphs of binodal surfaces for quaternary systems without
quaternary azeotrope (Fig.1).
Fig. 1. Classes and the types of binodal surfaces structures digraphs in systems without quaternary
azeotrope (хij’ , хij’’ - the top of the splitting simplex, Кk, Кl - critical points,
Кk,-Кl - critical line).
A classification of binodal surfaces digraphs structures was suggested. The first digit
indicates the number of singular points on the binodal surface boundary, the second - the
number of points on the surface (α and β – are the types).
All the digraphs are submitted to the rule of the algebraic sum of singular points indices.
Thus, the use of an approach based on a net-concentrations allowed to take into account all the
physical-chemical characteristics of splitting, which are reflected in the structure of binodal
surface.
project № 11-03-00295-a).
FLORY-HUGGINS PARAMETERS OF SYSTEMS:

PHOTOPOLYMERS - LOW-MOLECULAR LIQUIDS
Shpineva M.A., Konyukhov V.Yu.
Mendeleev University of Chemical Technology of Russia, Moscow
e-mail: volkon_1@mail.ru
Flexographic plates (photopolymers) during production and operation processes interact
with a variety of low-molecular liquids, as a result of such interaction they absorb solutions
i.e. swell to a varying degree. Plates’ swelling ultimately reduces print quality, so the study of
this process is highly relevant.
Process of polymer swelling is a superposition of two co-occurring processes. On the
one hand, it is a diffusion of the solvent into polymer matrix, on the other hand it is a
deformation of polymer matrix (grid) caused by absorption of liquid. As the swelling goes grid
stretches increasingly, causing tension in the material. The process stops when further solvent
diffusion is constrained by grid tension. The value of maximal polymer matrix deformation
depends on thermodynamic quality of the solvent, characterized by the value of χ. A
mathematical model describing diffusion of the solvent into the polymer and deformation of
the polymer matrix was proposed in [1].
Studies of photopolymers swelling were conducted in ethyl acetate, butyl acetate, ethyl
cellosolve, n-heptane, n-butanol, isopropanol and water. In chromatographic experiments
ethyl acetate, butyl acetate, heptane, isopropanol, n-butanol were used. the highest
thermodynamic affinity (minimum value of χ) towards flexographic plates have butyl acetate
and ethyl acetate as for them χ has the minimum value. For these solvents χ<0.5 and without
the grid polymers under consideration would dissolve to form a true solution. In the case of
heptane χ=0.55, and its properties are close to θ-solvent.
Flory-Huggins criteria can also be determined from the chromatographic data. the
equation for calculating χ out of chromatographic data is:
 RT  P10
χ = ln  − (B11 − V1 ) − ln 1  + 1 − 1 
r  r
0
 1 g 2 
P V M RT
Here P1° is the vapor pressure of the solvent (sorbate) at a column temperature, Vg is a
specific retention volume (corrected retention volume, divided by the weight of the polymer in
the column), M2 is the molar mass of the polymer (phase), B11 is the second virial coefficient
of the sorbate, V1 is the molar volume of the liquid sorbate [2].
For n-butanol, isopropanol and butyl acetate χ decreased with increasing T, for n-
heptane and ethyl acetate dependence with a maximum was observed.
It was interesting to compare the values of χ obtained by the two methods described at
close temperatures (T = 30°C). It is evident that there is a good correlation between χ values
which shows the correctness of used methods for χ determining.
References
1. Denisyuk E.Ya., Volkov E.R. Effect of the thermodynamic quality of the solvent on the
kinetics of polymer grids swelling. Vysokomolekularnie Soedineniya Seriya A. 2003, 45,
1160-1168.
2. Dzhvarsheyshvili A.I., Sherstneva M.K., Konyukhov V.Yu. Thermodynamics of
Photopolymer Interaction with Low-Molecular Liquids. XVI International conference on
chemical thermodynamics in Russia, Suzdal, July 1-6, 2007, V 1, P 260.
THERMODYNAMIC PROPERTIES OF DILUTED WATER AND WATER-SALT

SOLUTIONS OF PEG AND POLYMERIC ANIONIC SURFACTANTS
Shulyak I.V., Grushova E.I.
Belarusian State Technological University, Minsk
e-mail: IlyaSh@tut.by, Grushova.e@mail.ru
At the present time it is established that PEG and polymeric anionic surfactants can
intensify process of flotation concentration of sylvinite ores. Therefore, for development of
optimum reagent modes it is necessary to have data on behavior of molecules of PEG and
polymeric anionic surfactants in water and water-salt solutions.
The purpose of this work was research of temperature and salts influence on
thermodynamic properties of the diluted solutions of PEG of MW 400, 1500, 2000, 4000
20000 and polymeric anionic surfactants of the following structure: С12(14)H25(29)–O–(CH2 –
CH2О)n –CH2 –COONa, where n=4, 7, 10. Saturated at 293,15 solution of KCl and NaCl salts
was used as salt solution.
Kinematic viscosity of PEG (concentration of 0,250-1,650 g/dl) and polymeric anionic
surfactants (concentration of 0,170-2,000 g/dl) solutions in the temperatures range of 293,15 –
323,15 K were defined in this work. The values of kinematic viscosity were used for
calculation of intrinsic viscosity ([η]), the Huggins constant (Kh), apparent activation energy
of viscous flow (Ea), and also a constant of the Mark-Kuhn-Hauvink equation (MKH) for the
following systems: PEG – water, PEG – salt solution and polymeric anionic surfactants –
water.
It is established that change of [η] of water and the water-salt PEG solutions with
growth of temperature decreases and these dependences have linear character. It is connected
with increase of rotary mobility of macromolecules in solution, and weakening of PEG –
water intermolecular interaction. [η] values for water-salt solutions are less than that of water
solutions that testifies deterioration of thermodynamic quality of solvent in the presence of
electrolyte. In such conditions the macromolecular coil of PEG becomes of smaller sizes.
Kh dependence on temperature has difficult character for studied systems, and the
extreme is observed at temperatures 303,15 and 313,15К for low-molecular PEG. Apparently,
it is connected with structural transformations of solutions at these temperatures.
It is shown that Ea values in the temperature range of 293,15 – 323,15 are more than that
for water and increase with concentration growth. It testifies more ordered structure of PEG in
comparison with solvent.
Dependence of the MKH equation constants on temperature is defined for studied
systems. It is shown that values of parameter a = 0,60 – 0,79. It testifies that water is
thermodynamic - good solvent for PEG, and PEG macromolecules in solution are flexible.
Kuhn's segment is equal 13.1Å.
It is defined that with growth of temperature the value of [η] for polymeric anionic
surfactants (at n = 4, 7) decreases, and for polymeric anionic surfactants (at n = 10) increases.
Apparently, short ethoxy chains dividing an alkyl radical and –COO- group behave as the
hydrophile group that leads to lengthening of the radical, and for polymeric anionic surfactants
with n = 10 rather long ethoxy chain is well hydrated, and –COO- group improves
thermodynamic interaction between water and polymeric anionic surfactants. It also proves to
be true that Kh values for polymeric anionic surfactants (at n = 4, 7) increase with temperature
growth, and for polymeric anionic surfactants (at n = 10) decrease.
INFLUENCE OF LOW INTENSITY MILLIMETRIC COHERENT ELECTROMAGNETIC

WAVES ON COEFFICINET OF THERMAL EXPANSION
OF WATER AND AQUOEUS-SALINE SOLUTIONS
Simonyan G.S.
e-mail: sim-gev@mail.ru
The density of twice distillated water and aqueous-saline buffer 0.1 SSC (1 SSC = 0.15
М NaCl + 0.015 M Na citrate) which is radiated by none thermal millimetric electromagnetic
waves with resonance vibration frequency 50.3 GHz and none resonance-48.3 GHz for water
structure. The coefficient of expansion of water and buffer in the temperature range
293.15÷343.15K are determined by the follow equation:
1  dρ  d ln ρ
α =  =−
ρ  dT  dT
Table. The values of thermal expansion: α.104 K-1.

Solution 293 298 303 308 313 318 323 328 333 338 343
Water 2,31 2,52 3,00 3,42 3,79 4,1 4,4 4,77 5,05 5,32 5,64
4 7
Buffer 2,34 2,57 3,03 3,44 3,79 4,2 4,6 5,11 5,63 8,0 9,64
5 9
Water + 50,3GHz 2,30 2,53 3,02 3,41 3,81 4,1 4,4 4,75 5,07 5,35 5,67
4 6
Buffer +50,3GHz 2,35 2,57 3,04 3,45 3,81 4,2 4,5 4,70 5,01 6,6 7,9
8 9
It is known that water compared to other liquids has the lowest coefficient of thermal
expansion which is expalined by the structural features of water. In liquid phase molecules of
water are organized associates and the each molecule of water is rounded with 4÷5 molecules
of water. As following from Table with the increase of temperature α is increased for studied
solutions. Consequently, there is an increase in the molar volume. The increase of α with the
rise of temperature is different for studied systems. It is stronger for buffer, spatially for
temperatures higher than 313.15K. Perhaps this is due to the fact that the ions displace some
of the molecules of water from the voids of the hexagonal structure, as result of this increasing
the degree of hydration of ions and the proportion of linear hydrogen bonds.
Irradiation of water has a little effect on values α . In the temperatures higher than
313.15K coefficient α for irradiated solutions of buffer are lower than for none irradiated
solutions. The obtained experimental data can be explained by assuming that, due to the
possibility of exposure is difficult formation of linear hydrogen bonds due to the temperature
rise.
THERMODYNAMIC CHARACTERISTICS OF β-ALANINE DISSOLUTION

IN A (WATER+ALCOHOL) MIXTURES AT 298.15K
Smirnov V.I., Badelin V.G.
G. A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo
e-mail: vis@isc-ras.ru
β-Alanine is the simplest β-amino acid which plays an important role in a variety of
biological processes. β-amino acids despite their biological importance have received much
less attention than α-amino acids, but interest in β-amino acids has increased over the past
several years [1-6]. In this work we report the enthalpies of solution, ∆ sol H m , for β-alanine in
aqueous methanol (MeOH), ethanol (EtOH), 1-propanol (1-PrOH) and 2-propanol (2-PrOH),
with a view to gaining information on energy-related changes in the amino acid − alcohol
intermolecular interaction under the influence of the co-solvent content and its nature. The
alcohol content in mixtures ranged up to 0.4 mole fractions and at temperature 298.15K. One
should note that this is the first thermochemical investigation of β-alanine dissolution in the
aqueous solutions of alcohol. From the determined standard dissolution enthalpies ∆ sol H  of
β-alanine in aqueous alcohol solutions the enthalpy coefficients of pairwise interactions hxy,
and the enthalpies of transfer, ∆ tr H  were calculated and analyzed. We have ascertained that
the thermodynamic characteristics of β-alanine dissolution and transfer depend on both the
composition of a mixed solvent and the structure of an alcohol molecule. In the studied binary
solvents, the β-alanine molecule has a mixed solvation shell, which consists of both alcohol
and water molecules. At low concentrations of alcohol (x2 < 0.15) the molecule of β-alanine is
mainly hydrated and the endothermic effect of partial dehydration of theirs solvation shells of
β-alanine predominates over the exothermic effect of a direct interaction between the
molecules of β-alanine and polar groups of alcohol. The coefficients hxy are increased (in size)
in the following series: H2O+MeOH < H2O+EtOH < H2O+1-PrOH< H2O+2-PrOH. Such
sequence can be connected both with increasing hydrophobicity of alcohols and with the
increasing energy of intermolecular interactions between components of studied mixtures. It is
established that the obtained values of enthalpic coefficients of pair-wise interaction between
molecules of β-alanine and alcohol molecules correlate well with the values of enthalpic
coefficients of pair-wise interaction between the molecules of H2O and alcohol molecules.
This means that the strengthening of the pairwise interaction between the alcohol and H2O
molecules in the mixtures cause an increase of the endothermic contribution to hxy of β-
alanine − H2O interactions. The dependence of ∆ tr H  =f(x2) in (H2O + MeOH) mixture is
similar to that dependence in (H2O + EtOH) mixture and the dependence of ∆ tr H  =f(x2) in
(H2O + 1-PrOH) mixture is similar to that dependence in (H2O + 2-PrOH) mixture. In first
two mixtures on the dependences is no observed the maximums. Probably it is connected with
of destruction of alcohol self-associates in wider concentration range, their hydration with
further dehydration at interacting with the β-alanine molecules. In second two mixtures on the
dependences have explicit endothermic maxima around the mole fraction 0.15÷0.18 of
alcohol. With the increase the concentration of 1-PrOH and 2-PrOH in water to x2> 0.18÷0.22
the exothermic contribution from the direct interaction of β-alanine - propanol begins to
prevail in the total enthalpy effect of interactions and the dependence of ∆ tr H  =f(x2) curve
becomes opposite in direction.
THERMODYNAMIC PARAMETERS OF DISSOLUTION ISOMERIC

5-(NITROPHENYL)-FURAN-2-CARBALDEHYDES IN ORGANIC SOLVENTS
Sobechko I.B.1, Van-Chin-Syan Yu.Ya.1, Gorak Yu.I.2 Turitsa V.V.2, Kos R.V.2
1
National University "Lviv Polytechnic", Lviv, Ukrain
2
Lviv Ivan Franko National University, Lviv, Ukrain
e-mail: phys.chem.lp@gmail.com
Dissolution enthalpy of ortho-, meta-, and para-5-(nitrophenyl)-furan-2-carbaldehydes in
saturated solutions were determined based on the temperature dependence of its solubility in
organic solvents of different polarities. The samples of substances, having been purified by
recrystallization from a solution in DMF and ethanol, were used for research. Purity of the
substance was confirmed by DTA. Ethyl acetate, iso -propanol and dimethylketone were used
as solvents.
The solvents were purified by fractional distillation with subsequent identification of the
refractive index, before the experiments. The presence of impurities not exceeding 0.1% by
weight was defined by gas-liquid chromatography. Dissolution of substances was carried out
in a sealed glass vessel fitted with a teflon stirrer and thermometer. The water temperature in
the thermostat was maintained accurate within ± 0,1 °C. The rotation speed of the stirrer was
50 rpm. During the stirring all the solid phase was in suspension state. In preliminary
experiments it has been determined that at the chosen stirring mode noticeable changes of
solubility disappear after 45-60 minutes in all solvents. In all further experiments the
saturation of the solutions was carried out for 90 minutes under constant stirring. To confirm
the equilibrium establishing all experiments were carried out both in the mode of temperature
increasing, and in the mode of its decreasing.
Sampling was carried out by series from three samples. Samples were transferred to
weighing bottles. The solvent was removed at the temperature of 333-343K until constant
weight of dry residue. All necessary weighing were performed with accuracy ± 0,0002 g. The
experimental data are processed by least square method using linear form of Schroeder
equation: lnN2 = A- B/T and represented in the table, wherein: ΔsolH = -B•R. Errors of the
values refer to the significance level 0.95.
Table. Temperature dependence of solubility and dissolution enthalpy of isomeric 5-
(nitrophenyl)-furan-2-carbaldehydes in organic solvents
Solvent Range n S2·103 А - В, К ΔsolH
Т, К N2, % mol kJ/mol
5-(2-nitrophenyl)-furan-2-carbaldehyde
Ethyl acetate 276-319 1.5-8.2 36 3.00 7.828 3317 27.58±0.16
iso-Propanol 296-327 0.10-0.95 33 3.37 15.95 6723 55.97±0.33
Dimethylketone 276-318 2.7-16.0 31 2.30 9.269 3560 29.60±0.20
5-(3-nitrophenyl)-furan-2-carbaldehyde
Ethyl acetate 275-324 0.2-1.1 46 3.94 3.923 2748 22.85±0.15
iso-Propanol 300-344 0.03-0.36 35 10.29 11.17 5788 48.12±0.40
Dimethylketone 273-323 2.5-15.6 42 1.43 5.784 3235 26.90±0.10
5-(4-nitrophenyl)-furan-2-carbaldehydes
Ethyl acetate 303-343 0.17-0.59 38 5.24 4.061 3161 26.28±0.26
iso-Propanol 303-343 0.01-0.09 41 38.7 12.01 6451 53.63±0.83
Dimethylketone 299-324 0.18-0.45 37 0.760 4.133 3073 25.55±0.13
EFFECT OF SIZE AND SHAPE OF HARD PARTICLES ON BIAXIAL NEMATIC

STABILITY IN TERNARY SYSTEMS
Sokolova E.P., Vlasov A. Yu., Marinichev A.N.
e-mail: esok@AM7940.spb.edu
A peculiarity of mixtures of rodlike (R) and platelike (P) particles consists in the
formation of a biaxial nematic (Nb) phase, which may turn out to be either metastable or
stable with respect to demixing into the uniaxial nematic phases, a rod-rich N+ phase and a
plate-dominated N– phase [1, 2]. A growing interest towards the study of the biaxial phase in
a particular case of systems includ-ing long rods is motivated by development of concepts
addressing phase behavior and orientational order in carbon nanotubes /liquid crystal
dispersions [3]. The present communication is focused on the effect of doping the system by
the third component (an admixture) represented by long rods upon the stability of the biaxial
phase in a binary mixture of rods and plates with small aspect ratios. We employ the Zwanzig
off-lattice model [4] of a multicomponent nematic system of parallelepipeds, with their
symmetry axes pointing along one of the three coordinate axes, collective interactions of
particles being treated in the 3rd virial approximation.
The binary R–P sub-system consists of particles having equal volume and aspect ratios (
γR = 5, γP = 1/5), whereas the admixture rods (L) have aspect ratios within the interval 6 ≤
γL≤ 10. The pos-sibility of biaxial symmetry is inferred by exact calculation of the Gibbs free
energy along the sec-tions уL= const of the composition triangle (уL is the mole fraction of the
component L) at constant values of t* defined as proportional to the reduced temperature ( ).
The concentrations for uniaxial to biaxial symmetry transitions are located numerically from
the biaxial branch of the order parameters, assuming that close to the N+ – Nb and N– – Nb
bifurcation points the biaxial order parameter for each component is vanishingly small. v PT
kB /
In the R–P system under study, the biaxial nematic phase is metastable with respect to
the N+–N– demixing. Admixing of rods with γL 8 is shown to enhance the thermodynamic
stability for the Nb phase even at very low concentrations (namely, on the section уL = 0.01),
within a broad inter-val of t*. Data of calculations are discussed in connection with the study
[2] of the effect of polydispersity upon the properties of a biaxial phase in mixtures of plates
and rods with restricted orientations. 
References
1.Wensink H.H., Vroege G.J. // J. Phys.: Condens. Matter. 2004. V. 16. P. 2015–2027.
2. Martinez-Rat N Y., Cuesta J. A. // J. Chem. Phys. 2003. V. 118. No 22. P. 10164–10173.
3. Matsuyama A. // Liq. Cryst. 2011. Vol. 38. No 6. P. 729 –736.
4. Sokolova E.P., Tumanyan N.P., Vlasov A.Yu., Masters A. J. // Mol. Phys. 2006. V. 104. No
19. P. 2901–2918.
This work was supported by Russian Foundation for Basic Research (Grant # 11-03-
01106-a)
THE PRESSURE DEPENDENCE OF ISOTHERMAL COMPRESSIBILITY

OF LIQUID DIOLS
Solonina I.A. 1, Troitsky V.M. 2, Rodnikova M.N. 1, Sirotkin D.A. 1, Shirokova E.V. 1
1
e-mail: rodnikova@igic.ras.ru
2
GAZPROM VNIIGAZ, Razvilka, Leninsky District, Moskow region
Isothermal compressibility of three liquid vicinal diols (ethylene glycol – EG, 1,3-
propanediol – 1,3PD, and 1,4-butanediol – 1,4BD) as well as water was measured using the
unique customized facility [1] at the 298K in the pressure region 0.1-300 MPa. Pressure
dependence of isothermal compressibility was lowest for EG, largest – for 1,4BD, and also
crystallization of this diol was found at the pressure ~80 MPa.
Molecules of the diols have two hydroxyl groups, i.e. two centers of donor and four
centers of acceptors of protons. This allows assuming the presence of spatial network of
hydrogen bonds in liquid phase [2]. It is exactly the stability of this network that leads to
strong supercooling of these liquids and to low values of the coefficients of isothermal
compressibility and thermal expansion. The stability of hydrogen bonds O-H...O in network in
liquids depends on topology of network and on numbers and nature of its defects. The
increase of compressibility at the normal pressure can be represented as following order: EG <
1,3PD < H2O < 1,4BD. This sequence lasts up to 80 MPa with a low dependence from the
pressure. Isothermal compressibility of all investigated substances except 1,4BD weakly
depends upon pressure. The crystallization of 1,4BD occurs at the ~80 MPa. Its molecule
represents seven-membered cycle with intramolecular hydrogen bond which is most strong
between diol molecules. It was shown by IR-spectroscopy of gas and liquid phases of number
of diols from EG to 1,5-pentanediol [3]. Isothermal compressibility of other investigated
substances at the pressure range 0,1 – 300 MPa increases in the row EG < 1,3PD < H2O. We
offer value ∆βT/∆Р as a measure of stability – the more this value, the less network is stable.
Therefore stability of network of H-bonds in examined liquids could be arranged in this order:
EG > 1,3PD > H2O > 1,4BD.
References
1. V.N. Belonenko, V.M. Troitsky, Yu.E. Belyaev, V.G. Nikolashev. RF Patent № 2216007
(2001).
2. M. N. Rodnikova, Zh. Fiz. Khim. 67, 275 (1993).
3. Yu.Ya. Kharitonov, E.G. Hoshabova, M.N. Rodnikova, Izvestiya Akademii Nauk SSSR,
Chemical Series. 6, 1323 (1990)
CONSTRUCTION OF THE QUATERNARY Fe-Cu-Co-S SYSTEM AND SUBSYSTEMS

Starykh R.V., Sineva S.I., Ilatovskaya M.O.
Saint-Petersburg State Polytechnical University, Saint-Petersburg
e-mail: aessone64@mail.ru
Planning and optimization of pyrometallurgical processes are based on the knowledge of
the phase transformations, occurring when changing the temperature and composition of
technological products and intermediates. In particular, studying and constructing of the phase
equilibriums diagram quaternary Fe-Cu-Co-S system are caused by its high practical
importance in copper and cobalt metallurgy. However, there are no reliable published data on
the regularities of melting and crystallization of melts inside capacity of the discussed system.
Differential Thermal Analysis (DTA), Scanning Electronic Microscopy (SEM) and
Electron Probe Microanalysis (EPMA) have been chosen as the main methods for the
investigations, realized with the use of modern and high-precision equipment. DTA-
experiments and obtaining information about the temperatures of the liquidus and solidus the
samples has been realized using Setsys Evolution 1750 (Setaram); SEM and EPMA carried
using Tescan TS 5130MM (Czech) with the system of microanalysis INCA (Oxford
Instruments, UK).
For the correct study of phase transformations in quaternary Fe-Cu-Co-S system
requires reliable data on the phase equilibrium in the ternary boundary systems: Fe-Cu-S, Fe-
Co-S, Fe-Cu-Co and Cu-Co-S. Study area diagram of the Fe-Cu-Co-S system, as well as
ternary systems, has been limited in sulphur content by pseudo-ternary section, the corners of
which are responsible of the homogeneity areas of Fe1-хS, Cu2±хS and Co1±хS sulphides.
Experimental samples for the study of ternary and quaternary systems have been prepared by
alloying high purity metals and their sulphides in the given ratio in the presence of HP-argon
of the induction furnace. The obtained thermoanalytical data allow predicting the parameters
of phase transformations occurring in quaternary Fe-Cu-Co-S system and boundary
subsystems. And mathematical treatment (by third degree polynomials using technique of the
least squares) of the obtained results allows to visualize the phase transformations inside
capacity of the investigated the multicomponent system in the form of various projections
(liquidus and solidus surfaces, polythermal and isothermal sections).
The results of the investigations are the liquidus projections of the Fe-Cu-Co-S system
and its boundary subsystems in a wide range of compositions with identifying of an
arrangement of univariant transformations’ lines, and parameters of invariant transformations.
Also schemes of all multiphase reactions running in investigated system have been presented.
It explains the procedure and regularities of interaction of phases in the quaternary system.
THERMODYNAMIC PROPERTIES OF BOROSILICATE GLASSES AND MELTS

CONTAINING OXIDES OF HEAVY METALS (Cd, Zn, Pb)
Stolyarova V.L., Lopatin S.I., Shilov A.L., Shugurov S.M.
Saint Petersburg State University, Saint Petersburg
e-mail: stvl08@inbox.ru
Materials based on the glass-forming (CdO, ZnO, PbO)-B2O3-SiO2 systems have great
importance in the modern materials science and engineering. Owing to the unique
physicochemical properties of these systems such as low melting temperature, low viscosity,
the ability to absorb the ionizing radiation and to decrease the crystallization susceptibility of
glasses they are widely used as the base of optical glasses, radio protective glasses, crystals,
glazes, enamels and coatings. Because the preparation and usage of the materials mentioned
take place at high temperatures as usual information on the vaporization processes and
thermodynamic properties of these systems are required. These data are particularly important
from the point of view of the problems of the environmental control when vaporizing vapor
species of CdO, ZnO, PbO as the components of heavy metal evaporate to the gaseous phase,
for example, in the processes of the glass preparation or incorporation of nuclear wastes of
high level radioactivity.
In the present work, the study of vaporization processes and thermodynamic studies of
glasses and melts in the (CdO, ZnO, PbO)-B2O3-SiO2 systems was carried out by high
temperature mass spectrometric method. The choice of the sample compositions under study
was based on the relevancy to the frame of the glass-forming regions in these systems.
Individual oxides of the systems considered with the purity “purissimum speciale” and the
content of admixtures about 10-5-10-10 % were used for the sample preparations. Mixtures of
oxides with the required compositions were ground in an agate mortar to fine powders. Then
they were put into the SiO2 or Pt crucibles and heated in the furnace at the temperatures and
during the time required for sample preparation according to corresponding phase diagram.
Studies of the chemical vapor composition, measurements of the partial vapor pressures
and the activities of the components in the samples under consideration were carried out using
an MS-1301 mass spectrometer (developed by the Institute of Analytical Instrumentation of
the Russian Academy of Sciences, St. Petersburg, Russia). Partial pressures of vapor species
and the CdO, ZnO, PbO activities in the samples of the (CdO, ZnO, PbO)-B2O3-SiO2 system
were obtained by the differential mass spectrometric method. Samples were evaporated from
double effusion cells with the ratio of the effusion and evaporation areas of 1:100. The
installation was calibrated using the vapor pressure of gold recommended by IUPAC as the
standard. Experimental study was carried out at the ionization energy equal to 25 eV.
Values of thermodynamic functions found in the ternary melts studied in the temperature
range 1100-1300 K illustrated the negative deviations from the ideality. The generalized lattice
theory of associated solutions was used for modeling of thermodynamic properties in the
(CdO, ZnO, PbO)-B2O3-SiO2 melts and the relative numbers of bonds forming these melts
were calculated.
Financial support for this work from the Russian Fund for Basic Research according to
the project № 10-03-00705а is gratefully acknowledged.
LAWS OF CHANGE THE THERMODYNAMIC PROPERTIES OF THE BINARY

SYSTEM FORMED BY A COMMON SOLVENT AND REPRESENTATIVES
OF HOMOLOGOUS SERIES OF ORGANIC SUBSTANCES
Suntsov J.K.
Voronezh State University of Engineering Technologies, Voronezh
e-mail: jsyntsov@mail.ru
Further development of the thermodynamics of solutions is associated with the
consideration of molecular concepts [1-4]. In this work, an attempt was made to determine the
relation between to the thermodynamic functions of binary solutions and the molecular
weights (structure) of solution components. As object of research binary systems formed by n-
alcohols (a common solvent) and difficult esters of organic acids (the second components),
benzene and n-alkyl benzenes, fluoroarene and haloarenes are chosen. We studied liquid–
vapor phase equilibria and volume properties of binary systems formed by specified
components. Concentration and temperature dependences of the solution properties are
indicative of a complex character of molecular interactions in the solutions, which manifests
itself in deviations of binary systems from ideality. Lewis-Randal calculations do not allow us
to directly relate the thermodynamic function values of solutions to the molecular weight
(structure) of solution components. In order to determine this relation, the thermodynamic
functions of solutions were calculated using the standard state that was the ideal gas with the
temperature T, volume V, and composition of the real liquid [1-4]. It is established, that for
the solutions of constant molar concentrations, the Helmholtz energy (Ar, J/mol) was found to
depend linearly on the molecular weight of second component of solutions. The results
obtained allowed us to suggest the equation:
Ar = ( k1*x + b1)*M+ k2*x + b2 (1)
where x1 is the mole fraction of a common solvent in solution and M is the molecular weight
the second solution component, k1, k2, b1, b2 – factors. Equation (1) describes the Helmholtz
energy of solutions with an accuracy of < 1%. We believe that this law is general in character
and can be used to predict the thermodynamic properties of binary system solutions formed by
a common solvent and representatives of homologous series of organic substances. The
technique allowing with high accuracy to predict of thermodynamic properties of solutions of
binary systems is offered, using properties of two pure components and two solutions constant
molar concentrations. It accelerates process of research of thermodynamic properties of binary
solutions approximately in 340 times.
References
1. E. S. Rudakov, Molecular, Quantum, and Evolutional Thermodynamics (Inst. Fiz.-Org.
Khim. i Uglekhim. im. M. Litvinenko, Donetsk, 1998) [in Russian].
2. J. Suntsov . Legitimacies change of properties of binary systems on an example of solutions
formed by aliphatic alcohol and complex ethers of organic acids. XVIII international
conference “THERMODYNAMICS - 2003”, University of Cambridge (U. K.).
3. Y. K. Suntsov, Zh. Fiz. Khim. 82 (3), 410 (2008) [Russ. J. Phys. Chem. 82 (3), 410 (2008)].
4. Y. K. Suntsov, Zh. Fiz. Khim. 82 (4), 625 (2008) [Russ. J. Phys. Chem. 82 (4), 625 (2008)].
PHASE EQUILIBRIUMS A VAPOUR–LIQUID AND THERMODYNAMIC PROPERTIES

OF SOLUTIONS OF BINARY MIXTURES BUTANOL–ALIPHATIC KETONES
Suntsov J.K., Vlasov M.V.
Voronezh State University of Engineering Technologies, Voronezh
e-mail: fatemax@list.ru
Data about properties of the binary mixtures formed by the general solvent and
substances of homologous series are necessary for an establishment of interrelation of
structure of components with thermodynamic properties of solutions [1]. Existing design
techniques of properties of multicomponent systems based on properties of their binary
components [2].
The solutions of binary mixtures formed by n-butanol (the general component) and
substances of homologous series of aliphatic ketones (5 binary mixtures) are investigated. It is
established, that solutions of these systems possess significant deviations from an ideal state.
Value of energy of Gibbs, was not possible to connect enthalpies and entropies of the solutions
calculated on the basis of data about equilibrium a vapor-liquid with use of the standard of a
regular solution (a method of Lewis) with structure (molecular weight) of the components
forming these solutions. The ideal gas standard (T,V,x=const) [1] has been used For the
account of contributions of intermolecular interactions in change of thermodynamic functions
of solutions. For a case of transferring of a mole of a solution, from a condition without
interaction between molecules, in a condition with interaction (liquid), for change of energy a
Helmholtz (Ar), entropies (Sr), intrinsic energy (Ur) have been calculated values of
corresponding functions for substances of homologous series (xi=1) ketones and binary
mixtures. It is positioned, that values Ar, Ur and Sr substances in homologous series linearly
depend on molecular weight of an alkilketon (number of groups CH2 in a molecule). The
equation of kind Ar = kiM2 + bi is offered. By Correlation analysis it is established, that values
of factors ki and bi for isosteres Ar = kiM2 + bi solutions in turn linearly depend on
composition of systems. The established laws have allowed to offer the kind equation:
Ar = (k1∙x1+b1) ∙М2+k2∙x1+b2, (1)
where Ar - energy a Helmholtz, the J/mol; x1 - a molecular ratio of the general solvent; M2-
molar weight of substance of homologous series. The equation (1) the Helmholtz (Ar)
solutions of systems with accuracy 50 J/mol describes energy. The positioned law will be
agreed with a hypothesis, about the additive contribution of chemical groups to properties of
the solutions, the underlying theory of "group models” [2]. The equation (1) the energy of
Helmholtz (Ar) of solutions of systems with accuracy 50 J/mol describes. The established law
will be agreed with a hypothesis, about the additive contribution of chemical groups to
properties of the solutions, the underlying theory of "group models” [2].
The established law allows to predict thermodynamic properties of solutions of not
investigated binary mixtures. Accuracy of the forecast depends only on accuracy of
experimental data.
References
1. Rudakov E.S. Molekulyarnaya, kvantovaya i evolyucionnaya termodinamika /
E.S.Rudakov. - Nac. akad. nauk Ukrainy. In-t fiz. organ. himii i uglehimii im. L.M.
Litvinenko, M-vo obrazovaniya Ukrainy, Doneck, 1998. – 139 p. (In Russian).
2. Morachevskii A.G. et al. Termodinamika ravnovesiya jidkost' - par. – L.: Himiya, 1989. –
342 p. (In Russian).
INVESTIGATION OF THE FACTORS AFFECTING THE STABILITY CONSTANT

VALUES OF TRANSITION METALS COMPLEXES DETERMINED
BY CAPILLARY ELECTROPHORESIS TECHNIQUE
Sursyakova V.V.1, Popova O.V.1, Burmakina G.V.1,2, Rubaylo A.I.1,2
1
Institute of Chemistry and Chemical Technology SB RAS, Krasnoyarsk, Russia
2
Siberian Federal University, Krasnoyarsk, Russia
e-mail: viktoria_vs@list.ru
Evaluation of the stability constants of transition metals complexes with organic
compounds is an actual problem for differrent fields of chemistry, medicine, ecology and
industry. Сonventional methods for their determination are electrochemical,
spectrophotometric and spectroscopic methods. Recently, capillary electrophoresis technique
(CE) is widely used [1, 2]. This technique is rather novel and in this connection the aim of
present study is to investigate the factors affecting the stability constant values of transition
metals complexes determined by capillary electrophoresis technique:
- transition metal concentration-to-ligand concentration ratio,
- mode of ionic strength accounting,
- interactions between studying cations and spicies of background electrolyte (BGE),
- conditions of electrophoretic measurements,
- changes of BGE temperature owing to the presence of electrical potential gradient and
electrical current,
- matrix effects that is phenomenon of the correlation between measured ion
electrophoretic mobility and ratio of studying ions concentration to BGE ions
concentration,
- changing velocity of electroosmotic flow (EOF) during a run,
- equations for stability constants calculation.
Investigation of this factors was made by experimentally using as example the
complexes of iron (III) with sulfosalicylic acid and theoretically using dynamic mathematical
simulator of the CE [3]. The study was carried out using capillary electrophoresis system with
a diode-array detector Agilent 3DCE G1600A (Agilent Technologies, Waldbronn, Germany) of
the Center for Collective Use of the Siberian Branch of the Russian Academy of Sciences.
The findings allow to select the optimal conditions for determination of thermodynamic
stability constants of transition metals complexes by capillary electrophoresis technique and to
avoid the mistakes that were in a number of papers in russian and foreign journals in which
the authors used CE without careful observation of the CE theory and boundary conditions of
derived equations.
References
1. Timerbaev A.R., Foteeva L.S., Rudnev A.V., Abramski J.K., Połec-Pawlak K., Hartinger
C.G., Jarosz M., Keppler B.K. // Electrophoresis. 2007. V. 28. P. 2235–2240.
2. Ehala S., Kašička V., Marlik E. // Electrophoresis. 2008. V. 29. Р. 652-657.
3. Sursyakova V.V., Kalyakin S.N., Burmakina G.V., Rubaylo A.I. // Electrophoresis. 2011.
Vol. 32. Р. 210-217.
THERMAL DECOMPOSITION OF VANADYL ACETYLACETONATE

Tatevosyan S.S.1, Dementiev P.D.1, Berezina O.Y.2, Kirienko D.A.2, Zlomanov V.P.1
1
e-mail: stepan.voski@mail.ru
2
Petrozavodsk State University, Petrozavodsk
The VO2 films are used as reversible optical media for recording, storing and displaying
optical information elements of laser technology, visualization and detection of IR and
microwave radiation. For the preparation of VO2 thin films can be used vanadyl
acetylacetonate, which decomposes to VO2 when heated. Compared to (EtO)3VO, which also
is a possible precursor for producing VO2 films, vanadyl acetylacetonate are less toxic, less
afected by hydrolysis in solution and easily synthesized.
The final stage of the VO2 film synthesis from vanadyl acetylacetonate is its thermal
decomposition. As a consequence, the study of pyrolysis processes of vanadyl acetylacetonate
has the great scientific and practical interest.
In this work the pyrolysis of films and powders of VO(acac)2 are studied by IR-
spectroscopy, X-ray diffraction (XRD), thermogravimetry (TGA), mass spectrometry.
VO(acac)2 was obtained from vanadyl sulfate and freshly distilled acetylacetone [1].
VO2 films were synthesized from the VO(acac)2 solution in methanol by centrifugation,
followed by drying with an IR-lamp at 150°C and high temperature annealing.
From the data of TGA, XRD, IR-spectroscopy and mass spectrometry it can be assumed
that the thermal decomposition of VO(acac)2 can include next steps:
a) Sublimation and melting of VO(acac)2
b) Separation and decomposition of chelate rings
c) Creation of [VO6] octahedra - the centres of crystallization of vanadium oxide
d) Crystallization VO2, that is ordering [VO6] octahedra to form long-range order
IR-spectroscopy of films showed that at 150°C the processes of VO(acac)2
decomposition start:
lines of the C-C, C-O and C-H bonds are not observed and the vibrations which are
responsible to V-O bonds are appeared.
The final composition and structure of the films is depend on the temperature of
annealing and the used atmosphere. Annealing of the VO2 films below 600oC leads to an
amorphous structure, and above this temperature, they are crystallized. The increase of
temperature leads to the decomposition of VO2 and reduction to lower vanadium oxides.
Pyrolysis in a dry nitrogen atmosphere also leads to the reduction of vanadium, which is
associated with the a reducing atmosphere (CO, H2) of the decomposition of VO(acac)2.
Reduction can be avoided by the current of moist nitrogen over the films.
Reference
1. Inorganic Synthesis / Moeller T. – McGraw-Hill book company, inc, 1957. V. 5. P. 113–115.
SPECIFIC FEATURES OF DIMERISATION EQUILIBRIUM IN HARD SPHERE FLUID

Tkachev N.K., Zinatulina A.R.
Institute of High-Temperature Electrochemistry, Ural Branch of RAS, Ekaterinburg
e-mail: N.Tkachev@ihte.uran.ru
One of the fundamental problems of modern physical chemistry is the study of chemical
equilibrium in non-ideal systems. In this case, the equation of the mass action law (MAL) should
be written in the most general form, i.e., using the activities of participants of reaction.
Calculation of the activity coefficients and, thus, the position of chemical equilibrium is the
challenging problem of statistical thermodynamics, which is closely related to a variety of
interactions possible in given system.
Undoubted progress of the statistical theory of liquids and gases in recent decades has
created the base for the analysis of chemical equilibrium for a given type of interparticle
interaction for the cases of simple model pair potentials.
The problem of describing association equilibrium using the statistical theory of liquids
based on the integral equations for pair distribution function began to be developed recently.
Dimerization in the hard-sphere systems has been studied theoretically in [1, 2]. In works of
Cummings and Stell and the others the deviations from the ideal MAL and the dependence of the
dimerization constant on the density of the system were described.
In our opinion, the problem of the dissociation equilibrium in the hard-sphere fluid can be
formulated in a simpler way, if one keep in mind minimum of the free energy of hard-sphere
mixture of single atoms and dimers (with their own size). In this case the attention is attributed to
the dissociation energy of dimer and their bond length. In the present study, as well as in referred
works on this problem, we can consider these values as parameters of the model. The ideal part of
the free energy can be written as usual in the statistical theory of polyatomic gases, and the effect
of excluded volume forces can be taken into account, even with the help of a semi-
phenomenological approximation of the van der Waals type or, for example, the Percus-Yevick
approximation. It is important that the equilibrium concentration of dimers should be found by
minimizing the free energy.
We shall present a statistical-thermodynamic analysis of the equilibrium reaction
dimerization in hard-shere systems within several approximation. Clear formula was found for the
mean activity coefficient in the case of the model of van der Waals type, which describes both
positive and negative deviations from the ideality, depending on the volume change as a result of
the elementary chemical reactions. The Percus-Yevick approximation predicts similar results with
more severe deviations from ideal behavior. It is noteworthy that the calculation of chemical
equilibrium in this case leads to a system of coupled nonlinear equations, namely the MAL
equation and the equation of state. Generalization of the theory on non-spherical dimer shape will
be described and discuss as well.
At high pressures or weak chemical bonds in the dimer theory predicts unusual tempera-
ture dependence of the concentration of dimers which is characterizing by “anomalous”
dissociation in the low temperature region. Dependencies of the entropy and specific heat
capacity of the dimerising hard-sphere and hard-body fluid on temperature will be discussed
Thus the purpose of this report is to present the analysis of dimerisation equilibrium in
hard-sphere systems using simple models of statistical thermodynamics.
This work was supported by Russian Foundation for Basic Researches (RFBR N 12-03-
00346) and UB RAS (12-U-3-1011).
References
1. P.T. Cummings and G.Stell, Molec. Phys. 1987, 60, 1315.
2. M. S. Wertheim, J. Stat. Phys. 1986, 42, 477.
THERMODYNAMIC MODELING OF PHASE EQUILINBRIA IN HETEROGENEOUS

FLUID SYSTEMS WITH CHEMICAL REACTION IN THE LIQUID PHASES
Tsvetov N.S., Toikka A.M.
Department of Chemical Thermodynamics and Kinetics,

Faculty of Chemistry, St. Petersburg State University
e-mail: tsvet.nik@mail.ru
The study of thermodynamic properties of reactive systems and reaction-mass transfer
processes requires particular research and construction of phase diagram, using both
experimental and predictive methods. The state diagrams of systems with simultaneous
chemical and phase equilibria are of special interest. Many studies had been focused on the
obtaining of VLE data in reactive systems. More complex phase behavior is considered rarely,
e.g. example liquid-liquid-vapor equilibrium (VLLE). Chemical equilibrium (CE) studying of
complex phase behavior systems is of significant importance for the development of basic
thermodynamic theory.
Presented work is devoted to the study of phase equilibria in the n-propanol + acetic
acid + n-propyl acetate + water system in which esterification/hydrolysis reaction occurs. At
isothermal-isobaric conditions the composition corresponding to the chemical equilibrium
states should be presented as a chemical equilibrium surface in the composition simplex. For
every liquid composition the composition of vapor phase may be also calculated. The
dimerization of acetic acid in the vapor should be taken in the account. Accordingly the results
of calculation should be corrected.
VLE calculations were carried out at 293.15, 303.15 and 313.15 К. According to
previous studies, there are LLE surface and chemical equilibrium surface crossing in
composition tetrahedron of the n-propanol + acetic acid + n-propyl acetate + water system at
293.15 and 303.15 К. It means that heterogeneous chemical equilibrium composition occurs
in this case. Thus one should consider simultaneous VLLE and chemical equilibrium.
For activity coefficients calculations that are used for VLE and VLLE computation
UNIFAC based information system was applied. In previous works UNIFAC model was
successfully used for LLE and CE modeling in this and similar systems.
In this way phase diagrams of simultaneous chemical and phase equilibria in the n-
propanol + acetic acid + n-propyl acetate + water system at 293.15, 303.15 and 313.15 К were
obtained.
In this work the problems of the change of the states in the run of the reaction have been
considered. Particular interest is the case of reacting system passing through critical region of
LLE during the reaction. Experimental kinetic research of this reaction behavior in the LLE
critical region was performed.
This study was supported by Russian Foundation for Basic Research (grant RFBR 12-
03-00522а).
DIAGRAMS ELECTROCHEMICAL EQUILIBRIA STEEL ST.3

AND COOPER SULFATE WATER SOLUTIONS
Tyurin A.G., Biryukov A.I.
e-mail: tag@csu.ru
In this paper more precise diagram potential – pH of H2SO4 – H2O, diagrams are
constructed electrochemical equilibrium steel St.3 and copper in acidic sulfate solutions at
25ºC. Steel found in phases: ferrite (α – phase Fe), cementite (Fe, Mn)3C. In the analysis of its
corrosion-electrochemical behavior should be considered as separate phases as non-metallic
inclusions MnS sulfide and oxide SiO2. Thus, the general diagram of the electrochemical
equilibrium steel St.3 includes both components of the equilibrium diagram of the potential –
pH ferrite, cementite inclusions of manganese sulphide and silica.
St.3 of steel corrosion potentials and copper in sulfuric acid solutions occur in the region
of stability of sulfuric acid in the chart potential – pH of H2SO4 – H2O. Therefore, along with
the hydrogen electrode, the electrochemical dissolution of these metals in strongly sulfate
solutions must take into account the competing cathodic reaction:
HSO4- + 9H+ + 8e = H2S + 4H2O; E°298 = 0,289 V.
Based on the diagram of the electrochemical equilibrium became St.3 in acidic sulfate
solutions showed that in these conditions the steel can be spontaneously sulfide passivation
(two-phase mixture piretita (FeS1 + x) and marcasite (FeS2)), instead of sulfate and / or oxide
passivation.
According to the literature on the behavior of copper in sulfuric acid solutions is
assumed that the passivation of copper occurs at the expense the formation of the metal
surface layers Cu2O, CuO or CuSO4 • 5H2O. Potentials of copper corrosion in these
conditions occur in the region of stability of copper sulfides in the diagram potential – pH of
Cu – H2SO4 – H2O. In this case, according to the state diagram of Cu – S, can form
passivation film consisting of a maximum of five sulfide: Cu / Cu2S / Cu9S5 / Cu9S6 / Cu7S6 /
CuS. Thus, in sulfuric acid solutions on copper sulfide formed, not oxide-sulfate passivating
film.
THERMODYNAMICAL ANALISYS OF TRANSFER CHARGE PROCESS

OF LiAsF6 IN METHYL ACETATE
Tyunina E. Yu1., ChekunovaM. D 2
1
G. A. Krestov Institute of Solution Chemistry, Russian Academy of Science, Ivanovo
2
Ivanovo State University of Civil Engineering and Architecture, Ivanovo
e-mail: marchekunova@mail.ru
Purposeful search for electrolyte compositions for lithium and lithium-ion sources of
electric energy must be conducted on the basis of information of charge and mass transport in
organic liquid electrolytes and polimer electrolytes. Key for development and optimization of
lithium batteries is the investigation of conductivities of noaqueous electrolytes in wide
temperature range. This work is a logical continuation of cycle of investigatons that were
connected with the revelation of the effect the nature of the solvent on transport properties of
lithium hexafluoroarsenate solutions in aprotic solvents. The specific conductivity of solutions
of LiAsF6 in methyl acetate was determined at 253.15K, 263.15K, 273.15K, 283.15K,
293.15K, 303.15K, 313.23 and 323.15K in concentration range 0.11-2.26 mol/kg.
The concentration dependence of conductivity of solutions was described by Castell-
Amis equation. The temperature dependence was described by the Arrehenius expression. The
activation energy values for conductivity vary from 3.6 to 10 kJ⋅mol-1 for investigated system.
The values of conductivity of investigated system were compared with values of conductivity
for solutions of LiAsF6 in propylene carbonate (ε=64.95) (PC), γ-butyrolactone (ε=39.1) (γ-
BL), tetrahydrofuran (ε=7.4) (THF). The analysis shows, that for LiAsF6 solutions in
investigated solvents the values of activation energy for conductivity increase in the order
LiAsF6-THF < LiAsF6-MA < LiAsF6-γ-BL < LiAsF6-PC. The given systems can dispose in
row according to increasing of conductivity LiAsF6-PC < LiAsF6-γ-BL < LiAsF6-THF <
LiAsF6-MA. For LiAsF6 solutions in PC and γ-BL the ion-migration mechanism of charge
transfer is realized [1], and the low values of activation energy conform to higher magnitudes
of conductivity. The basic determining factor of ion movement is medium viscosity. For
LiAsF6 solutions in low permittivity solvents, it is not entirely correctly to consider the ion
movement as movement of balls in viscous medium. It should be noted, that the values of
activation energy for conductivity of LiAsF6 solutions in low permittivity solvents
approximately 3 times smaller than these magnitudes for LiAsF6 solutions in PC and γ-BL. It
can points out on realization of ionotropic mechanism.
Most likely, in LiAsF6 solutions with low permittivity solvents the general conductivity
of solutions is assembled of ionotropic (in concentrated region) and ion migration (in dilute
solutions) mechanisms of charge transport. In work [2] it was shown, that the infrared spectra
of LiAsF6 solutions in methyl acetate over concentration range 0.1- 0.5 mol dm-3 suggest the
existence of contact ion pair, solvent separated ion pair, and possibly dimers and microwave
complex permittivities for LiAsF6 solutions over this same concentration range confirm the
existence of both contact and solvent separated ion pairs and indirectly confirm the existence
of contact dimmers. When increasing of ionophorc concentration the mesh of these ion pairs
or dimers is formed. The adding of electrolyte stimulates the transfer of charge on ionotropic
mechanism. The rate-determining reaction probably is the reorientation of the dipole of an
ionic pair in a proper manner.
References
1. Tyunina E. Yu., Afanasiev V. N., Chekunova M. D. // J. Chem. Eng. Data. 2011. V. 56(7). P.
3222-3226.
2. Salomon M., Uchiyama M., Xu M., Petrucci S. // J. Phys. Chem. 1989. V. 93, P.4374-4382.
SELENIUM CONTAINING POLYMERIC NANO-STRUCTURES SELF-ORGANIZING

Valueva S.V., Vylegzhanina M.E., Kutin A.A., Sukhanova T.E.
Institute of Macromolecular Compounds, Russian Academy of Sciences, Saint-Petersburg
e-mail: svalu67@mail.ru
One of the most promising methods for obtaining of the aggregately stable nanoparticles
of non-metals is presented by recovery of their ionic forms of polymer solutions. This paper
presents the results of studying by methods of molecular optics (MO) (static/dynamic light
scattering and streaming birefringence) and microscopy (AFM and TEM) of selenium
containing nano-structures stabilized by water-soluble polymers such as polymethacrylic acid
(PMA), polyvinyl pyrrolidone (PVP) and polyelectrolyte complexes (PEC) of sodium dodecyl
sulfate (SDS) with cationic copolymer (CC) of N-vinylpyrrolidone and N,N,N,N – thriethyl
methacryloyloxyethyl ammonium of the iodide of variable composition γ
(γ=SDS/CC=0.5÷4.0).
It was found that during a process of Se0 nano-particles self-organizing in water
solutions of PMA, PVP and PEC at mass ratio selenium/polymer (ν=0.025÷0.2) the highly-
ordered spherical nanostructures characterized by high molecular mass Мw = (24-200)×106
and density Ф*=0.02÷0.17 g/cm3 were forming. In such a case a complex of macromolecule –
nanoparticle obtained under conditions of complete saturation of adsorption capacity (ν=0.1)
is near the border of its thermodynamic stability. It was also found that average density Ф* of
PMA-Se0 (Ф*=0.02÷0.08 g/cm3) depends strongly on Se0 concentration in the solution and
increases with increase of ν, in such a case deterioration of thermodynamic state is observed.
It has been shown that increase of γ parameter within the range 0.5÷4.0 (at ν = 0.1) results in
significant changes of morphology of the nanostructures stabilized by PEC, their sizes and the
second virtual coefficient А2*. Since the value of А2* for the nanostructure PEC- Se0 with γ =
0.5 makes up А2*= 0.2×10-4 cm2mole/g2, characterizing this solution state as close to the ideal
one and the value of А2* for a nanostructure with γ =4.0 is negative (А2*= -0.8×10-4
cm2mole/g2) that testifies a bad thermodynamic quality of the solution. When increasing γ the
molecular mass of the PEC- Se0 nanostructures formed in water is increased by 20 times, their
density is increased by 6 times and the mean-square radius of gyration is increased by 1.5
times (from 40 nm to 60 nm). It was found that separate spherical dense nanostructures with
an average radius ~ 60 nm (γ = 4.0), but in case when γ = 0.5 except the spherical
nanostructures of 30-90 nm size, it is possible to observe associates characterized by the
average size ~150 nm. For PVP-Se0 nanostructure it was found that in the area where ν ≥0.1
separate dense nanostructures with an average radius ~50 nm dominate, in such a case А2*=
0.2×10-4 cm2mole/g2. In area where ν≤0,05 it was possible to observe isolated spherical dense
nanostructures with the average radiuses of 5–25 nm as well as associates characterized by the
sizes ~200 nm, in such a case А2*= -1.52×10-4 cm2mole/g2 that testifies poor thermodynamic
property of the solution.
Hence, Se0 nanoparticles represent active adsorptive surfaces where high local
concentrations of polymer can be reached, in such a case high molecular close-packed
nanostructures having a form close to spherical one can be formed.
THERMODYNAMICS OF HYDROGEN BONDING IN ORGANIC COMPOUNDS:

FROM COMPLEXES 1:1 TO MULTI-PARTICLE SUPRAMOLECULAR CLUSTERS
Varfolomeev M.A., Solomonov B.N.
e-mail: vma.ksu@gmail.com
Physical-chemical properties and reactivity of organic compounds significantly depend
on hydrogen bond formation. H-bonds influence on mechanism, rate and equilibrium of
chemical reactions, cause conformational stability of supramolecular structures.
Determination and analysis of thermodynamic functions of hydrogen bond formation is one of
the main tasks in hydrogen bonding studies. In present work new approach was suggested to
solve this task. It’s based on the joint application of thermochemical, spectroscopic and
quantum-chemical methods.
All systems with solute-solvent hydrogen bonds can be divided into four basic groups:
1) there is no intramolecular hydrogen bonds in solute molecules, solvent isn’t associated by
intermolecular hydrogen bonds; 2) ) there is no intramolecular hydrogen bonds in solute
molecules, solvent is associated by intermolecular hydrogen bonds; 3) there is intramolecular
hydrogen bonds in solute molecules, solvent isn’t associated by intermolecular hydrogen
bonds; 4) there is intramolecular hydrogen bonds in solute molecules, solvent is associated by
intermolecular hydrogen bonds. In the first of these groups, we are only dealing with the
formation of complexes of a certain composition, basically 1:1. It should be noted that in the
literature a large number of methods for estimation of H-bond energy in such systems exist. A
lot of data on thermodynamic functions of hydrogen bonds in complexes 1:1 were obtained
using these methods. In the other groups, not only formation of hydrogen bonds, but also their
breaking takes place caused by competition for binding sites. In 3 and 4 groups multi-particle
supramolecular complexes are often formed in the solution. In such complexes effect of
hydrogen bonds cooperativity plays important role. The energies of formation of such
complexes are practically unknown. In this paper, we propose new approaches to the
determination and analysis of the thermodynamic functions of the hydrogen bonds in all of
these types of systems in a variety of organic compounds and their mixtures, including some
of the ionic liquids.
Different systems with intramolecular and intermolecular hydrogen bonds were studied.
Comparison of thermodynamic and spectroscopic parameters of hydrogen bonds of organic
molecules with various functional groups was carried out. Strength of hydrogen bonds in
complexes containing different quantity of molecules was studied. Special attention was paid
on the determination of hydrogen bond cooperativity factors in multi-particle supramolecular
structures formed by organic non-electrolytes. In present work new relationships between
structure of studied molecules and thermodynamic functions of hydrogen bonds were found.
Influence of hydrogen bonds on the thermodynamics of practically important reactions was
studied.
NEW THERMODYNAMIC DATA OF THE In-Pb-Sn-Zn SYSTEM

Vassiliev V.P., Lysenko V.A., Sevastyanova L.G., Panyushkin V.V., Buslov I.V.
Lomonosov Moscow State University, Chemistry Department, Moscow
e-mail: valeryvassiliev@yahoo.fr
The purpose of this work is systematic study of thermodynamic properties and
miscibility gap in liquid quaternary In-Pb-Sn-Zn system and theirs subsystems by means of
EMF method and thermodynamic modeling of these systems [1-3]. This information is
necessary for separation and affinage of Pb-Zn melts in metallurgical processes, in which the
most common admixtures are Cu, In, Sn. These admixtures can change significantly the wide
miscibility gap of the Pb-Zn system [4] (Fig.1), which is due to the large difference in the
densities of components and weak chemical interaction between zinc and lead. The
electrochemical cell: (-) Zn ZnCl2 + KCl + LiCl In-Pb-Zn (+) was used for determination of
thermodynamic properties in the range of temperatures 660-830 K. Temperature calibration is
performed by zinc melting point in the cell (692.65K).
We measured the EMF vs. temperature for the series of quaternary alloys of different
compositions. The Fig.2 presents the obtained results for selected 5 alloys. The points E(T) at
the right of Fig.2 belong to the homogeneous liquid (liq), the points with the less inclination
and occupying the central part belong to heterogeneous one (liq1+liq2), and values E(T) at the
left part of Fig.2 (below Tm(Zn)) belong to the heterogeneous liq3+solid area. The points of
intersection of homogeneous (liq) and heterogeneous (liq1+liq2) areas give the points on
surface of immiscibility.
(project No. 11-08-01154).
References
[1] V.Vassiliev , Y.Feutelais , M.Sghaier , B.Legendre. Thermochim. Acta, 315 (1998) 129-
134.
[2] David N., Vassiliev V., Hertz J. at al. Z. Metallknd. 95B (2004) 1-8.
[3] V.P. Vassiliev, V.A. Lysenko, Weiping Gong. J. Alloys and Comp. (in press).
[4] N. David, J. Hertz, J.M. Fiorani. Z. Metallkd. 94 (2003) 8-11.
Fig. 1. Calculated Pb-Zn phase diagram [4]. Fig. 2. Experimental values E(T)
of the In-Pb-Sn-Zn system.
THERMODYNAMIC PROPERTIES AND DENSITY

OF IMIDAZOLIUM-BASED IONIC NANOFLUIDS
Paulechka Y.U., Blokhin A.V., Kabo G.J., Shevelyova M.P., Kabo A.G.,Levitskaya T.N.
Belarusian State University, Chemistry Faculty, Minsk, Belarus
e-mail: paulechka@bsu.by
Stable dispersions of nanomaterials in room-temperature ionic liquids (ILs) are called
ionic nanofluids (INF). In this work we present the results of thermodynamic investigation for
INF containing carbon nanotubes. Due to unique combination of thermal and electrical
properties of the components these materials have a number of potential applications as heat-
carrier fluids, pigments for solar batteries, electrolytes in batteries and supercapacitors.
The stacked-cup multi-walled carbon nanotubes (MWCNT) were dispersed in 1-butyl-3-
methylimidazolium tetrafluoroborate [C4mim]BF4 and hexafluorophosphate [C4mim]PF6 ILs
to obtain the desired INF by thorough grinding. Heat capacity and parameters of phase
transitions were determined in an adiabatic calorimeter both for INF and the individual
components. The specific heat capacity of INF in the liquid, crystalline and glassy states was
found to be an additive quantity of specific heat capacities of the components. The triple-point
and glass-transition temperatures of INF agreed well with the corresponding values for pure
IL. It was confirmed that the presence of CNT favored crystallization of ILs.
The enthalpy of formation of [C4mim]BF4-containing INF was found in an isoperibol
calorimeter to be equal to zero within the experimental uncertainty. This result indicates that
the energy of interactions between CNT and ILs is comparable in its magnitude to the sum of
surface excess enthalpies of ILs and nanotubes in vacuum. The additivity in the themal
properties together with the enthalpy of formation allows one to predict thermodynamic
properties of similar INF from the data on individual components.
The apparent volume of INF linearly depends on mass fraction of MWCNT over the
studied mass fraction range thus proving that the specific wetting surface area of CNT remains
constant in all the systems. If MWCNT were suspended in various liquids and the systems
were degassed, their apparent density was found to be close to the density of hexagonal
graphite. At the same time, the apparent density of MWCNT in INF prepared according to the
conventional procedure was lower than that of graphite. This difference was caused by high
viscosity of INF whose degassing did not occur even when the samples were exposed to
vacuum. Based on the obtained data, we estimated the average structural parameters of
MWCNT such as the internal diameter, the wall thickness, and the number of carbon layers in
a nanotube.
CONCENTRATION DEPENDENCE OF FRACTIONS OF FREE AND INVOLVED

IN COMPLEXES MOLECULES OF HF–(CH3)2CO AND HF–(C2H5)2CO SOLUTIONS
Yukhnevich G.V., Tarakanova E.G.
N.S. Kurnakov Institute of General and Inorganic Chemistry,
e-mail: gvyukhn@igic.ras.ru
The stable H-bonded heteroassociates (HA), which are present in binary liquid systems
(BLS) HF–Solv (Solv is an organic solvent), determine, to a great extent, the reactivity and
thermodynamic and spectral properties of these systems. Usually three different types of HA
containing from 1 to ~10–12 HF molecules per Solv molecule can be formed in HF–Solv
solution. Each type of these molecular complexes exists in a wide concentration range.
The aim of this study was to determine the relationship between free and involved in the
composition of various HA molecules of the HF–(CH3)2CO and HF–(C2H5)2CO solutions in the
whole range of the HF concentrations. Tree types of HA with the stoicheometric ratios of the
molecules equal to 1:1, 4:1, and ~12:1 are formed in each of these BLS.
The experimental and computational methods for obtaining the required fractions of free
and involved in different complexes molecules of solution were proposed and applied for the first
time. The first method is appropriate under the condition that the IR spectrum of the solvent
molecule contains a band, whose frequency and integral intensity (A) can be measured as the
molecule passes from the free state to the composition of all HA formed in the BLS. The second
method is based on the consideration of the balance between free and involved in various HA
molecules of the solvent and HF. This method requires the knowledge of molar ratios of the
components of the BLS at which each HA appears in the solution.
The absorption spectra i) of acetone and eight HF–(CH3)2CO solutions, whose molar ratios
of components were varied from 1:20 to 8.9:1; ii) of diethylcetone and ten solutions HF–
(C2H5)2CO, whose ratios of components were varied from 1:12 to 12:1, where taken as the initial
ones. For the estimation of the fractions of Solv molecules existing in different states, at first, the
experimental values of the integral intensities of the carbonyl group bands (ACO) were obtained
(the envelopes of the νCO bands of free and involved in HA Solv molecules were decomposed into
Lorentzian functions). Then, in order to attribute the integral intensity of the Lorentzian
corresponding to each HA to the fraction of Solv molecules in its composition, the data on the
change in ACO depending on the environment were obtained by the density functional calculation
(B3LYP/6-31++G(d,p)). Based on the obtained results, we plotted the experimental dependences
of the fractions of Solv molecules existing in each of four possible states on the logarithm of the
molar ratio of components of the BLS.
Similar data were obtained by the calculation of the balance between free and involved in
various HA Solv and HF molecules. At all studied molar ratios of the BLS components, except for
the highest one, the estimates of the fractions of free and bound in different complexes Solv
molecules performed by two methods are well consistent. The agreement of experimental and
calculated results indicates the reliability of these data and the possibility to perform exact
estimations by the experimental method up to molar fraction of HF ∼0.85.
Based on the calculated data, we also plotted the dependences of the molar fractions of Solv
and HF molecules and the fractions of solution molecules involved in each of three HA on the
molar fraction of HF. It is shown that in both studied BLS the main part of the molecules exists in
the HA composition, starting with the HF molar fraction ~0.3, whereas 90%–100% molecules are
associated at an HF content of ~0.5–0.9 molar fraction. The obtained concentration dependences
can be used for the determination of the corresponding equilibrium constants and the
thermodynamic parameters of the formation of various HA.
THERMODYNAMICS OF CONGRUENT AND INCONGRUENT PHASES

AND PHASE PROCESSES
Zlomanov V. P. 1, Zavrazhnov A.Ju. 2
1
e-mail: zlomanov@inorg.chem.msu.ru
2
Department of Chemistry, Voronezh State University, Voronezh
Thermodynamics of congruent and incongruent phases and phase processes is
discussed using P-T-x diagrams of two-component systems. The concept of congruence is of
great significance in the synthesis of nonstoichiometric solids because, in the case of
noncoincidence between the growth medium (vapor, melt) and solid compositions, there are
fluxes of rejected material and the corresponding kinetic instability of the crystallization front.
A phase can be congruent and incongruent in different temperature intervals. A phase
obtainable from the phases that are in equilibrium with it by combining them in appropriate
proportions is called a congruent phase. A phase that cannot be obtained from the coexisting
phases is called incongruent. The concepts of congruent and incongruent phases should not be
confused with the concepts of congruent and incongruent phase processes. Phase processes
are changes in the state of the system such that the masses of some phases increase owing to
the decrease in the masses of others without changes in the intensive parameters (temperature,
pressure, phase compositions). A phase process in which one phase forms or disappears is
called congruent. A phase transition in which more than one phase forms or disappears is
called incongruent. Depending on the temperature and pressure the same phase SAB can be
involved both in congruent and in incongruent phase processes. Compositions of the phases
involved in the congruent phase process are different and are represented by the solidus,
liquidus, and vapor lines in the Т–х projection. The melt and solid phase compositions
coincide only at the congruent melting point. At the temperatures corresponding to the eutectic
nonvariant points the SAB phase is involved in the incongruent phase processes:
V + SA = L + SABand SAB + L = V + SB.
After that the usage of the terms congruently and incongruently melting compound are
considered.. Sometimes, a congruently melting compound is understood as a compound
melting without dissociation or decomposition. However, a solid melt phase transition is
accompanied by the breaking and relaxation of chemical bonds in the solid and by long range
disordering. Therefore, the term melting without decomposition is not quite correct. The
overall compositions of the phases coincide only at the congruent melting point which is
below the highest melting point: Tk m AB , < T maxm AB . An incongruently melting compound is
sometimes understood as a solid compound that decomposes into a solid phase and a liquid
upon melting. The compositions of the resulting phases differ from the composition of the
parent phase. However, in some temperature range the “incongruently melting compound” can
be involved in the congruent melting process: SAB = L + V. An essential feature differentiating
congruently and incongruently melting compounds is that the highest melting point of a
congruently melting compound is higher than the temperatures of the nearest nonvariant
points. The highest melting point of an incongruently melting compound is intermediate
between the temperatures of the nearest nonvariant points of the system.
ТЕРМОДИНАМИЧЕСКИЕ ХАРАКТЕРИСТИКИ ОБРАЗОВАНИЯ КОМПЛЕКСА

Cu(II) С L-ФЕНИЛАЛАНИНОМ В РАСТВОРИТЕЛЯХ H2O-EtOH
Буров Д.М.1, Леденков С.Ф.1, Вандышев В.Н.2
1
Ивановский государственный химико-технологический университет, Иваново
e-mail: wildbat333@gmail.com
2
Институт химии растворов им. Г.А. Крестова Российской академии наук, Иваново
Фенилаланин способствует формированию и стабилизации пространственной
трехмерной структуры белков, что необходимо для их корректной работы в организме.
Он может также превращаться в тирозин, который является прекурсором
нейромедиатров: дофамина и эпинефрина.
Нами было изучено влияние состава водно-этанольных растворителей и фактора
сольватации на кислотно-основные и комплексообразующие свойства L-фенилаланина.
С помощью метода потенциометрического титрования были найдены константы
диссоциации L-фенилаланина и константы устойчивости его комплексов с ионами Cu2+.
Устойчивость комплекса [CuPhe]+ растет с увеличением мольной доли спирта в смеси
вода-этанол в соответствии с уравнением lgK= lgKH2O + b⋅XEtOH . Это уравнение
применимо также к другим аминокислотным комплексам меди (глицинатным,
аланинатным, тирозинатным), константы устойчивости которых в водном растворе
различаются на несколько порядков. При этом значение коэффициента b остается
практически неизменным, что может быть объяснено взаимодействием одних и тех же
функциональных групп различных лигандов с центральным ионом.
Полученные данные позволили рассчитать энергии Гиббса переноса из воды в
бинарные растворители (XEtOH =0÷0,7мол. д.) ионов Phe-, [CuPhe]+, а также L-
фенилаланина. Увеличение ΔtrG°(Phe-) указывает на ослабление сольватации лиганда в
этанольных растворах. Сольватация комплексного иона [CuPhe]+ неоднозначным
образом зависит от состава бинарного растворителя: с ростом содержания этанола
комплекс вначале десольватируется, а затем сольватация усиливается. Cольватация L-
фенилаланина в этаноле несколько ослабляется [1].
С помощью термохимического метода определены стандартные энтальпии
переноса стехиометрической смеси ионов [Na+ + Phe-] из воды в водно-этанольные
растворители и рассчитаны энтальпии переноса анионного лиганда Phe- (метод
TATB/TPTB). Значения ΔtrНº(Phe-) положительны вплоть до концентрации XEtOH =0,5
мол. д., что также указывает на десольватацию.
Стандартные энтальпии комплексообразования [CuPhe]+ в бинарных смесях H2O-
EtOH были найдены из калориметрического эксперимента. При увеличении
концентрации этанола в растворителе от 0 до 0,7 мол. д. экзотермичность реакции
возрастает от -19.98±0.67 до -59.15±2.27 кДж/моль.
Устойчивость и экзотермичность образования аминокислотных комплексов [CuPhe]+,
[CuAla]+, [CuHTyr]+, [Cu(HTyr)2] увеличиваются с ростом содержания этанола в растворе.
Наиболее вероятной причиной этого является ослабление сольватации лиганда в этаноле,
что облегчает процесс комплексообразования. Влияние растворителя на
термодинамические функции комплексообразования слабо зависит от строения и размеров
углеводородного фрагмента лиганда. При этом термодинамические характеристики
сольватации аминокислотных лигандов заметно различаются. Симбатность изменения
функций lgKуст=f(XEtOH) для различных аминокислотных комплексов объясняется участием
в координации одних и тех же функциональных групп лигандов.
1. Д.М. Буров, С.Ф. Леденков, В.Н. Вандышев // Журн. физич. химии. 2013. № 5.
ТЕРМОДИНАМИКА ФАЗОВЫХ ПРЕВРАЩЕНИЙ В СИСТЕМАХ

Nd2S3 – Er2S3, SrNd2S4 – SrEr2S4
Елышев А.В., Андреев О.В., Солодовников А.О., Харитонцев В.Б.
Тюменский государственный университет, Тюмень
e-mail: sheffield87@inbox.ru
Соединения Ln2S3, SrLn2S4 являются перспективными оптическими материалами.
Соединения Ln2S3 прозрачны в области спектра от 0.5 до 20-25 мкм, имеют ширину
запрещённой зоны ΔЕопт = 2,5 – 2,9 эВ. Соединения SrLn2S4 образованы 5s-, 4f-
элементами, что создает возможность формирования в матричных структурах
необходимые концентрации ионов редкоземельных элементов и определяет
перспективность соединений как люминофорных и лазерных материалов.
Впервые спрогнозированы, а затем построены методами физико-химического
анализа фазовые диаграммы систем Nd2S3 – Er2S3, SrNd2S4 – SrEr2S4 (рис.)
T, K - 1 T,K
Ж
- 1 2300 SrS+Ж -2
2300
-2 SrS+(SrNd2S4)+Ж Ж+TP (SrEr2S4) - 3
Ж -3 -4
TP(Nd2S3)+Ж TP (SrNd2S4)+Ж
- 4 2100 2110
2100
TP(Er2S3)+Ж
1900
55% 1950 1900
γ-Nd2-2xE2xS3 1770 75%

1700
45% 98% 1700
(x = 0 - 0.45) TP(γ-Nd2S3) 88%
+ 33%
α+γ TP(d-Er2S3) 1500
1500
d-Nd2-2xEr2xS3
TP (SrNd2S4)+TP (SrEr2S4)
(x = 0.98 -1) 1300 1300
α-Nd2-2xEr2xS3
(x = 0 - 0.4) TP(α-Nd2S3)
+ 1100
TP(d-Er2S3) 1100
40%
973 26% 90%
Nd2S3 20 40 60 80 Er2S3 900

мол. % Er2S3 SrNd2S4 20 40 60 80 SrEr2S4
мол. % SrEr2S4
Рисунок. Фазовые диаграммы систем Nd2S3 – Er2S3, SrNd2S4 – SrEr2S4. Результаты ВПТА: 1 –
начало плавления; 2 – полное расплавление. Состояние образцов по результатам методов РФА, МСА,
ДМА: 3 – однофазный; 4 – двухфазный; 5 - данные ДТА.
Составлены балансные уравнения (Табл.) фазовых превращений и их теплоты.
Теплоты превращений определены на установка Jupiter STA 449 F3. НИР
государственного задания (шифр 3.3763. 2011 (7-12))
Таблица
Балансные уравнения эвтектических и эвтектоидных фазовых превращений в системах
Nd2S3 – Er2S3, SrNd2S4 – SrEr2S4. ( ) – ориентировочные значения
Координаты
Вид фазового ∆Hпл,
нонвариантных точек Уравнение фазовых превращений
превращения кДж/моль
Состав Т, К
0.44TP γ-Nd2S3 (0.46Er2S3; 0.54Nd2S3) +
Эвтектическое 75 мол. %
1770 K 0.56TP δ-Er2S3 (0.98Er2S3; 0.02Nd2S3) ↔ Ж (47)
плавление Er2S3
(0.75Er2S3; 0.25Nd2S3)
0.98TP α-Nd2S3 (0.41Er2S3; 0.59Nd2S3) +
Эвтектоидное 42 мол. %
1435 К 0.02TP δ-Er2S3 (0.98Er2S3; 0.02Nd2S3) ↔ TP (7)
превращение Er2S3
γ-Nd2S3 (0.42Er2S3; 0.58Nd2S3)
0.61TP SrNd2S4 (0.36SrEr2S4; 0.64SrNd2S4) +
Эвтектическое 55 мол. %
1950 К 0.39TP SrEr2S4 (0.85SrEr2S4; 0.15SrNd2S4) ↔ (58)
плавление SrEr2S4
Ж (0.55SrEr2S4; 0.45SrNd2S4)
КОНЦЕНТРАЦИОННЫЕ ЗАВИСИМОСТИ ВЯЗКОСТИ И КОЭФФИЦИЕНТА

АКТИВНОСТИ В ВОДНЫХ РАСТВОРАХ ЭЛЕКТРОЛИТОВ
Сухарева Н.И., Галай Ю. В., Герасимова Н.П.
Могилёвский государственный университет продовольствия,
Могилев, Республика Беларусь
e-mail: suhareva2008@tut.by
В настоящем исследовании проведен графический анализ зависимости динамической
вязкости водных растворов электролитов от мольной доли растворённого вещества.
Уравнение: 1/((η/η0) − 1) = –n/В + 1/B ×1/х (где, η и η0 - вязкости раствора и растворителя)
линейно описывает зависимость вязкости водного раствора электролита от его мольной
доли. Проведена линейная аппроксимация указанной зависимости в узких диапазонах
массовых долей (от 0,02 до 0,04; от 0,04 до 0,06 и т.д.) в растворах следующих
электролитов: хлоридов никеля (II), кобальта (II), лития и лантана (III), сульфатов никеля
(II), кобальта (II), лития и меди (II). Интервал температур: от 00С до 1000С, максимальный
интервал массовых долей от 0,02 до 0,40. Проведена линейная аппроксимация указанной
зависимости для растворов электролитов в узких диапазонах массовых долей (от 0,02 до
0,04; от 0,04 до 0,06 и т.д.).
Нами выявлена аналогия в концентрационных зависимостях вязкости и
коэффициента активности в растворах анализируемых электролитов. По характеру данных
зависимостей данные электролиты можно разделить на две группы. Первую группу
электролитов характеризуют отрицательные значения параметров В или n в диапазоне
массовых долей (0,08 – 0,10) (растворы хлоридов никеля, кобальта, лития и лантана,
сульфатов кобальта и меди). Мы предполагаем в данном интервале концентраций
образование за счет водородных связей устойчивых кластеров воды. Интересен тот факт,
что растворы указанных электролитов характеризуются началом увеличения коэффициента
активности приблизительно в этом же диапазоне концентраций. Можно предположить, что
массовая доля воды, равная ≈ 90% – 92% (m(H2O) ≈ 5моль/кг), способствует разрушению
внешнесферных комплексов (или гидраторазделенных ионных пар) за счет образования
циклопентамерных кластеров воды. В интервале массовых долей (0,10 – 0,12) происходит
разрушение кластеров воды. Только для растворов сульфата меди (из всех исследованных
нами) в диапазоне массовых долей (0,12 – 0,14) опять наблюдается отрицательная
гидратация. К электролитам второго типа можно отнести сульфаты лития и никеля, для
которых минимум коэффициента активности наблюдается только перед образованием
насыщенного раствора. Метод вискозиметрии также фиксирует в данном случае
отрицательную гидратацию.
Характер температурных зависимостей вязкости в водных растворах электролитов
определяется их концентрацией. Интервал массовых долей 0,02 - 0,04 для всех
проанализированных соединений характеризуется резким и скачкообразным изменением
количественных характеристик процессов гидратации (В и n) с увеличением температуры.
Параметр В при температурах (150С, 300С, 600С) минимален, а число гидратации в
значительной степени возрастает. Обращает на себя внимание температура 850С. При 850С
вискозиметрический анализ констатирует максимальную силу взаимодействия ионов
электролита с молекулами воды и минимальное число гидратации в растворах. С
увеличением концентрации растворов кривые, описывающие функциональные
зависимости В = ƒ(Т) и n = ƒ(Т) носят все более плавный характер. В диапазоне массовых
долей от 0,12 до 0,28 числа гидратации в растворах хлоридов лития и никеля практически
не зависят от температуры. Небольшие величины радиусов катионов лития и никеля
объясняют такую аналогию.
FOR NOTES
Section 4
Thermodynamics
of the surface
phenomena and self-
organization phenomena
in the fluid systems
MICROCALORIMETRIC STUDY ON THE EFFECT OF MELAMINE AND PHENOSAN

DERIVATIVES ON PHOSPHOLIPID'S AND BIO-MEMBRANES
Alekseeva O.M., Shibryaeva L.S., Krementsova A.V., Mill E.M., Binyukov V.I.,
Krivandin A.V., Shatalova O.V., Goloshchapov A.N.
Emmanuel Institute of Biochemical Physics RAS, Moscow, Russia
e-mail: olgavek@yandex
In our work were tested 3 types of biologically active substance (BAS): plant growth
stimulant - melafen, and antioxidants – derivatives of phenozan, with the aim of studying of
its actions on the biomembrane’s structures and functions. The first - melamine salt of bis
(hydroxymethyl) phosphinic acid) is being used, as a stimulator for plants az aqueous
solutions under the concentrations of 10-10 - 10-9 M. But it is the inhibitor under the bigger
concentrations. The second and third are the derivatives of phenozan-acid (β - (4-hydroxy-3,5-
di-tert-butylphenyl) propionic acid: phenoksan - (β - (4-hydroxy-3,5-di-tert-butylphenyl)
potassium propionate] ) - shall be used as the antioxidant and the adaptogen, and ICHFANs -
are hybrid multitarget antioxidants. ICHFANs – are quaternized by long chain
alkylhalohenides (with amount of carbon atoms from 8 up to 16) alkyl-dimethyl- [β - (4-
hydroxy-3,5-di-tert-butylphenyl ) propionilethyl] ammonia halogenides. ICHFANs influence
to the structural and functional properties of biologic objects under concentrations 10-14 and
10-4 M. The micro calorimetric test held in a wide concentration range (10-21 M - 10-3 M). As
the experimental objects 2 types of membranes were used: 1) erythrocyte ghosts - the
appropriate membrane model of animal cells (with 5 identified thermo induced phase
transitions of protein’s micro domains), and 2) artificial phospholipid's membranes, were
formed in water media of phosphate buffer from neutral saturated
dimyristoilphosphatidylcholine phospholipid (DMPC). The hydration process (at the
temperature above of phase transition) of subtle dried DMPC film permited to receive of
multulammelar liposomes by the diameter of 2000 A. Such structures reflect the nature of
multilayer membranes in living cell. For liposome DMPC the temperature maximum of
phase-transition is 23,4о. This is why at room temperature all BAS enters through the
fluctuated pores (2-9 nm), arising in phase transition's temperature and temporal interval, and
contacts with all layers of multulammelar liposome. The aqueous solutions of melafen and
phenoksan, and ICHFANs emulsion were added to DMPC liposomes right before
measurements of thermo inducted characteristics. Erythrocyte ghost, that are the lipid bilayer
with proteins incorporated, were treated by BAS in ghost preparation process. To identify of
melafen action we used the different speed of heat supplied to model. In control when the
speed was decreased the phase-transition temperature, and the enthalpy, and the cooperativity
few changed. The enthalpy, the maximum temperature and the cooperativity of thermo
inducted transition has changed considerably under the presence of melafen in ultra small (10-
17
, 10-16 M) and big (10-6, 10-5 M) concentrations. The change are small under the
concentrations of 10-13 10-12 M. Phenoksan and ICHFANs changed the structures of objects,
as ghosts, and liposomes DMPC, while ICHFAN-С16 (with the longest alkyl deputy) built the
own phase in liposomes membrane. The melafen unaltered (in all concentration range) the
multulammelar structure of liposomes from mixture of nature phospholipids - egg lecithin.
Phenoksan and ICHFANs perturbated these objects. The actions of BAS on model objects
were correlated with their effects on animal cells. The ion permeability and the erythrocytes
morphology, the calcium signaling in thymocytes, leucocytes and cells of ascetic Ehrlich
carcinoma, signing on apoptosis were changed.
Section 4 — Thermodynamics of the surface phenomena and self-organization phenomena… ♦ 339
MOLECULAR DYNAMICS SIMULATION OF MELTING AND CRYSTALLIZATION

OF METALLIC NANOCLUSTERS
Bembel A.G., Samsonov V.M., Vasilyev S.A.
e-mail: vsa812@yandex.ru
Metallic nanoclusters are of interest in view of many potential applications in
nanotechnology. Particularly, Ni and Au nanoclusters demonstrate unusual magnetic
properties and, respectively, can be used as nanosized memory elements. Following to our
previous work [1], we have repeated computer experiments on Ni nanoclusters using our own
computer program where isothermal molecular dynamics and tight-binding potential are used.
In general our new results agree with former results [1] demonstrating hysteresis of melting
and crystallization of nanoclusters. Computer experiments on Au nanoclusters have revealed
some specific features compared to Ni-nanoclusters. It is also of interest that our results on the
size dependence of the melting temperature shown in Fig. 1 demonstrate much better
agreement with experimental data [2,3] then molecular dynamics results [4] obtained using
the same many-body potential.
Fig 1. Dependence of the Au nanocluster melting temperature on the number of atoms the
cluster consists of: 1 and 2 – molecular dynamics results (1 – ours, 2 – [4]), 3 and 4 – direct
experiment ([2] and [3], respectively)
References
1. Samsonov V.M., Kharechkin S.S., Gafner S.L., Redel' L.V., Gafner Yu.Ya. //
Crystallography Reports. 2009. V. 54. P. 526.
2. Buffat Ph., Borel J-P. // Phys. Rev. A. 1976. V. 13. P. 2287.
3. K. Dick, T. Dhanasekaran, Z. Xhang, D. Meisel // J. Am. Chem. Soc. 2002. V. 124. P.
2312.
4. Goloven’ko Zh. V. Diss. Cand. Sci. Barnaul, 2012.
THERMOGRAVIMETRIC STUDY OF CEMENT HYDRATION IN THE PRESENCE

OF VARIOUS TYPES OF POLYCARBOXYLATE SUPERPLASTICIZERS
A. Benmounah1, M. Samar1, R. Kheribet1, M. Saidi2and B. Safi1.
1
Research Unit, Materials, Processes and Environment (UR/MPE),
University of Boumerdes, Algeria
e-mail: benmounah2000@yahoo.fr
2
Department of Materials Engineering, Faculty of Engineering,
University of Boumerdes, Algeria
In this work, we studied the influence of three polycarboxylate superplasticizers of

different manufacturers (SP1: Aeternum-3, SP2: Viscocrete Tempo12 and SP3:
Medaflow145) on the hydration process of four different types of cement (C1: cement
sulphate-resistant, C2: cement with pozzolane addition, C3: cement with blast furnace slag
addition and C4: cement with limestone addition). For this, a thermogravimetric study was
carried using the technique of differential thermal analysis (DTA-TGA). Thermal analysis
techniques such as differential thermal analysis (DTA) and thermo-gravimetric analysis
(TGA) were used to give more qualitative and quantitative information .This analysis
technique is to follow the loss weight of a sample of material heated to a temperature high
enough to cause its complete dehydration. In practice, the maximum temperature is imposed
between 950 and 1100 ° C. The results obtained by the thermogravimetric study showed that
polycarboxylates used act differently on the cement hydration of same type, and each type of
cement. Also, a supplementary study was carried on the physical and mechanical properties of
mortars based on four different types of cement with three superplasticizers mentioned (with
W/C ratio of 0.35). The results of this study have shown that:
- SP1 has increased the strength mechanical of four cements and all curing ages. This
reflects its good interaction with the cement.
- SP2 also gave good strength with all cements used.
- SP3, did not improve strength mechanical and contrary to other superplasticizers has
decreased strength of C1 and C2. This is due to its poor compatibility with these cements.
All the results obtained through this study clearly show that the action of three types of
polycarboxylate superplasticizers on the rheological and physico-mechanical properties of
cement differs from one provider to another and from one type of cement to the other. For a
rational use, tests are necessary before use.
CLUSTER INDIFFERENT TO THERMODYNAMIC FLUCTUATIONS

AS THE BASEMENT OF THE SIMPLE THERMODYNAMIC MODEL
FOR THE SURFACE TENSION CALCULATIUONS IN LIQUID-VAPOR SYSTEMS
Cherevko A.G.*, Maryasov A.G.**
*Siberian State University of Telecommunications and Informatics, Novosibirsk
e-mail: cherevko@mail.ru
**V.V.Voevodsky Institute of Chemical Kinetics and Combustion of SB RAS, Novosibirsk
e-mail: maryasov@kinetics.nsc.ru
It was shown [1] that in overcooled liquid-vapor system a liquid cluster having
temperature fluctuations range of the size of system overcooling is indifferent to
thermodynamic fluctuations of its temperature, internal energy, and entropy. We refer such
clusters as CITFs below. CITF has size large enough to account it as a classic object in terms
of the Landau criterion so that it is possible to use phase characteristics for systems with flat
liquid-vapor interfaces. Experimental data analysis showed [2, 3] that for different types of
substances having different types of molecular bonding such as noble gases with dispersion
interatomic interaction, metals, salts (haloids of alkali metals) with ionic interactions the
surface tension temperature dependence is quite satisfactory described by the relation
σ =σ 0 1 + χ (TB − T ) / ( 6TM )  . Here σo is surface tension on the phase coexistence curve, T,
TB, and TM are system temperature, substance boiling and melting temperatures, respectively,
and χ is semiempirical coefficient.
We have supposed the latter coefficient is substantial property of a substance and it is
defined mostly by the molecular evaporation mechanism. The approach for calculation of the
coefficient χ is developed. The model is rather simple, it is based on the configurational
surface entropy change in the single evaporation act when one molecule leaves a cluster
surface. Clusters are considered as spherical objects of dense packed molecules having some
relaxed vacancies ('voids', see [4]) in their structure. The random distribution of voids is
suggested in both bulk and surface layer of a cluster. In a bulk each molecule has 12 closest
neighbors, molecule at the surface has 9 neighbors, some of those are voids. Molecules of
non-metallic substances evaporate from the surface layer. Metal molecules evaporate from
'islands' [4] above the surface layer where molecule has just 3 closest neighbors. The
evaporation rate depends on the number of broken contacts which define the energy barrier,
neighboring voids reduce the activation energy. Calculations of the coefficient χ using the
model described demonstrate satisfactory agreement with those obtained from experimental
data [2, 3]. The model allows also to estimate the void volume, it is approximately one half of
the molecular volume of a substance, this is in a good agreement with generally accepted
interpretation [5].
References
1 Cherevko A.G. // High Temperature. 2010. V. 48. P. 315 – 317.
2 Cherevko A.G. // Colloid. Journal. 2009. V. 71. N 6. P. 869 – 876.
3 Cherevko A.G. // Colloid Journal. 2011. V. 73, No. 1. P. 128–134.
4 Smirnov B.M., Berry R.S. Phase Transitions of Simple Systems. Berlin: Springer, 2007.
247p.
5 Kraftmaher Y. Modulation Calorimetry. Theory and Application. Springer, 2004. 93 p.
PHASE TRANSFORMATIONS IN THE LIMITED VOLUME

Fedoseev V.B. *, Fedoseeva E.N.**
*
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences
**
Lobachevsky State University, Nizhny Novgorod
e-mail: fedoseev@phys.unn.ru
Features of nucleation of new phases and phase transitions in nanoscale materials are an
actual problem of modern chemical thermodynamics.
In this report we discuss about two types of phase transitions in multicomponent
systems. There are solution – crystal and partially miscible liquids. It was calculated the
surface of the Gibbs function of two-component heterogeneous systems, and described its
change depending on the system size, temperature and concentration. Gibbs function is
constructed using the surface energy of all (exterior and interior) boundary and chemical
potentials of components. The model uses approach of an ideal or real solution. The size and
concentration of the system is completely determined by the quantity and conditions of the
conservation of matter during phase transformations.
Analysis of the Gibbs function extremums determines specific system state. Gibbs
function of the system "solution – crystal" can have two extremums and singular points
corresponding homogeneous state. Minimum corresponds to either global or metastable
thermodynamic equilibrium; the maximum (unstable equilibrium) corresponds to the critical
nucleus. The free energy of the equilibrium state and the state corresponding critical nucleus
converge with decreasing size of the system. If the size of the system is further reduced, the
state of unstable equilibrium disappears and the single minimum of free energy of the system
is the state of homogeneous solution. Gibbs function of liquid – liquid systems can have two
or three minimums (figure: the equimolar mixture model). Potential barrier separates from
each other.
The most interesting feature of small systems is the possibility of the existence in these
systems more than one stable and metastable states. The changing of some parameters (for
example: the system size, temperature, concentration) leads to inversion of stable and
metastable states.
Some general regularities are reproduced in the simulation. If the system is decreased,
the size of the critical nucleus increases, the energy of the critical nucleus increases and the
concentration of the saturated solution is growing. The size effect for the composition of
coexisting phases is more complex.
These theoretical results are verified by experiment.
This work is sponsored RFBR grants 13-03-97064-r_povolj'e_а.
CONDENSATION OF CHARGED COLLOID PARTICLES ON A SOLID WAFER

DUE TO ELECTROSTATIC CORRELATIONS: A THEORETICAL STUDY
Frolov A.I.1, Budkov Yu.A.1, Brilliantov N.V. 2, Kiselev M.G.1
1
Institute of Solution Chemistry of RAS, Ivanovo, Russia
e-mail: aif@isc-ras.ru
2
Department of Mathematics, University of Leicester, Leicester, UK
There are several experimental evidences on the condensation of the charged colloid
particles from their diluted solution on a solid wafer [1]. This condensation is a first-order
phase transition, which results in the formation of a new dense phase on the wafer. In the
present work we developed a theoretical model of the interface between a charged colloid
particle solution and a solid wafer. The colloid solution is described in the framework of the
hard core one component plasma model [2]. Contrary to the DLVO theory, in our theoretical
model we take the electrostatic correlations between charged particles in the solution into
account, and we completely neglect the dispersion interactions between the colloid particles.
However, the colloid particles interact with the wafer surface via dispersion attraction. This
attraction leads to the local increase of the colloid particle concentration at the wafer surface.
The increase of the charged colloid particle concentration increases the strength of the
electrostatic correlations between them at the surface. In a certain range of the model
parameters (the Bjerrum length in the bulk colloid solution and the strength of the particle
interaction with the wafer surface) the electrostatic correlations between colloid particles lead
to condensation of the colloid particles on the wafer surface: an abrupt drastic increase of the
colloid particle concentration at the surface (a first-order phase transition). The appearance of
the charged colloid particle condensation on the wafer surface at certain state parameters was
confirmed by molecular dynamics simulations of the highly asymmetric electrolyte in the
framework of the restrictive primitive model.
The conclusion from this work is: the strong electrostatic correlations can lead to
condensation of the charged colloid particles on a solid wafer from their diluted solution (the
first-order phase transition at the surface).
References
[1] Ishikawa, Kitano, J. Jpn. Soc. Microgravity Appl. 2011, 28, S17–S22
[2] Brilliantov, Malinin, Netz, Eur. Phys. J. D 2002, 18, 339–345.
HIGH SELECTIVITY OF GUEST EXCHANGE IN CALIXARENE CLATHRATES

Galyaltdinov S.F., Ziganshin M.A., Gorbatchuk V.V.
A.M. Butlerov Institute of Chemistry, Kazan Federal University, Kazan
e-mail: sgaljalt@ksu.ru
In the present work, guest exchange in tert-butylthiacalix[4]arene (1) clathrate was
studied [1] using simultaneous thermogravimetry, differential scanning calorimetry, and
evolved gas analysis by mass-spectrometry (TG/DSC/MS analysis) and X-ray powder
diffraction.
The studied host is very selective in usual sense, with discrimination of close
homologues, being able, for example, to bind methanol and to exclude ethanol [2]. For this
host, a change in clathrate stability was studied as a result of sample preparation by guest
exchange instead of direct saturation of host with guest vapor according to the next scheme:
25°C
1 ⋅ 1.90(DCE) + xG (vap)  →1 ⋅ xG ⋅ yDCE + (1.90 − y )DCE (vap)
Besides, a host ability to remember the guest participating in the exchange was
analyzed. Both these properties have not been reported before a present work, boosting the
ways for development of new methods for effective encapsulation and genuine molecular
recognition.
This exchange can give clathrates of 1 with much higher thermal stability than those
prepared by direct saturation of guest-free calixarene 1 with vapors of the same guests. In
several cases, these clathrates can be prepared only by guest exchange. Otherwise, the
saturation of the initial 1∙1.90DCE clathrate with a second guest gives a guest-free host. When
headspace of liquid water is used in the exchange, the resulting contents of 1,2-dichloroethane
in clathrate may be controlled by variation of clathrate/water ratio, while water does not enter
the solid phase above the trace level. For water and two organic guests, this level is still
enough to catalyze decomposition at 25°C of the clathrate, which otherwise is stable up to
91°C.
A genuine molecular recognition of methanol by 1 was observed in formation of a
metastable loose polymorph of 1 that remembers this compound after its release from a guest-
exchange product. The written memory of methanol can be read in DSC experiment. No other
guest studied can be thus remembered by 1. This is a first example, where methanol can be
remembered by host, and the first one, where memory of gone guest was found possible only
after guest exchange.
This work was supported by the Russian Foundation for Basic Research (Grant No. 11-
03-90445).
References
1. Galyaltdinov, S. F.; Ziganshin, M. A.; Drapailo, A. B.; Gorbatchuk, V. V. J. Phys. Chem. B
2012, 116, 11379−11385.
2. Gorbatchuk, V. V.; Tsifarkin, A. G.; Antipin, I. S.; Solomonov, B. N.; Konovalov, A. I.;
Lhotak, P.; Stibor, I. J. Phys. Chem. B 2002, 106, 5845–5851.
COMPUTER SIMULATION OF THE VESICLE TO MICELLE TRANSFORMATION

BY BILE SALTS
Haustein M., Wahab M., Schiller P., Mögel H.-J.
TU-Bergakademie Freiberg, Institute of Physical Chemistry,
Freiberg, Germany
e-mail: martin.haustein@student.tu-freiberg.de
The solubilization of vesicles or membrane patches of non-soluble lipids by bile salts is
a fundamental process in fat digestion. Bile salts are well-known for their ability to solubilize
different lipids and cholesterol into mixed micelles and to aid their further processing in the
small intestine. By using molecular dynamics simulations (MD) with solvent free coarse
grained models for 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) and sodium
cholate (NaCh) the following mechanism of the vesicle to micelle transition has been studied.
It consists of the following stages: 1.) Adsorption of bile salts on the vesicle membrane,
2.) enhanced pore formation with increasing bile salt concentration at the pore rim, 3.)
development of protrusions from large local shape fluctuations, 4.) detachment of protrusions,
consisting of mixtures of lipids and bile salts, as wormlike micelles, 5.) incorporation of
additional bile salts into the micelles with following decay into smaller ones, and 6.)
enlargement of pores up to complete destruction of the vesicle (Fig. 1).
By using powerful massive-parallel graphics processors, we have been able to simulate
large systems containing a DPPC-vesicle of physiologically relevant size (30nm - 50nm) over
long times (1 — 3 μs) in solutions of NaCh at different concentrations. The process of
complete solubilization of a 30 nm vesicle could be observed within one week of CPU time,
starting from the raw vesicle until wormlike protrusions were detached.
Fig. 1. Snapshot of a vesicle undergoing transition into wormlike micelles.

DETERMINATION OF THE SOLUTION/SALT INTERFACIAL ENERGY

AND THE DISJOINING PRESSURE FROM MEASURED
DELIQUESCENCE/EFFLORESCENE HUMIDITIES OF HYGROSCOPIC PARTICLES
Hellmuth O.a, Shchekin A.K.b, Shabaev I.V.b
a
Leibniz Institute for Tropospheric Research (TROPOS), Leipzig
b
e-mail: olaf@tropos.de
The simulation of atmospheric clouds is one of the most uncertain parts in numerical
weather prediction and climate modelling. One prerequisite for more sophisticated cloud
treatment is a better understanding of aerosol and hydrosol formation via vapour ↔ liquid ↔ solid
phase transitions. Here, we discuss the requirements for the modelling of the growth and
shrinking of a hygroscopic (soluble) nanoparticle in ambient air with varying humidity.
Soluble substances (mostly salts) are able to absorb water molecules from the ambient air.
The water uptake continues until the hygroscopic particle completely dissolves in the absorbed
water, in this way forming a pure solution droplet. The transition from partial to complete
dissolution is called deliquescence, and the RH threshold at which a soluble particle completely
dissolves is called deliquescence humidity (DRH). For highly soluble salts such as NaCl and
small condensation nuclei, deliquescence occurs at subsaturation of the ambient water vapour
with respect to a flat surface of pure bulk water (RH<100%). The reverse process, called
efflorescence, leads to the formation of a solid crystal within the solution drop by homogeneous
nucleation. Efflorescence is driven by the solution supersaturation, depending on RH and
temperature (T). The humidity, at which efflorescence sets in, is called efflorescence humidity
(ERH). The difference between DRH and ERH results in a hysteresis effect. Owing to the high
atmospheric variability of RH and T, hysteresis effectively impacts the partitioning between solid
and aqueous phases of tropospheric salt particles.
Employing the mechanical and thermodynamic concept of disjoining pressure, Shchekin,
Shabaev, and Rusanov (SSR) derived a generalised Gibbs–Kelvin–Köhler equation for the
external vapour/liquid equilibrium and a generalised Ostwald–Freundlich equation for the internal
solution/solid equilibrium of a soluble particle embedded in a solvent vapour1,2,3. These
equilibrium conditions allow the determination of the particle size evolution as a function of RH
(“humidity growth factor”) for both partially and completely dissolved residual core. A challenge
for application of this theory to atmospheric systems is the answer to the closure problem, namely
the determination of the solution/salt interfacial energy and the disjoining pressure. Employing
the SSR theory in combination with classical nucleation theory (CNT)4 , we propose a method to
derive both closure parameters from measured values of DRH and ERH. In the presentation we
apply the method to a nonideal aqueous NaCl solution drop. Apart from atmospheric applications,
the results might also be of importance for metallic corrosion in salt stocks.
References
1. Shchekin, A.K. and Rusanov, A.I., J. Chem. Phys. 129, 154116 (2008).
2. Shchekin, A.K., Shabaev, I.V., and Rusanov, A.I., J. Chem. Phys. 129, 214111 (2008).
3. Shchekin, A.K., and Shabaev, I.V., Colloid J. 72, 432 (2010).
4. Hellmuth, O., Khvorostyanov, V.I., Judith A. Curry, J.A., Shchekin, A.K., Jürn W. P.
Schmelzer, J.W.P, Feistel,R., Djikaev, Y.S., Vladimir G. Baidakov, V.G. (2013): Selected
Aspects of Atmospheric Ice and Salt Crystallisation, 513 pp. In: Schmelzer, J.W.P, Hellmuth,
O. (Eds.): Nucleation Theory and Applications. Special Issues. Review Series on Selected
Topics of Atmospheric Sol Formation: Volume 1, Joint Institute for Nuclear Research,
Dubna, 2013 (in press).
THERMODYNAMIC CHARACTERISTICS OF ADSORPTION

OF CERTAIN ORGANIC COMPOUNDS ON A MONOLAYER
OF UNSUBSTITUTED β-CYCLODEXTRIN
Kopytin K.A., Pivovarova N.A., Kudryashov S.Y., Onuchak L.A.
e-mail: kirko87@inbox.ru
Study of the thermodynamics of complex formation of cyclodextrins and their
derivatives can be carried out under different conditions. The most common variant, when the
formation of complexes of different organic molecules with cyclodextrins occurs in bulk
liquid phases. Little consideration of the remaining issues related to education inclusion
complexes in thin films and monolayers on the basis of cyclodextrins. Possible that the
process of the formation of inclusion complexes considered at the phase boundary «gas –
liquid». However, it should be noted that in this case there are some experimental difficulties,
and the difficulties in the interpretation of the results. Another possibility to study the
thermodynamics of complex formation at the interface is the study of processes in the
adsorption system «gas – solid». For this dense or sparse monomolecular layers of
macrocyclic molecules are applied to the surface of the solid in contact with a gas phase
containing molecules «guest».
We have investigated adsorption of organic compounds of different nature on
monolayer unsubstituted β-cyclodextrin (β-CD) deposited on graphite carbon support with a
flat surface – Carbopack Y (CpY) by the method of inverse gas chromatography.
A comparison of Henry constants of adsorption showed that an increase of the Henry
constants of adsorption observed for alcohols of normal structure and compounds with the
small size of the molecules (80-100 Å3) by modification. This growth is due to an increase in
the heat of adsorption (10-15 kJ/mol). This indicates an increase in the retention of these
compounds on the modified adsorbent compared to the original, and the strengthening of
intermolecular interactions «adsorbate – adsorbent». In general, the growth of the heat of
adsorption indicates that the screening surface CpY monolayer β-CD offset increased
interaction with adsorbate molecules β-CD in two dimensions due to partial access
macrocyclic cavity. This conclusion is confirmed by the data on the values of the entropy
change of adsorption on the two adsorbents. It is shown an increase in the change of entropy
of adsorption (in absolute value) at ≈ 15-40 J/(mol·K) for all the compounds in which it was
found an increase of the heats of adsorption. Apparently, the axis of the cylindrical cavity of
the molecule β-CD is parallel or at an acute angle to the surface CpY and is available only for
small volume of molecules. Thus, the complex formation in the case of unsubstituted β-CD is
difficult and is observed in the case of compounds with molecules small volume.
The work was supported by the Ministry of Education and Science as part of the state
task grant N 3.3209.2011.
SIMULATION OF ARGON, METHANE AND ETHANE ADSORPTION ON GRAPHITE

Kudryashov S.Yu.
Samara State University, Samara, e-mail: kstasu@mail.ru
In this work adsorption equilibrium of argon, methane and ethane was studied on
homogeneous open graphite surface in small coverage of the adsorbent (Henry's region) by the
Gibbs ensemble Monte Carlo (GEMC) method. Henry constants of adsorption at various tem-
peratures were calculated in the atom-atom approximation for the potential adsorbate energy
in the adsorbent force field. Adsorbate molecules are considered to be non-interacting with
each other. The summation of atom-atom potentials for the carbon atoms in the graphite lat-
tice gives the following formula for the potential energy of i-th atom polyatomic molecules:
πκ ∞
πκ ∞
∑ (z d + k ) + Bi ∑ (z d + k)
−4 −10
Φ ( zi ) = −Ci i i ,
2d 4 k =0 5d 10 k =0
where d = 0.3354 nm – the distance between planes in the graphite crystal, κ = 38.285 nm-2
– the number of carbon atoms per 1 nm2 of the graphite crystal basal plane, the coordinate zi
is distance between i-th atom and graphite plane; constants Ci and Bi see in Table.
Table. Parameters for Lennard-Jones (6,12) potential It was assumed that the CH-
ϕ (r ) = ε[(σ r )12 − 2(σ r ) 6 ] distance in quasi-rigid methane molecule
is 0.1087 nm, bond angles corresponding
ε k, σ , C = 2 N A εσ6 , B = N A εσ12 ,
Atoms point group Td, ethane molecule consist-
K nm J∙nm6∙mol-1 J∙nm12∙mol-1
ing of two quasi-rigid CH3-groups with
Ar − C graphite 57.92 0.3819 2.9886 4.6372·10-3 symmetry C and internal rotation barri-
3v
H − Cgraphite 20.63 0.3424 0.5523 0.4446·10-3 er 12,175 kJ∙mol-1, the CC- and CH-
Csp3 − Cgraphite 30.49 0.3816 1.5664 2.4197·10-3 distances are 0.1536 and 0.1091 nm,
Lorentz – Berthelot combining rules: CCH-angle is 110.91°. The model system
ε A - B = ε A - A ε B- B , σ A - B = ( σ A - A + σ B- B ) 2 consists of parts I and II that are in ther-
mal and material equilibrium and have
volumes VI = VII = V 2 . Both subsystems adsorbate fills slit pore. In adsorption subsystem I is
one of the pore wall is a flat surface of graphite, the opposite wall of the pore inert, in subsys-
tem II both walls pore inert. The pore width L must be much greater than the distance at
which the “adsorbate – adsorbent” attractive forces manifested. In the whole system (I + II)
used canonical NVT Metropolis scheme with probability of system state ( N I , N II , T ) :
literature (see Fig.).
N!  Φ + Φ II  ,
P( N I , N II , T ) = const exp − I 
N I ! N II!  kT 
where Φ I , Φ II – the total potential energy
(J) of the molecules in subsystems I and II,
N I , N II – number of molecules in sub-
systems, N I + N II = N = const .
If N I is the value, the averaged
over the equilibrium segment of Markov
chain, then the Henry constant (in
µm≡cm3∙m-2) is
Γ 2 NI − N .
K1,c = = L
cG N − NI Fig. Temperature dependences of the Henry constant.
The results of the simulation were in
good agreement with the data found in the
THERMODYNAMICS OF SORPTION OF ORGANIC COMPOUNDS ON COMPOSITE

SORBENT BASED ON SUPRAMOLECULAR LIQUID CRYSTAL
AND СHIRAL MACROCYCLE
Kuraeva Yu.G., Onuchak L.A., Kuvshinova S.A., Burmatnova T.S.
e-mail: kuraeva81@mail.ru
The objective of this work was to study the thermodynamics of sorption of organic
compounds of different classes by a mixed system based on supramolecular LCD 4-(3-
hydroxypropyloxy)-4'-formilazobenzene (HPOFAB) and macrocyclic heptakis-(2,3,6-tri-O-
acetyl)-β-cyclodextrin (Acetyl-β-CD) in distribution of gas chromatography mesophase
conditions.
Based on the experimental data for 24 organic compounds, including optically active, it
was calculated chromatographic retention values, standard and excess thermodynamic
functions of sorption. It was found that the introduction of the macrocycle in LC leads to most
of the compounds to increase retention (alkanes, monohydric alcohols, xylenes, camphene, α-
pinenes), with the exception for optical isomers of limonene, menthol and butanediol-2,3. It is
shown that for all the sorbates in the mesophase and in the isotropic phase sorbent observed
positive deviations from Raoult's law ( γ i > 1). The observed increase in the retention of most
∞
of sorbates was due to a decrease Raoult's factors in case of adding Acetyl-β-CD to the LC
because of the reduction of the order parameter and better incorporation of molecules in a
binary phase sorbent. In addition, in the structure of the mixed NF there are cavities of Acetyl-
β-CD, which can form complexes of the type "guest-host". Reducing retention (limonene,
menthol, butanediol-2, 3) can be explained by the increase in the activity of Raoult's
coefficients, caused by dissolution deterioration of sorbates apparently because of steric
restrictions.
It was found that the binary sorbent "HPOFAB - Acetyl-β-CD" has enantioselectivity
towards to low-polarity (camphene pinenes, lemons) and polar (menthol, butanediol-2,3)
optically active compounds in both rigid crystal region and in the mesophase . Comparison of
the thermodynamic functions of sorption showed that the separation of the enantiomers can be
explained by difference in the values of the standard enthalpy of adsorption of the
dextrorotatory and levorotatory isomers of each pair of studied sorbates.
SURFACE TENSION OF MICELLES IN SOLUTIONS OF SURFACE ACTIVE

SUBSTANCES OF HOMOLOGOUS SERIES OF SODIUM ALKYL SULFATES
Kuznetsov V. S., Usol’tseva N.V., Zherdev V.P.*
Ivanovo State University, Nanomaterials Research Institute, Ivanovo
e-mail: nv_usoltseva@mail.ru
*Ivanovo State University of Civil Engineering and Architecture
Research of tension of deflected surfaces is a traditionally actual and in general still
unsolved task of thermodynamics, physics and molecular mechanics [1]. This work offers the
semiempirical method of determination of surface tension (ST) of spherical micelles in
solutions of homologous series of colloid surface active substances, in particular – sodium
alkyl sulfates (AS Na).
The method is based on approximation of surface tension’s dependence on a flat boarder
cmc
water – hydrocarbon (W/H) on the length lc of H – radical of units of homologous series (γ ∞
(lc)) and a following substitute:
cmc
dγr/dr = d γ ∞ /dlc (1)
cmc
At that the meanings of γ ∞
are received from experimental isotherms of surface
tension in the field of CMC for members of studied homologous series and a known rule of
additivity of surface tension on the boarders water-air and H-layer-air (Antonov’s rule) [2].
The determined approximation and the substitution (1) are used in Laplace’s equation for
surface tension of spherical units after its differentiation on a radius of tension r by its
constants T, V and the pressure in an exterior phase. At that Laplace’s pressure difference of
ΔPl = Wl/V, where V – is the volume of a micelle with radius r, Wl – work on overcoming ΔPl
at the transfer of H-radical from water phase into a hydrophobic core [3].
For homologous series of sodium alkyl sulfates the following functions having asymptotic
character have been received (as the whole thermodynamics of micelle formation [3]).
cmc
γ ∞ = exp (a-b/lc), (2)
γ~∞cmc mJ / m 2
b = 6.773 Å, γ ∞ = 1 ⋅ mJ / m
ccm 2
where a = 3.591,
cmc cmc cmc
(Wl/4πr2 γ ∞ ) = ωl/ γ ∞ = (2/3)exp(b/lc - 1); γr/ γ ∞ = 2-exp (b/lc) (3)
The data received for micelles of AS Na in the solution are discussed in the report.
nc 8 10 12 14
lc, Å 11,62 14,15 16,68 19,21
mJ
cmc 2 30,25 32,56 33,85 34,44
γ∞ , m
cmc
ωl/ γ ∞ 0,52 0,41 0,33 0,28
cmc
γr/ γ ∞ 0,22 0,39 0,50 0,58
References
1. D. I. Zhuchovitskiy // Russian J. Phys. Chem. 2001. Vol. 75. No 7. P. 1159.
2. A. A. Abramzon. Surface-active matters. Leningrad : Chemistry, 1981.
3. A. I. Rusanov. Thermodynamic base of mechanochemistry. S-Petersburg : Science, 2006.
MOLECULAR MECHANISM OF CELLULOSE ACETATES STRUCTURE FORMATION

IN SOLVENT PRESENCE
Lirova B.I., Lutikova E.A., Granitova O.V., Kotel’nikova O.A., Filina T.E.
Ural Federal University, Yekaterinburg, Russia
e-mail: bella.lirova@usu.ru
Cellulose derivatives are the polymers with enhanced hardness of macromolecule chains
capable to form liquid-crystal (LC) mesophases at dissolution in melts and solutions.
Of special interest for film nanomaterials development is the ability of some organic
solvents in vaporous state to initiate alignment processes in cellulose acetates (CA). In the
films modified by solvent vapors there appears steady-state effect of induced anisotropy. The
influence of solvents on the phase behavior of polymer systems depends on their interaction
with macromolecules and the presence of intra- and intermolecular hydrogen bonds in a
polymer. The aim of the work was to study by IR-Fourier spectroscopy method the molecular
mechanism of structural rearrangements in CA films in the course of sorption of solvents of
various chemical compositions.
The CA films with different degrees of acetylation and containing 54.5 and 60.2%
acetate groups were studied. Nitromethane (NM), dimethylsulfoxide (DMSO), and
tetrachloroethane (TCE) were used as solvents. The phase state was estimated by an Olympus
ВХ-51 polarizing microscope. The IR-spectra were taken by a Nicolet 6700 Thermo Scientific
IR-Fourier spectrometer with a DTGS detector. The intermolecular interaction of AC with
NM, DMSO, and TCE in the course of the sorption of their vapors was determined by the
changes of absorption bands of stretching vibrations of hydroxyl (νО-Н) and carbonyl (νС=О)
macromolecular groups.
The splitting of absorption bands complicated profile line (by a PEAK RESOLVE
software) showed that in the course of sorption of NM and DMSO vapors by AC films the
rearrangement of various (in energy value) intra- and intermolecular hydrogen bonds in
macromolecules takes place. The nature and strength of interchain associates and solvate
complexes in AC films containing NM and DMSO were discussed and the enthalpy of their
formation was determined. The amount of intramolecular and different (in energy) types of
intermolecular H-bonds in AC films in the course of solvents sorption was calculated. It was
established that in AC films in the presence of strong-donor solvent DMSO (donor number
DN SbCl5 =28.9) much wider spectrum of energetic interactions (due to formation of strong
solvates of ОН…O=S and ОН…ОН…O=S types) are observed when compared with NM
(DN SbCl5 =2.7). The number of intermolecular H-bonds О(3)-Н´(3)…О(5) и О(2)-Н(2)…О'(6)
between neighbor pyranose cycles, that according to present conceptions stabilize rigid spiral
conformation of macromolecules, retains in the course of NM sorption which favors the
formation of LC state in the system. At DMSO sorption intramolecular H-bonds are broken
but redistribution of H-bonds system and the dipole-dipole interaction of S=O and C=O polar
groups of solvent and polymer in AC films under the action of DMSO lead to conformational
rearrangement of macromolecules and their ordering which agrees with X-ray structural
analysis. However the formation of anisotropic state due to the enhancement in
macromolecule chains flexibility was not observed. In the course of TCE sorption the
rearrangement of H-bonds system in AC is negligible. The primary solvation of TCE acetate
groups of AC due to the dipole-dipole interaction leads to initial polymer structure
disordering.
THE DEPENDENCIES OF THE ELASTIC MODULUS AND THE COEFFICIENT

OF THERMAL EXPANSION VERSUS OF SIZE AND SHAPE OF NANOCRYSTAL
Magomedov M.N.
Institute for Geothermal Research of Daghestan SC RAS, Russia
e-mail: mahmag4@mail.ru
On basis of the model nanocrystal in the form of a rectangular parallelepiped with variable
shape of the surface (RP-model) [1], is developed the method for calculation of the dependencies
of the elastic modulus (B) versus of the number of atoms (N) and the shape of surface for
nanocrystal at the defined temperature (T) and density. It was received:
B ( N , T ) = B (T ) in − Pls ( N , T ) ⋅ ∆Bsf ( N , T ) , (1)
where Bin is the elastic modulus of macro crystal (at N = ∞), Pls is the Laplace pressure.
Let us now assume that the interatomic interaction in a nanocrystal of a simple single
component compound is governed by the Mie–Lennard-Jones pair potential [2, гл. 3]:
D   ro   ro   .
b a
ϕ( r ) =  a   − b   (2)
(b − a )   r   r  
 
Here, D is the depth of the potential well, ro is the coordinate of the minimum of the potential
well, b and a are parameters: b > a.
Then by means of RP-model the expression for ∆Bsf from (1) is received in the form:
∆Bsf ( N , T ) ≅ [1 − λ( N , T )].
ab (3)
6
1,0 For crystals from the elements of IVa subgroup
B* of carbon: C-dia, Si, and Ge, was received: λ(N, T) ≈
0,9 10 – 3 << 1, that allows to simplify (3) as: ∆Bsf = a b /
12
0,8 4300
K C - diamond 6. The calculations have shown that isothermal
K
elastic modulus decreases at reduction of the size of

00
10
0,7
nanocrystal the more noticeably, than lower
K
20
Tm * = Tm(N) / 4300 K temperature. The decrease of the relative elastic

0,6
modulus: B* = B(N, Tm)/B(Tm)in , the weaker, than
0,5 lg(N) the decrease of the relative melting temperature: Tm*
= Tm(N)/Tm(∞).
1 2 3 4 5 6
The calculation of the isobaric coefficient of
100
90
α p
* thermal expansion (αp) have shown that at the
80 isomorphic reduction of N along of isotherm the
100 K
70 relation: αp* = αp(N, T)/αp(T)in , increases the more
1000 K
60 noticeable, than lower temperature.
50 On Figs. are shown the isomorphic of
40 functions B(N)*, Tm(N)*, and αp(N)* for diamond
30
along the different isotherms. The parameters of the
20
potential (2) were such, either as in [1]. The
4300 K
isomorphic are received for the nanocrystal in the
10
shape of cube, because it the most energy stable
0
1 2 3 4 5 6 shape of RP-model. The melting temperature of the
lg(N) diamond took as: Tm(∞) = 4300 K.
This study was supported by the Presidium of the
RAS (project no. 12.1.19) and the RFBR (projects no. 10–02–00085-a and 12–08–96500-r-yug-a).
1. Magomedov M.N. // Physics of the Solid State. 2010. Vol. 52. No. 6. P. 1283 – 1292.
THERMODYNAMICS OF SORPTION OF Pb 2+ IONS

ON THE RESIN DUOLITE C-467
Mamedova M.T.
Nakhchivan Branch of the National Academy of Sciences of Azerbaijan, Nakhchivan
e-mail: memmedova-melahet@mail.ru
In this work was studied the thermodynamics of sorption of Pb2+ ions from aqueous
solutions by ion exchanger Duolite C-467. For the preparation of aqueous solutions of Pb2+
ions the Pb(NO3)2 salt was used. The initial concentration of the solution changed from
0.002mol/l to 0.2mol/l. Sorption was studied at 25-450C temperature range, under static
conditions, with constant mixing. Temperatures regime created and maintained by a
thermostat. The contact time of the sorbent with a solution was 30 minutes.The amount of the
Pb2+ ions was determined by the titrimetric method. The ratio of liquid and solid phase
(solution and sorbent) is 300: 1 (L: S = 300: 1).
As a sorbent used ion exchanger Duolite C-467 (produced in Germany). Duolite C467 is
a resin of macroporous structure. Its polystyrenic matrix, crosslinked with DVB, contains
aminophosphonic groups. The chemical nature of these groups is such that they form
complexes with metal ions. Duolite C-467 may be distinguished from aminodiacetic resins by
its greater specificity for various cations and by the greater stability of the complexes formed
with cations of low atomic mass. Functional groups of the resin are-CH2-NH-CH2-PO3Na2,
ionic form as shipped Na+.
Experiments show that with increasing temperature and the initial concentration of
solution adsorption of Pb2+ ions on Duolite C-467 increases. At all temperatures, the sorption
isotherm is well described by the Langmuir equation.
Based on the experimental data we calculated the equilibrium constant (K), the diffusion
coefficient (D), change in the isobaric-isothermal potential ( ∆G ), the activation energy ( E a ),
entropy ( ∆S ) and entalpiya ( ∆H ) sorption.
The results are presented in the table (for 250C).
С0 , К D ⋅ 10 −9 ∆S , C / mol ⋅ K ∆G, KC / mol E a , KC / mol ∆H , KC / mol
mol/l
0.2 48 5.6 -25.28 -9.6 8.63 -17.1
0.02 180 5.6 -39.52 -12.9 4.6 -24.6
0.002 1300 3.2 -66.82 -17.8 3.54 -37.7
As the table shows, the sorption of Pb2+ ions on Duolite C-467 (at 250C) is an
exothermic process at all studied concentrations, but with increasing concentration entalniya
of the process decreases, in other words, the sorption of Pb2+ ions is difficult. Increasing the
activation energy with increasing concentration is also related to this fact. This can be
explained with the energy costs of the system resulted from the overcoming resistance, which
has an ion exchanger to the diffusion of cations of the metal-chelating due to increased
"viscosity" of cations in the resin phase compared to the solution.
Gibbs energy values show that the sorption process occurs spontaneously and with
increasing concentration of the solution in the system rapidly established equilibrium.
INFLUENCE OF POLYELECTROLYTE ON DYNAMIC SURFACE PROPERTIES

OF BSA SOLUTIONS
Мilyaeva О.Y., Noskov B.A.
St. Petersburg State University, Department of Chemistry, St. Petersburg
e-mail: strekoza88-88@mail.ru
Aqueous solutions of the mixtures of proteins and polyelectrolytes have been widely
studied in recent years [1, 2]. The interaction between proteins and polyelectrolytes can lead to
the formation of soluble complexes. These complexes are able to aggregate further at higher
concentrations and to form coacervates. The interest in these systems is caused by their
applications in biocatalysis, biosensoring, for separation and purification of proteins, and drug
delivery.
In this study the dynamic surface elasticity of mixed solutions of bovine serum albumin
(BSA) and poly(dimethyldiallylammonium) chloride (PDMDAAC) was measured as a
function of the surface age, polyelectrolyte concentration and solution pH.
The addition of polyelectrolyte does not influence the dynamic surface properties of
protein solutions at pH below the isoelectric point of BSA. At the same time, significant
changes of the kinetic dependencies of dynamic surface properties at higher pH have been
observed indicating the interaction between the components. The acceleration of the changes
of the surface properties can be connected with the decrease of the electric adsorption barrier
due to the decrease of the total charge of the protein/polyelectrolyte complex.
The appearance of local maxima of the kinetic dependencies of the surface elasticity for
BSA solutions at pH above the protein isoelectric point shows that the additions of
PDMDAAC have a weak denaturing effect. The influence of the polyelectrolyte on the
dependence of the dynamic surface elasticity on the surface pressure becomes noticeable only
when the latter quantity exceeds ~12 mN/m. This effect differs significantly from the
influence on surface properties of conventional strong denaturing agents (GuHCl, urea and
ionic surfactants) [3]. We can assume a partial destruction of the protein tertiary structure
leading to the appearance of some tails and loops in the surface layer and thereby to non-
monotonical kinetic dependencies of the dynamic surface elasticity. The flexibility and
mobility of BSA molecules in the surface layer probably increases only slightly. At the same
time, it is impossible to exclude another possibility that the local maximum of the surface
elasticity for BSA-PDMDAAC adsorption layers, unlike the case of other studied systems, is
caused by the appearance of a special relaxation mechanism, for example, the matter exchange
between the assumed aggregates at the surface and the surrounding adsorption layer.
The work was financially supported by the Russian Foundation of Basic Research
(RFBR No. 11-03-00801_a) and the National Science Counsel of Taiwan (joint project RFBR
No. 09-03-92002-HHC_a).
References
1. C.L. Cooper, P.L. Dubin, A.B. Kayitmazer, S. Turksen, Curr.Opin.Colloid.Interface.Sci.
10 (2005) 52.
2. E. Kizilay, A.B. Kayitmazer, P.L. Dubin, Adv Colloid Interface Sci. 167 (2011) 24.
3. B.A. Noskov, A.A. Mikhailovskaya, S.-Y. Lin, G. Loglio, R. Miller, Langmuir 26 (2010)
17225.
SELFORGANIZATION IN COLLOIDAL SYSTEMS BY ENTROPIC

AND CAPILLARY FORCES
Mögel H.-J., Krüger S., Wahab M., Haustein M., Schiller P.
Technische Universität Bergakademie Freiberg. Freiberg/Germany
e-mail: hans-joerg.moegel@chemie.tu-freiberg.de
Beside direct pair interactions between molecules or colloidal particles, entropic and
capillary forces are very important interactions to establish appropriate thermodynamic
conditions for selforganization and restructuring in equilibrium systems. Using
thermodynamics and various mesoscopic theoretical concepts together with Monte Carlo
simulation techniques, we have demonstrated effects of these forces for stabilizing and
structure formation in biological membranes, amphiphilic aggregates, porous solids and
photonic crystals. If menisci appear in colloidal systems, e.g. fluid-fluid or fluid-air surfaces,
resulting capillary forces usually exceed all other forces. As an example, we consider
shrinking and swelling of a porous solid due to capillary forces. Combining thermodynamics
with capillary and elasticity theory both the adsorption isotherm and the volume change can be
described in dependence on pore size distribution and reduced vapour pressure of the
environment. We compare the results with experimental data for porous vycor-glas.
Furthermore, we consider entropic depletion forces between anisometric colloidal particles,
forces between adsorbed peptides and embedded proteins due to partial demixing of lipid
components in bilayer membranes in a vicinity of the membrane particles. The impact of
elastic membrane distorsions on the forces between the adsorbed or imbedded membrane
particles will be discussed. We compare the thermodynamic fluctuation theory of bilayer
membranes with Monte-Carlo-Simulations. In a second example, the medium mediated
attraction force of embedded proteins in a bilayer membrane due to membrane demixing and
elastic deformation will be evaluated and confirmed by Monte Carlo simulations. By means of
Monte Carlo simulations we could show that helical fiber structures can form from non-chiral
molecules based on the hydrophobic effect. Simple rigid surfactant molecules can self-
assemble into size restricted anisometric associates with constant negative Gaussian curvature
based on the hydrophobic effect.
DIFFERENTIAL ENTHALPIES AND ENTROPIES OF SODIUM CLORIDE

ADSORPTION AT THE SOLUTION/AIR INTERFACE
Osadchaya T.Yu., Fedorova A.A.
e-mail: physchem@isuct.ru
The surface tension of sodium chloride solutions in water, ethanol–water (xethanol = 0.1,
0.18, 0.3) and dimethylformamide (DMF)–water (xDMF = 0.14, 0.3) solvents have been measured
by capillary rise method at 298 and 303К. The excessive adsorption isotherms have been
calculated. And within thermodynamic models of the ions adsorption [1] the total adsorptions,
differential enthalpies and entropies of adsorption have been defined.
The calculations the thermodynamic characteristics of adsorption show that the values of
total adsorption at solution/air interface decrease with an increase in ethanol concentration in
water solution, but increase with an increase in DMF concentration. The temperature rise leads to
increasing of the total adsorption in water and ethanol-water solutions, and opposite trend is
observed in DMF-water solvents.
The Gibbs energy changes are negative for all study systems. Differential enthalpies and
entropies of electrolyte adsorption at solution/air interfaces change within -300÷150 kDg/mol and
-400÷30 Dg/mol∙K, respectively. The sign of these characteristics depend on solute concentration
and solvent nature. In particular, in the case of sodium chloride adsorption from water, the
process is endothermic for all solute concentrations and the entropies are positive too. However,
the transition from water to ethanol-water solvents leads to its decreasing and values sign
changes. So, in solvent with 0.3 mole ethanol fractions the calculated values are negative for all
sodium chloride concentrations. DMF additives to water solutions reduce the thermodynamic
characteristics of adsorption. Moreover, the sign changes of differential enthalpies and entropies
values are observed in this solvent as the solute concentration increases. In the adsorption system
with DMF mole fraction equal 0.14 the enthalpies have negative values till over 0.07 mol/kg
sodium chloride concentration, but in the case of increasing of DMF mole fraction up to 0.3 the
process already preserve exothermic character till 0.3 mol/kg.
On the basis of the calculated adsorption characteristics, some peculiarities of surface
layers formation at solution/air interface can be discussed. In particular, the data obtained allow
us to conclude that the types of concentration dependencies of differential enthalpies and
entropies of sodium chloride adsorption are connected with solvation interaction character in bulk
phase. This character is defined by nature and structure of water-organic solvent. As a result of
solvation interactions in protic solvent (an alcohols and water) the chloride-ions is localized at the
interfaces. In DMF-water solvents in the area of low DMF concentration, where the water-similar
structures are realized, the identical tendency is observed. However, with increasing of DMF
content in solution the cations primary adsorption and anions displacement from interface are
occurred. Besides the sodium chloride solvation is characterized by high enthalpies; and when the
molecules transit into surface layer, the desolvation changes the adsorptions heats of sodium
chloride in water solution till endothermic values. When the ethanol is added to water, the
desolvation enthalpies decrease and the magnitudes of thermodynamic characteristics become
negative. The additives of aprotic solvent - DMF reduce the endothermic effect of the sodium
chloride dissolution. As a result, with increasing of DMF concentrations in solution, the
desolvation contribution in the process of surface layers formation causes the appearance and
extension the area of negative enthalpies and entropies of adsorption.
Reference
1. Fedorova A.A., Ulitin M.V. // Russian Journal of Physical Chemistry. 2009, V.83,
№ 1 P. 113-118.
THERMODYNAMIC MODELLING OF SYSTEMS CONTAINING LIQUID CRYSTALS

Pestov S.M.
e-mail: pestovsm@yandex.ru
Liquid crystals (LC) have found a wide application in thermography, photonics as well as in
display technologies [1, 2]. A huge range of applications sets a lot of requirements to physical
properties of liquid crystalline materials (LCM). Modern LCM are multicomponent mixtures
needing to have a constant and reproducible composition with a wide temperature range of the
certain mesophase type.
Physico-chemical basis of LC material science is the phase diagram. Systems containing
thermotropic liquid crystals are the most interesting and difficult objects for physico-chemical
analysis [3]. Analysis of literature data has shown that more than 70 % of published phase
diagrams with LC contain errors in interpretation of thermal analysis and microscopy
measurements. The goal of the submitted work is to develop thermodynamic methods to predict
the phase diagram type and to obtain reliable data on LCM properties.
Comparative analysis of the existing prediction methods for phase diagrams is made.
Dependence of the invariant point position on components properties is analyzed. Activity
coefficients of components and the excess thermodynamic functions of the mesophase formation
are estimated. Thermodynamic model for description of the intermediate smectic phase formation
in nematic LC systems is proposed. Our measurements and estimations of surface properties of
LCM are in enough good coincidence.
Phase diagrams of LC – non-mesogen systems are important both for the solvent selection
for purification of mesogens and for choice of components (dichroic dyes, low viscosity addMore
than 200 calamitic nematic (smectic-nematic, smectic) LC – solvent systems are investigated.
Complete phase diagrams and solubility curves are obtained by DTA, visual analysis, polarizing
microscopy and solubility methods. Solubility curves of LC that belongs to different homologues
series (cyanobiphenyls, phenylbenzoates, benzoic acids, cholesteryl esters) are investigated. The
possibility to reveal the solid state polymorphism of mesogens by investigation of LC - non-
mesogen systems is demonstrated.
itives) for LC mixtures. Usage of the thermodynamic methods to predict the phase diagram
type, to calculate the solubility curves and invariant point position seems to be very interesting.
Excess thermodynamic functions for melting are calculated. The models based on the solubility
parameter (usage of Hildebrand and Hansen solubility parameters, the Flory-Huggins equation)
are applied for the demixing prognosis. Applicability of the group-contribution methods to
estimate activity coefficients of components (ASOG, UNIFAC models) is checked on the
solubility curves calculation. Data on thermodynamic and physical properties for mesogens are
taken from [4] or calculated using the group-contribution methods. Restrictions and advantages of
the considered thermodynamic methods are discussed. Correlations between alkyl chain length of
LC and their solubility in solvents of different polarity are determined.
References
1. Tomilin M.G., Pestov S.M. // Opt. Zh. 2012. V. 79. № 9. P. 66-80.
2. Tomilin M.G., Pestov S.M. Properties of liquid crystalline materials. SPb.:
Polytechnika, 2005. 296 p. (in Russ.)
3. Molochko V.A., Pestov S.M. Phase equilibria and thermodynamics of systems
containing liquid crystals. Moscow: Print. Center MITHT, 2003. 242 p. (in Russ.)
4. Pestov S.M. Physical properties of liquid crystals. / Landolt-Boernstein. N.S. VIII/5A.
Berlin: Springer, 2003. 492 p.
THERMODYNAMICS OF INCLUSION COMPLEXES WITH ORGANIC VAPOR

ADSORPTION ON THE SURFACE OF THE SUPRAMOLECULAR BILAYER
COATING IN «GAS — SOLID» SYSTEM
Pivovarova N.A, Kopytin K.А., Kudryashov S.Y., Onuchak L.A.
e-mail: kirko87@inbox.ru
The use of molecular organization at the interface produces organized monolayer and
thin films with controlled architecture. The intermolecular forces of various nature are
appearing the driving force in obtaining such film structures by the method of layer-assembly
(LbL – Layer by Layer). Approach based on the structural organization of LbL-method allows,
including various building blocks in multilayer different ways. Cyclodextrins and their
derivatives can perform as one of component of such bilayer structures. The orientation of
these compounds in the bilayer structure, and, consequently, the complexing properties will
depend of the structure and properties of preadsorbed orienting layer. Such an approach will
provide self-assembled films, which can be used as modifiers of adsorbents, catalysts, in
sensor technologies and in nanoscale devices.
It is determine the thermodynamic characteristics of the adsorption of organic
compounds at various spatial and electronic structure on graphite carbon adsorbent Carbopack
Y (CpY) and adsorbent CpY, coated bilayer of preadsorbed polyethylene glycol (PEG) and
unsubstituted β-cyclodextrin (β-CD).
It was found that assembling of two series of alternating monolayers (PEG and β-CD)
layer by layer on the surface of CpY sharp decreases adsorption constants of all studied
compounds than CpY. This effect is observed due to the screening surface graphite substrate
bilayer film modifier. However, an increase of the heats of adsorption is observed in the case
of aliphatic alcohols. It is significant that as the branched alkyl chain alcohol increase in the
number of carbon atoms falling heat of adsorption is found. Aliphatic alcohols such behavior
indicates that the main contribution to the intermolecular interaction makes no hydrogen
bonding and complex formation of the type «guest – host», as in the cavity of the molecule
can penetrate only a certain value. The increase in the heat of adsorption was found for the
cyclic compounds also. The rise of the entropy change in absolute value confirmed the
complexation with β-CD in the bilayer also. Weakening effect of the complex formation of
investigated aromatics compounds due to the fact that, despite the large amount of their
molecules, they have a «flat» structure, therefore, fewer contacts with the macrocyclic cavity
of β-CD.
Thus, the analysis of the thermodynamic properties can be concluded that complexation
of β-CD with a wide range of organic compounds can take place in the case of bilayer
adsorbent when the molecular size commensurate with the volume of macrocyclic cavity
unsubstituted β-CD.
STUDY OF COMPLEXATION IN THE «POLYDIMETHYLSILOXANE –

PERMETHYLATED β-CYCLODEXTRIN» BASED ON INVERSE
GAS CHROMATOGRAPHY
Platonov V.I., Onuchak L.A., Kuraeva Yu.G.,
e-mail: kuraeva81@mail.ru
Despite the large number of papers devoted to analytical aspects of enantioselectivity,
the thermodynamics of adsorption and complexation polymer systems with cyclodextrin is not
studied well enough.
Purpose – by inverse gas chromatography to study the thermodynamic characteristics of
the gas phase adsorption of organic compounds of different classes of binary stationary phase
«polydimethylsiloxane permethylated β-cyclodextrin» and to determine the thermodynamic
characteristics of the process of complexation "sorbate - macrocycle" in the polymer solution.
The stationary phase consisted of a polydimethylsiloxane additive heptakis-(2,3,6-tri-O-
methyl)-β-cyclodextrin (Me-β-CD) (10% wt.). As sorbates used 24 organic compounds
(arenes C6 – C8, cyclic and heterocyclic compounds, alkanols C2 – C5, optically active
compounds – (±)-camphene, (±)-limonene, (±)-menthol). Binding constant (stability)
kavitates «sorbate – macrocycle» K1 1:1 composition was calculated assuming a constant
structure of the polymer solvent in the presence of solutes. Kavitat enthalpy of formation in
the polymer solution ΔH ∗ was defined as the difference between the change in internal
energy of sorption (heats of adsorption) obtained on columns with binary and single stationary
phases.
Of the 24 studied sorbates only nine (alcohols C2 – C5, nitromethane, the optical isomer
of menthol) values ΔH ∗ are negative and range from -0.7 kJ/mol (2-propanol) to -12 kJ/mol
(menthol). For these values K1 of polar compounds are quite large (4.9 – 14.3) and decrease
with increasing temperature. For decalin, arenes, limonene, camphenes and polar compounds
such as butanone-2, tetrahydrofuran, pyridine, complexation occurs in athermal or slightly
endothermic binding process «sorbate – macrocycle» ( ΔH ∗ ≥ 0 ), which allows to conclude
that the dominant role of entropy deposit ( ΔS ∗ > 0 ) to the value of the free energy ΔG ∗ and
the binding constants K1 . For these compounds the weak interaction «sorbate – macrocycle»
offset by increases the number of possible conformations of molecules associated in kavitat
due by the presence of the free cavity of the macrocycle, and a change in the structure of a
linear polymer molecules near the Me-β-CD in the shape of a truncated cone height 8,8 Å. For
this group of compounds are small values K1 as the temperature increases.
THERMODYNAMICS OF DROPLET FORMATION ON SOLID PARTICLE

WITH ELECTRIC CHARGE LOCATED AT THE PARTICLE SURFACE
Podguzova T.S., Warshavsky V.B., Shchekin A.K.
e-mail: tpodguzova@mail.ru
Vapor nucleation on charged solid particles is a wide-spread fundamental phenomenon in
nature and technology. Although intensive studies in this field had been started from the end of
XIX century, there still stay questions in thermodynamic description of charge-induced droplet
formation which have to be answered. A few years ago, several experimental and theoretical
works [1-4] gave a new insight on this subject and raised the questions on the role of the charge
location with respect to the particle surface, the effects of wettability of the particle and the
deviation of the shape of the formed droplet from the spherical one.
Two years ago we have considered [5] the generalization of the classical J.J. Thomson and
Tohmfor-Volmer thermodynamic formulas by taking into account the disjoining pressure of the
thin liquid films in the central electric field of uniformly charged particles. Here we present our
recent results in thermodynamics of droplet formation in the axisymmetric electric field of a solid
dielectric nanoparticle carrying a discrete charge located at (attached to or absorbed in) the
particle surface. New equations for the chemical potential of a condensate molecule in the liquid
film around the particle, the work of the film formation and the film shape as functions of the
number of condensate molecules in the film and the value of an electric charge and its location
with respect to the particle surface have been derived analytically. The radius of the nanoparticle
and dielectric constants of the particle and condensate are the parameters of the theory. The
derived equations have been solved analytically, and a deviation of the condensed film shape
from the spherical one in the axisymmetric electric field of the discrete charge has been found
numerically.
By contrast to the classic theory for uniformly or centrally charged particles, our results
show the thermodynamic tendency to formation of non-spherical enveloping liquid film around a
dielectric nanosized particle even in the case of one elementary electric charge at the particle
surface. Being applied to the nucleation on the nanosized uniformly charged particles, the
conventional Kelvin-Thomson formula predicts that the radius of the droplet corresponding to the
maximum of the curve of the condensate chemical potential, as well as the radii of equilibrium
droplets, can be smaller than the radius of the charged particle. It caused doubts in complete
wetting of the condensation center in this case and formation of an enveloping droplet. We have
found that when the charge is near the surface of the particle and dielectric constant of the particle
is low then that for the condensate, the maximum of the curve of the condensate chemical
potential as a function of the number of condensate molecules in the film is located outside the
particle as well as the branch of this curve corresponding to stable enveloping liquid shells. The
addition of the disjoining pressure effects just strengthens this tendency.
This work was supported by the Program of Development of St. Petersburg State University
(grant 0.37.138.2011) and the Russian Foundation for Basic Research (grant 12-03-01145a).
References
1. C.-C. Chen, H.-C. Cheng, J. Chem. Phys. 126, 034701 (2007).
2. P. M. Winkler, G. W. Steiner, G. P. Reischl, A. Vrtala, P. E. Wagner, M. Kulmala, Science,
319, 1374 (2008).
3. P. M. Winkler, A. Vrtala, G. W. Steiner, D. Wimmer, H. Wehkamaki, K. E. Lehtinen, G. P.
Reischl, M. Kulmala, P. E. Wagner, Phys. Rev. Lett., 108, 085701 (2012).
4. B. Skinner, M. S. Loth, and B. I. Shklovskii, Phys. Rev. E., 80, 041925 (2009).
5. K. Shchekin, T. S. Podguzova, Atmospheric Research, 101, 493 (2011).
THERMODYNAMIC CHARACTERISTICS OF HYDROGEN ADSORBED ON THE

LIQUID PHASE HYDROGENATION CATALYSTS BASED ON PALLADIUM
Prozorov D.A., Barbov A.V., Merkin A.A., Shepelev M.V.
Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
Palladium catalysts are widely used in various processes of organic synthesis. According
to the known theoretical principles, laws of hydrogen adsorption on transition metals will
determine the activity and selectivity of the catalysts in the liquid phase hydrogenation
reactions. However the literature data about the interaction energy of the active centers of the
palladium catalyst surface with hydrogen are contradictory. The purpose is the study of
hydrogen adsorption from solutions on the catalysts containing palladium.
We used the samples of catalysts – palladium on carbon, with the metal content of 2.5 to
10 %. The samples of the catalysts prepared by deposition of transition metal from palladium
chloride solutions on the surface of activated carbon grade AR-B. The specific surface of the
samples, determined by low-temperature nitrogen adsorption at 77 K was 650 ± 30 m2/g. The
solvents were are selected aqueous solution of sodium hydroxide and sulfuric acid of varying
concentration. The heat of hydrogen adsorption and the maximum amount of adsorbed
hydrogen on palladium catalysts in different solvents and the composition at a temperature of
303 K was carried out by adsorption–calorimetric method [1].
Studies are shown that palladium catalysts are capable of absorbing large amounts of
hydrogen - to 51 sm3/g.Pd and their surface is energetically heterogeneous. With the
increasing amount of adsorbed hydrogen adsorption heat decreased from 158 to 5 kJ / mol.
The values of the heats of adsorption of hydrogen depend on the dispersion of particles of
palladium applied to coal, the nature and composition of solvents.
Within the model with a discrete surface heterogeneity for the ideal of the surface [2,3]
the thermodynamic characteristics of individual forms of hydrogen, such as the amount of
adsorbed hydrogen adsorption coefficient and the heat of adsorption of individual hydrogen
forms. The calculated results for palladium catalysts are shown that the observed dependence
of the heats of adsorption on the amount of adsorbed hydrogen can be described only in case
of the existence of forms of molecular and atomic hydrogen.
References
1. Ulitin M.V., Barbov A.V., Lefedova O.V., Gostikin V.P. // Izv. Vyssh. Uchebn.
Zaved. Khim. Khim. Tekhnol. 2005. V. 48. N 7. P. 62-72.
2. Barbov A.V., Shepelev M.V., Filippov D.V., Ulitin M.V. // Russian Journal of
Physical Chemistry A. 2010. Т. 84. № 9. С. 1605-1610.
3. Barbov A.V., Shepelev M.V., Denisov S.V., Ulitin M.V. // Izv. Vyssh. Uchebn.
Zaved. Khim. Khim. Tekhnol. 2007. V. 50. N 8. P. 25-29.
THERMODYNAMIC STUDY ON THE HENRY REGION ADSORPTION

OF SOME HETEROCYCLES ONTO POROUS GRAPHITIC CARBON AND PHENYL
BONDED SILICA GEL FROM AQUEOUS ORGANIC SOLUTIONS INCLUDING
ADDITIVES OF VARIOUS MACROCYCLIC COMPOUNDS
Saifutdinov B.R., Pimerzin А.А.
e-mail: sayf_br@mail.ru
Macrocyclic compounds are well known host molecules capable of forming inclusion
complexes with a wide variety of organic molecules. Inclusion processes at the interface and in
the bulk solution play a key role on the regulation of adsorption selectivity in solid-phase
extraction, purification, concentration, and high-performance liquid chromatography (HPLC). For
purposeful change of adsorption selectivity in liquid phase–solid systems we must know the
contributions of separate processes (solute transfer from bulk solution to the adsorption layer,
adsorbate complexation by macrocyclic compound at the interface and in the bulk solution,
solvation, association etc.) into changes of thermodynamic characteristics of adsorption.
Unfortunately, our knowledge about these contributions into effective enthalpy, entropy, and
Gibbs energy changes on adsorption from liquid phase on the surface of solids is poor.
In this paper we have attempted to fill existing gaps in our understanding using quasi
equilibrium HPLC method for a systematic thermodynamic study of the adsorption of solutes on
the surface of solids from aqueous organic solutions including additives of supramolecular
macrocycles.
We studied the fundamentals of the adsorption of 17 derivatives of 1,3,4-oxadiazole and
1,2,4,5-tetrazine from aqueous acetonitrile, methanol, and propanol-2 solutions with different
concentrations of various macrocycles onto porous graphitic carbon (PGC) and phenyl bonded
silica gel (PBS). As macrocycles we used α- and β-cyclodextrins, calyx[4]arene, and 5,10,15,20-
tetrakis(p-methoxyphenyl)porphyrin. The solute distribution coefficients (Kc) and Henry
adsorption constants (K1,c) were determined by HPLC method under quasi equilibrium conditions
at extremely low degrees of surface coverage (Henry region). Henry region adsorption of various
heterocycles was obtained as a function of temperature ranging from 313.15 K to 333.15 K with a
step of 5 K. From the van’t Hoff plot of Kc, the enthalpy and entropy changes were determined.
First, adsorption data were acquired and the influence of the nature of solute, macrocyclic
compound, and organic solvent, as well as temperature on these data was assessed. Then, the data
were analyzed according to the linear Gibbs energy relationship, enthalpy–entropy compensation,
and other exothermodynamic methods. Linear correlation showing compensation effect for
adsorption from various solutions onto PBS was observed. The influence of the nature and
concentration of macrocyclic compound in the compensation temperature was demonstrated. We
found that chemistry of solid surface of PGC and PBS and the nature of organic component of
solution and macrocyclic compound play an important role in the enthalpy–entropy compensation
phenomenon. Finally, the dependences of the thermodynamic characteristics of adsorption on the
organic solvent and macrocycle concentrations were determined. The introduction of macrocyclic
additives capable of molecular recognition into aqueous organic solutions essentially changes and
complicates of these dependences, thus opening the great opportunities for the regulation of the
adsorption selectivity of liquid phase–solid surface systems.
This work was supported by grant no. 12-03-01108-a from the Russian Foundation for
Basic Research.
APPLICABILITY OF THERMODYNAMICS TO NANOSIZED OBJECTS

AND SIZE DEPENDENCE OF SURFACE TENSION
Samsonov V. M.
e-mail: samsonoff@inbox.ru
On the one hand, a number of works has been published up to the present time devoted
to alternative approaches to nanothermodynamics. On the other hand, there are some papers
denying applicability of thermodynamics to objects of order of 1 nm in size. Though it was
already discussed before [1,2], it is necessary to emphasize that in fact one should talk about
applicability of thermodynamics not to a single nanoparticle but to an ensemble of them, with
no dependence whether Hill’s [3] or Gibbs’ method [4,5] is used. The problem of the
applicability of thermodynamics to nanosystems closely relates to the problem of the size
dependence of the surface tension. The problem of the applicability of thermodynamics to
nanosized objects and its relationship with the problem of the size dependence of the surface
tension σ will be discussed on the basis of thermodynamic treatment and using results of
computer experiments including ours [6] presented in Fig.1. It is noteworthy that R* = 1
(diameter of order of 1 nm) is the smallest droplet size for which σ * can be determined.
1,2 σ∗ 1
1,0
0,8
0,6
2
0,4
0,2
R*
0,0
2 4 6 8 10 12 14 16 18 20
Fig. 1. Dependences of the reduced surface tension σ * = σ a 2 ε ( a and ε are parameters of
Lenard-Jones’s potential) on the reduced droplet radius R* = R a : 1 – the reduced temperature
=
T * T=
Tc 0.7 , 2 – T * = 0.8 ( Tc is the critical temperature).
RFBR №13-03-00119
References
1. Samsonov V.M. // Russian Journ. Phys. Chem. A. 2002. V.76. P.1863.
2. Samsonov V.M., Bazulev A.N., Sdobnyakov N.Yu. // Central Europ. Journ. Phys. 2003.
V.1. P.474.
3. Hill T. Thermodynamics of small systems. Part. 1. W.A. Benjumin, inc., publishers.,
New-York – Amsterdam, 1963.
4. Gibbs J. W. The collected Works. V. 1. Longmans, Green and Co. 1928.
5. Rusanov A.I. Phasengleichgewichte und Oberflachenerscheinungen. Academie-Verlag,
Berlin, 1978.
6. Samsonov V.M., Khashin V.A., Dronnikov V.V. // Colloid. Journ. 2008. V.70. P.763.
THERMODYNAMICS OF SORPTION OF SOME BENZIMIDAZOLE DERIVATIVES ON

NON-POLAR SORBENTS FROM AQUEOUS-ACETONITRILE SOLUTION
Safronova I.A., Teplova E.A., Shafigulin R.V., Bulanova A.V.
e-mail: irinasa2007@yandex.ru
Now the study of sorption of biologically active substances (BAS) from polar solutions
on non-polar surfaces by reversed-phase high-performance liquid chromatography (RP HPLC)
is important in connection with a possible simulation of pharmacokinetics of drugs in the
body. Important factors in the chromatographic behavior of the sorbates are not only their
structure, composition of the eluent, but also the temperature. Effect of temperature on the
retention characteristics of substances in HPLC is studied sufficiently, at the time, as a study
of this effect allows us to calculate the enthalpy and entropy of sorption of substances from
liquid solutions, and explore the mechanism of sorption on non-polar sorbent substances of
different structure.
The aim of this research work is study of sorption of some benzimidazole derivatives in
RP HPLC on non-polar octadecyl silica gel from aqueous-acetonitrile eluent.
The experiment was performed on a «Milichrome A-02» microcolumn liquid
chromatograph (Novosibirsk, Russia) with UV - spectrophotometric detector.
Chromatographic column with octadecyl silica gel (SilC18) was used (the size of the column:
75x4- mm). As the eluent a mixture of acetonitrile – water (95:5 by volume) was used. Eluent
was degassed before the chromatographic analyses by installing UZDN-2T. Eluent flow rate
was 50 ml/min. The temperature of the column was supported by a solid-state electric
thermostat and varied in the range from 308 to 328 K in steps of 10 K. Injection volumes was
5 mcl.
In work based on the experimental data the values of heat effects of sorbate transition
from volume solution into surface layer sorbent and values of entropy factor were calculated
on the basis relationship of logarithm of retention factor from reciprocal temperature
lnk=f(1/T). It has been established that the internal energy is defining in the sorption of
benzimidazoles on non-polar sorbent as against entropy component because degrees of
freedom for sorbate transition from volume of aqueous-acetonitrile eluent into surface layer of
octadecyl silica gel was variable slightly.It appears that this is due to a complex mechanism of
sorption of benzimidazoles molecules on the surface of as a sorbent, and in its volume. The
influence of molecular structure of sorbates on the thermodynamic characteristics of sorption
was shown. It has been found that with the increase of the value of the polarizability increases
thermal effects for transition of benzimidazoles from aqueous-acetonitrile solution in layer of
octadecyl silica gel on account of increased dispersive interactions of benzimidazoles
molecules from non-polar sorbent and as a consequence of increasing the contacting area of
sorbates molecules with the surface of octadecyl silica gel.
This work was supported by the Ministry of Education and Science of the Russian
Federation within the framework of the state task grant № 3.3209.2011.
THERMODYNAMIC THEORY OF DELIQUESCENCE AND EFFLORESCENCE

IN NANOSIZED AEROSOLS
a
Shchekin A.K., aShabaev I.V., bHellmuth O.
a
St. Petersburg State University, St. Petersburg, Russia
b
Leibniz Institute for Tropospheric Research, Leipzig, Germany
e-mail: akshch@list.ru
Microphysical mechanisms involved in formation of thin films and small new phase
embryos in finite systems have a bright appearance in thermodynamic peculiarities of small
aerosols formed on soluble nanoparticles.
If soluble particles are placed into solvent vapor, condensation starts with formation of
liquid films and gradual dissolution of the particles. Depending on relative humidity of vapor,
initial size of nuclei and their solubility, the condensing droplets can exist either in the form of
thin liquid film around partly dissolved nucleus or in the form of the homogeneous droplet of
solution of the substance emerging from completely dissolved nucleus.1-3 There is a limiting value
of the vapor relative humidity and corresponding value of the vapor chemical potential above
which nuclei necessarily completely dissolve in droplets. The dissolution is called the
deliquescence transition, and the corresponding value of the vapor relative humidity is called the
deliquescence humidity. If we noticeably decrease vapor chemical potential below its saturation
value, a reverse (efflorescence) transition occurs, at which a solid nucleus crystallizes and grows
in the droplet; then, the final state will be the state of droplet in the form of film of saturated
solution around the nucleus.
If the nuclei are placed into supersaturated vapor, there are several possibilities. First, the
deliquescence transition as well as subsequent growth of the droplets and complete phase
transition into liquid state can occur without any activation barrier. Second, the deliquescence
transition may be barrierless, but the droplets of solution stay for some time in a metastable state
before they overcome the activation barrier to irreversibly grow. Third possibility is realized,
when the deliquescence activation barrier is the only barrier for subsequent phase transition, and
there is no a metastable state for droplets with completely dissolved nuclei. The fourth possibility
assumes that the deliquescence activation barrier is large enough to prevent deliquescence
transition and subsequent condensational growth.
To understand the thermodynamic peculiarities of heterogeneous nucleation on soluble
nuclei one needs to study the complex behavior of the extreme and saddle points of the work of
droplet formation and the relevant activation barriers for deliquescence, efflorescence and phase
transition as a function of the chemical potential of vapor, the initial size and the solubility of
condensation nucleus. This study has been undertaken previously partly only, and we will
summarize and extend it in this report, including the case of non-ideal solutions.
A special analysis will be given for the minima and saddle points of the work of droplet
formation. It will be demonstrated that, upon variations in the relative humidity of the vapor-gas
atmosphere around the droplets, the crossover in thermodynamically stable and unstable variables
of the droplet state takes place in the vicinity of the saddle point of the work. The physical
meaning of stable and unstable variables in the deliquescence and efflorescence transitions has
been clarified.
This work was supported by the Program of development of St. Petersburg State University
(grant 0.37.138.2011).
References
1. K. Shchekin and A. I. Rusanov, J. Chem. Phys. 129, 154116 (2008).
2. K. Shchekin, I. V. Shabaev, and A. I. Rusanov, J. Chem. Phys. 129, 214111 (2008).
3. K. Shchekin and I. V. Shabaev, Colloid J. 72, 432 (2010).
APPLICATION OF THE GRAND THERMODYNAMIC POTENTIAL

TO A SOLID–LIQUID–FLUID SYSTEM WITH A THREE-PHASE CONTACT LINE
Tatyanenko D.V., Shchekin A.K.
e-mail: dtat@mail.ru
Recently, a generalized definition of the grand thermodynamic potential Ω that incorporates
the immobile component of the crystalline lattice of a solid has been proposed [1]:
Ω = F − ∑i µi N i − µ βj N j (1)
with μi the chemical potential and Ni the number of molecules of a mobile component i, µ βj the
chemical potential of the component j which is immobile in the solid and mobile in an adjacent
fluid phase β (an equilibrium solution, melt or vapor), Nj the number of molecules of the
component j. In the absence of the mentioned adjacent fluid phase with the mobile component j in
equilibrium with the solid, µ βj should be taken [1] equal to the normal-to-the-interface
component of the chemical potential tensor [2] in the solid.
Using this definition, we can formulate thermodynamics of the solid–fluid two-phase
system. We define Gibbs’ surface tension σ as the specific surface excess of Ω, which is
common for fluids and solids and independent of the dividing surface location. It has been shown
that the difference between thermodynamic σ and mechanical γ definitions of the surface tension
for a solid interface at an arbitrary location of the dividing surface is determined by non-
uniformity and bulk anisotropy of the chemical potential tensor in the solid [1,3].
For a three-phase system including a solid in contact with two fluids, the thermodynamic
line tension κ can be defined as a line excess of Ω per unit three-phase contact line. Thus, for a
three-phase system (with fluid phases α, β and a solid phase γ) it decomposes into
Ω = − pαV α − p βV β + ω γ V γ + σ αβ Aαβ + σ αγ Aαγ + σ βγ Aβγ + κL (2)
with p the pressure, V the volume, ω the bulk density of the grand potential, A the area of an
interface, L the length of the three-phase contact line. Greek superscripts mark phases (single) and
corresponding interfaces (double).
The quantity κ is in a similar relation with the mechanical line tension τ [4] as σ with γ for
surfaces. Definition (2) with use of (1) allows one to consider strictly shifts of the solid–fluid
dividing surfaces and derive corresponding fundamental equations and relations between
thermodynamic and geometric quantities (such as the contact angle and the contact line
curvature). Thus, the grand thermodynamic potential (1) allows deriving the generalized Young
equation for a contact angle of a small droplet [5] for arbitrary solid–fluid dividing surfaces. This
might be useful in thermodynamics of sessile nanodroplets (and even smaller critical droplets at
heterogeneous nucleation) where line tension effects are substantial and the droplet can be formed
on a precursor film of a thickness comparable with the droplet height [6].
References
1. Rusanov A.I., Shchekin A.K., Tatyanenko D.V., J. Chem. Phys. 131 (16), 161104 (2009).
2. Rusanov A.I., J. Colloid Interface Sci. 63, 330 (1978).
3. Rusanov A.I., Tatyanenko D.V., Shchekin A.K., Colloid J., 72 (5), 673 (2010).
4. Rusanov A.I., Colloids Surf. A, 156 (1–3), 315 (1999).
5. Rusanov A.I., Shchekin A.K., Tatyanenko D.V., Colloids Surf. A, 250 (1–3), 263 (2004).
6. Checco A., Guenoun P., Daillant J., Phys. Rev. Lett. 91 (18), 186101 (2003).
THE ADSORPTION THERMODYNAMICS ON MICROPOROUS ADSORBENTS

AT THE SUPERCRITICAL TEMPERATURES
Tolmachev A.M., Kuznetsov T.A., Kryuchenkov N.G., Fomenkov P.E.
Lomonosov Moscow State University, Chemical Faculty, Moscow
e-mail: amtolmach@yandex.ru
On the example of the description of experimental isotherms of adsorption of methane,

krypton, xenon, nitrogen, oxygen and carbon dioxide on the AUK and PAU-10 microporous
active carbons possibility of the description of isotherms of adsorption for the first time is
shown at temperatures above critical by Dubinin-Radushkevich equations and the equations of
absolute adsorption of Tolmachev-Aranovich [1], when replacing pressure of saturated vapor
adsorptive, used as standard pressure at temperatures lower critical, on standard pressure
∗
( Ps ) which are linear extrapolation of dependences of a logarithm of pressure of saturated
vapor adsorptive (lnPs) on the return temperature in area of temperatures above critical.
Possibility of linear extrapolation is confirmed with the joint analysis experimental and
calculated by a method of molecular dynamics the isotherms of adsorption in a wide interval
∗
of temperatures [2]. It appeared that lnns, analog of equilibrium standard pressure ( Ps ),
linearly changes as function of the return temperature in a wide interval of temperatures lower
and higher (on 300-400K) critical and tangents of tilt angles of two dependences are identical.
In the report are discussed:
- Change of parameters of the equations in a wide interval of temperatures;
- Calculation of thermodynamic functions of adsorption and coefficients of activity of
the adsorbates (the complexes of molecules of an adsorbate with the adsorptive centers of
adsorbent and the free adsorptive centers) and their dependence on structure of the pores of
adsorbent and temperature;
- The description of dependences of coefficients of activity of components of the
adsorptive solutions from its composition at various temperatures by the equations of the
NRTL model and the analysis of temperature dependence of parameters of these equations.
Work is performed with Russian Fund of Basic Researches support, the project No. 11-
03-00446-a).
References
1. A.M.Tolmachev, T.A.Kuznetsova, I.A.Godovikov // Protection of Metals and
Physical Chemistry of Surfaces. 201 . V. 47. No. 3. P. 227-231.
2. A.M.Tolmachev, K.M.Anuchin, A.V.Bibin, N.G.Kryuchenkova, A.A.Fomkin//.
Colloid Journal. 2012 . V. 74 . No. 3. P. 392-399.
КИНЕТИКО-ТЕРМОДИНАМИЧЕСКИЕ ХАРАКТЕРИСТИКИ СОРБЦИИ Zn2+, Cd2+

и Pb2+-ИОНОВ КАТИОНИТАМИ ДАУЭКС МАС-3 и АМБЕРЛАЙТ IRP-64
Аббасов А.Д., Гейдарова Ф.Ф., Джафарли М.М., Мамедова Ф.С.
Институт природных ресурсов Нахчыванского отделения
НАН Азербайджана, Нахчыван
e-mail: ada.nat.res@mail.ru
В представленной работе приведены результаты кинетики и термодинамики сорб-ции
Zn , Cd2+ и Pb2+ -ионов слабокислотными полиакрилатными катионитами Амбер-лайт IRP-
2+
64 и Дауэкс МАС-3 в Н+-форме. В сухом состоянии Амберлайт IRP-64 имеет сорбционную

емкость в порядке 10 мг-экв/г, а Дауэкс МАС-3- примерно 3,8 мг-экв/мл.
Целью данной работы являлось изучение сорбционного равновесия, скорости его
установления и вычисление термодинамических параметров исследованных систем.
Термодинамическое описание обмена изученных ионов катионитами было проведено при
допущении идеальности твердой фазы, т.е. без учета коэффициентов активности ионов в
сорбированном состоянии.
Во всех случаях скорость сорбции изученных ионов катионитом Дауэкс МАС-3 вы-
ше, чем Амберлайт IRP-64. В то же время скорость сорбции ионов свинца обеими катиони-
тами ниже, чем цинк- и кадмий-ионов. По-видимому, это обстоятельство связано с боль-
шими размерами и тяжестью ионов свинца. Полученные кинетические данные позволили
констатировать наличие внутридиффузионного контроля процессов в выбранной
концентрации сорбируемых ионов Кажущаяся константа обмена K существенно мен-яется
при изменении степени заполнения катионитов. Одна из возможных причин этого явления,
по-видимому, наличие в катионитах функциональных групп, характеризу- ющихся
различными термодинамическими константами обмена, т.е. химической неоднородностью
сорбентов. В изученных системах основной вклад в определение высо-кой
избирательности на ионитах вносит уменьшение энтропии. На катионите Дауэкс МАС-3
величина энтропийного множителя во всех случаях меньше, чем на катионите Амберлайт
İRР-64. По-видимому, этот фактор обусловливает возможность без снижения
избирательности сорбции значительного ускорения процессов и уменьшения энергии
активации на изученных катионитах по сравнению с обычными смолами.
___________________________________________________________________________
Di, D0, Ea, ∆S 0 , ∆H 0 , ∆G 0 , K , λ2 e ∆S / R
см2/сек см2/сек кДж/моль Дж/моль.К кДж/моль кДж/моль см2
___________________________________________________________________________________________________
_ Zn2+ - Дауэкс MAC -3
6,50 ·10-7 1,01 · 10-4 12,5 - 50,187 -19,55 - 4,59 6,39 5,97·10-8
Cd Дауэкс MAC -3
2+
8,15 · 10-7 4,51 · 10-4 15,65 - 37,74 -15,47 - 4,22 5,5 2,67·10-7
Pb 2+- Дауэкс MAC -3
1,45 · 10-8 1,22 · 10-4 22,4 - 48,58 -18,03 - 3,55 4,2 7,24·10-18
___________________________________________________________________________________________________
_
Zn 2+ -Амберлайт IRP-64
5,65∙10 -7
2,05 ∙ 10 -4
14,60 -44,30 -17,62 -4,42 5,95 1,21·10-17
Cd2+-Амберлайт İRP – 64
6,54 ∙ 10-7 1,24 ∙ 10-3 18,70 - 29,33 - 12,85 -4,11 5,25 7,34·10-17
Pb2+- Амберлайт İRP – 64
1,16 ∙10-8 3,29∙10-4 25,40 -40,36 -15,75 -3,72 4,5 1,95·10-17
Большее сродство ионитов к изученным ионам обусловлено уменьшением энтропии

системы. Энтальпийный фактор определяет самопроизвольное протекание процессов
сорбции изученных ионов исследованными ионитами.
ВЛИЯНИЕ ПРЕБЫВАНИЯ ВОДЫ В СИЛЬНОМ ЭЛЕКТРИЧЕСКОМ ПОЛЕ

НА ЕЕ ПОВЕРХНОСТНЫЕ СВОЙСТВА
Атаев Г.М.
Институт физики Дагестанского НЦ РАН, Махачкала
e-mail: ataev@mail.ru
В последнее время появился интерес к изучению последствий влияния
магнитного поля на структуру воды и ее физико-химические свойства (см., напр., [1]).
Представляло интерес проверить изменение свойств воды после воздействия
электрического поля. В связи с этим и было предпринято данное исследование
Было исследовано температурное поведение межфазного натяжения (МФН) в
бинарной смеси бидистиллированная вода – н-нонан степени чистоты «чда». Вода
предварительно выдерживалась в однородном электрическом поле величиной около
106 В/м в течение нескольких часов. Было выполнено по три серии измерений, в
которых поочередно использовалась вода, подвергшаяся и не подвергшаяся
воздействию поля. Исследования велись методом лежащей капли в диапазоне
температур от комнатной до 100°С. Исследуемые вещества помещались в герметичную
высокотемпературную оптическую ячейку постоянного объема, которая находилась в
воздушном термостате. Термостатирование осуществлялось с помощью регулятора
температуры ВРТ-3; температура измерялась миниатюрным платиновым термометром
ТСПН-3. Линейные размеры внутри
45 σ, мДж/м
2
оптической ячейки измерялись
катетометром В-630. Измерение МФН
происходило путем
фотографирования капли цифровым
40
фотоаппаратом Panasonic Lumix DMC
FZ8 и последующей обработки
полученного изображения на
компьютере. Ошибка измерения
Т, С поверхностного натяжения при
35
20 40 60 80 100 калибровке не превышала 1%, что
означает ошибку измерения МФН в
Рис. 1
пределах 2%.
Результаты приведены на рис. 1.
Здесь светлые кружочки соответствуют значениям, полученным без поля, а темные
треугольники – значениям, полученным после воздействия поля. Отсюда можно
сделать следующие выводы. Продолжительное воздействие на воду сильного
электрического поля привело к уменьшению МФН на величину 1.5 мДж/м2, что
составляет около 3.5% при комнатной температуре. С ростом температуры эта разность
сохраняется.
1. Ran Cai, Hongwei Yang, Jinsong He, Wanpeng Zhu. The effects of magnetic fields on
water molecular hydrogen bonds. Journal of Molecular Structure. 938 (2009). P. 15–19.
ТЕМПЕРАТУРНАЯ ЗАВИСИМОСТЬ ПОВЕРХНОСТНОЙ СВОБОДНОЙ ЭНЕРГИИ

КРИСТАЛЛ–ЖИДКОСТЬ НА МЕТАСТАБИЛЬНОМ ПРОДОЛЖЕНИИ
КРИВОЙ ПЛАВЛЕНИЯ И ВБЛИЗИ КОНЕЧНОЙ КРИТИЧЕСКОЙ ТОЧКИ
(МОЛЕКУЛЯРНО-ДИНАМИЧЕСКИЙ ЭКСПЕРИМЕНТ)
Байдаков В.Г.
Институт теплофизики Уральского отделения РАН, Екатеринбург
e-mail: baidakov@itp.uran.ru
При отрицательных давлениях и температурах ниже температуры тройной точки
метастабильные кристалл и жидкость могут равновесно сосуществовать на плоской
межфазной границе. Точка прекращения такого равновесия – конечная критическая
точка, есть точка встречи кривой плавления со спинодалью растянутой жидкости. В
этой точке критического состояния достигает только одна фаза – жидкая.
Нами в молекулярно-динамических экспериментах методами разделяющего
потенциала и термодинамического интегрирования Гиббса–Кана в системе леннард-
джонсовских частиц рассчитана поверхностная свободная энергия кристалл–жидкость
γ. Исследуемые модели содержали до 250 000 взаимодействующих частиц с
ориентациями кристаллической фазы относительно межфазной границы (100), (110) и
(111). В методе разделяющего потенциала поверхностная свободная энергия
рассчитывалась согласно ее определению через обратимую работу образования
единицы площади межфазной границы. Данный метод использовался для расчета γ при
температуре тройной точки= t / ε 0.692 , где kB – постоянная Больцмана, ε –
Tt* k BT=
параметр потенциала Леннарда-Джонса. При T * > Tt* и T * < Tt* рассчитывались
плотности соответствующих фаз, поверхностная энергия и поверхностное напряжение,
по которым методом термодинамического интегрирования Гиббса– Кана определялась
поверхностная свободная энергия.
Установлено, что в области положительных давлений γ является монотонно
возрастающей функцией температуры. При всех температурах γ (100) > γ (110) > γ (111) .
Величина анизотропии в γ не превышает 6 %.
Поверхностная свободная энергия уменьшается по мере приближения к конечной
критической точке, принимая в ней значение γ K* = γσ2 / ε = 0.361 , где σ – параметр
потенциала. В тройной точке усредненное по ориентациям значение γ t* =0.420 . При
подходе к конечной критической точке возрастает корреляционный радиус в жидкой
фазе, что приводит к асимметрии профиля плотности. Сохранение резкой межфазной
границы со стороны кристаллической фазы и неограниченный рост толщины
межфазного слоя со стороны жидкости приводят к обращению в ноль в конечной
критической точке поверхностной энтропии. Критический индекс поверхностной
свободной энергии кристалл – жидкость при этом близок к критическому индексу
поверхностного натяжения для критической точки жидкость–газ. Установлена
корреляция между γ, теплотой фазового перехода, температурой и плотностью,
позволяющая прогнозировать температурную зависимость γ простых веществ.
Работа выполнена при поддержке программы Президиума РАН № 2 (проект 12-
П-2-1008) и РФФИ (проект 12-08-00467).
ТЕРМОДИНАМИЧЕСКИЕ ХАРАКТРИСТИКИ ГИДРАТАЦИИ

БИФУНКЦИОНАЛЬНЫХ ПОЛИМЕРНЫХ СОРБЕНТОВ
Бондарева Л.П., Гапеев А.А., Челноков Д.А.
Воронежский государственный университет инженерных технологий, Воронеж
e-mail: larbon@mail.ru
Сорбционная очистка воды и выделение различных компонентов на полимерных
сорбентах осуществляется, как правило, в динамических условиях, в переносе вещества
определяющую роль играет растворитель, как в фазе ионообменника, так и раствора. Кроме
того важнейшим фактором, определяющим селективность сорбции, является состояние воды
в полимере. Таким образом, целью настоящего исследования стало определение
термодинамических характеристик: энергии Гиббса, энтальпии гидратации и энтальпии
дегидратации бифункциональных ионообменников в различных ионных формах, в том числе
количественная оценка степени гидратации, соотношений энергетически неравноценной
воды в фазе аминофосфонового и аминокарбоксильного полимерных сорбентов.
Исследования проводили на макропористых хелатообразующих ионообменниках
Purolite S930 и Purolite S950, предназначенных для извлечения из водных растворов
катионов тяжелых металлов и связывания органических ионов, в том числе аминокислот.
Полимерная матрица сорбентов представляет собой полистирол, сшитый
дивинилбензолом, с привитыми аминофосфоновыми (S950) и аминокарбоксильными
(S930) функциональными группами. В работе использовался комплекс экспериментальных
методов: изопиестирования, дериватографии, ИК-спектроскопии; определение энтальпий
гидратации ионообменника в различных ионных формах проводилось на калориметре
переменной температуры с изотермической оболочкой.
Набухание Purolite обусловлено наличием в гидрофобной матрице аминофосфоновых
или аминокарбоксильных групп и подвижных ионов. Установлено, что способность
поглощать воду зависит от природы функциональных групп: количество воды
поглощенной Purolite S930 в 2,5 – 4 раза меньше, чем Purolite S950. Поскольку натриевая
форма ионообменников сильнее ионизирована, чем медная и никелевая, она имеет
максимальную способность к гидратации, однако двухзарядные ионы являются
дополнительными центрами поглощения воды. Глобулярная структура протонированных
ионообменников, образующаяся за счет водородных связей, препятствует гидратации
полиамфолитов в водородной и аланиновой формах. Для всех изученных форм
ионообменников выделены три вида гидратной воды, различающихся типами связи с
полимером: воду ближней гидратации – структурно-связанную и сорбционно-связанную;
средней гидратации – капиллярную; дальней гидратации – осмотическую (свободную
воду). Обнаружено различие величин энтальпий гидратации и дегидратации для всех
изученных форм Purolite S950, сделано предположение о том, что часть прочносвязанной
воды остается в ионообменнике даже после высушивания под вакуумом.
Величину и знак свободной энергии Гиббса (∆гG) определяет соотношение
энтальпийного и энтропийного вкладов. Различия в ∆гG могут быть обусловлены либо
разницей в энтальпии сорбции воды полимером, либо изменениями в его структуре,
отражающимися в величине энтропии. Энергия Гиббса максимальна для натриевых форм
полиамфолитов, минимальна для протонированной, при этом количество связанной воды
уменьшается в ряду ионных форм Ni2+ > Cu2+ > Н+ > Ala± > Na+. Максимальные значения
энтальпии наблюдаются при гидратации натриевых форм полиамфолитов, минимальные –
аминокислотных, соотношение величин энтальпий и свободных энергий гидратации
медной и никелевой форм различны.
ТЕРМОДИНАМИКА АДСОРБЦИИ ПАРОВ ОРГАНИЧЕСКИХ СОЕДИНЕНИЙ

ДЕНДРИМЕРАМИ
Герасимов А.В., Горбачук В.В., Зиганшин М.А.
Казанский (Приволжский) федеральный университет, Казань
e-mail: Alexander.Gerasimov@ksu.ru
Выяснение связи селективности рецептора и его сродства к субстрату со
структурными характеристиками взаимодействующих молекул является актуальной
проблемой современной физической химии. Решение этой проблемы важно для
создания интеллектуальных систем распознавания вкуса и запаха, материалов для
связывания и хранения паров и газов, которые можно использовать при решении задач
экологии и энергетики.
Наличие сверхразветвленной структуры с внутренними полостями обеспечивает
повышенную селективность, хорошее сродство и высокую чувствительность рецептора
к субстрату, а также достаточную термическую и кинетическую стабильность
продуктов их взаимодействия. Такими свойствами обладают фосфорсодержащие
дендримеры, способные связывать разнообразные органические вещества и газы
благодаря наличию жесткой молекулярной структуры, внутримолекулярных полостей и
каналов.
В настоящей работе впервые проведено комплексное исследование рецепторных
свойств фосфорорганических дендримеров. с разным размером молекулы по
отношению к летучим органическим соединениям и воде. Определены
термодинамические параметры образования, состав и параметры стабильности
продуктов насыщения фосфорсодержащих дендримеров. Показано, что с ростом
номера поколения имеет место немонотонное изменение рецепторных свойств
дендримеров. Причем эта зависимость различна для различных групп гостей и
определяется как природой, так и размером молекул гостя.
Установлено, что использование разработанных в настоящей работе методик
нанесения рабочего покрытия и его регенерации позволяет получать сенсоры с
воспроизводимыми рабочими характеристиками.
Обнаружено, что гидратация не оказывает заметного влияния на рецепторные
свойства фосфорорганических дендримеров по отношению к парам гидрофобных
соединений, что позволяет использовать эти макромолекулы в качестве рабочих
покрытий в сенсорах в широком диапазоне влажности воздуха.
Обнаруженные линейные соотношения типа «структура-свойства» для различных
гомологических рядов гостей позволяют говорить о наличии различных по
селективности сорбционных центров в структуре фосфорорганических дендримеров.
Показано, что различие в селективности связывания изученными дендримерами
является достаточным для создания массива сенсоров, позволяющего эффективно
распознавать индивидуальные пары различных органических соединений, причем
трехсенсорная система является наиболее эффективной.
Работа выполнена при финансовой поддержке РФФИ № 12-03-31788 мол_а.
ИССЛЕДОВАНИЕ СОРБЦИОННОГО КОНЦЕНТРИРОВАНИЯ КОБАЛЬТА

МОДИФИЦИРОВАННЫМИ УГЛЕРОДНЫМИ ВОЛОКНАМИ
Григорьева А.В., Валинурова Э.Р., Кудашева Ф.Х.
e-mail: bbelka91@list.ru
Использование активированных углеродных волокон является одним из наиболее
перспективных методов извлечения тяжелых металлов из производственных растворов.
Как показали исследования, преимуществом данного сорбционного метода является
возможность многократного использования сорбента в цикле «сорбция – десорбция»,
что значительно увеличивает экономическую эффективность сорбционной очистки, а
также возможность применения метода для извлечения органических токсикантов из
объектов окружающей среды.
Целью данной работы явилось изучение процесса комплексообразования ионов
кобальта с поверхностью углеродного гидратцеллюлозного волокна,
модифицированной хелатообразующими реагентами, с помощью атомно-силовой
микроскопии.
Модифицированные образцы углеродных волокон получали жидкофазным
окислением концентрированной азотной кислотой, обработкой 0.2%-ным водным
раствором 1,10-фенантролина и 2.5%-ным раствором О-оксихинолина в 6%-ной
уксусной кислоте. Изучение сорбции проводили при двух различных температурах:
25ºС и 35ºС. Исследование морфологии поверхности углеродного волокна
осуществляли на атомно-силовом микроскопе Agilent Technologies 5500 Scanning Probe
Microscopy. АСМ съемки проводили полуконтактным способом, с помощью
кантилевера толщиной 4,0±1мкм, длиной 125±10 мкм, высотой 30±7,5 мкм с
жесткостью балки 10-130 Н/м при резонансной частоте 204-497 кГц. Выбирали
изображения в наиболее информативных представлениях и обрабатывали с
использованием программы Pico Image Basic.
Взаимодействие кобальта с функционально-аналитической группой приводит к
образованию комплекса, молекулы которого равномерно распределяются по
поверхности модифицированного углеродного волокна. Была установлена зависимость
степени извлечения кобальта модифицированными углеродными волокнами и
параметров сорбции от температурного режима. Построены изотермы сорбции ионов
кобальта на исходном и модифицированных углеродных волокнах и рассчитаны
теплоты адсорбции.
Показано, что жидкофазное окисление активированного углеродного волокна
азотной кислотой способствует росту степени извлечения кобальта из воды на 25%, а
предварительная обработка углеродного волокна фенантролином - на 4% и 8-
оксихинолином - на 11 %. Установлено, что увеличение температуры сорбции на
10ºС повышает степень извлечения кобальта пропитанными волокнами до 57 % и 83 %
соответственно.
ИССЛЕДОВАНИЕ РАЗМЕРА И ФОРМЫ МИЦЕЛЛ

НЕКОТОРЫХ ОТЕЧЕСТВЕННЫХ ПАВ
Гусев С.В., Кудряшова О.С.
Естественнонаучный институт Пермского государственного национального
исследовательского университета, Пермь, e-mail: goosess@mail.ru
Структурно-организованные жидкие среды все чаще привлекают к себе внимание
исследователей, так как имеют очевидные перспективы применения во многих
областях науки и нанотехнологии. Значительный интерес вызывают мицеллярные и
микроэмульсионные системы на основе поверхностно-активных веществ (ПАВ).
Наличие наноуровневой структуры в таких системах определяет их особые свойства.
Благодаря своей высокой солюбилизирующей способности по отношению к
различным объектам, ПАВ активно используются в аналитических методах
экстракционного концентрирования. При некоторой температуре водные растворы
ПАВ становятся мутными вследствие образования новой фазы (фаза, обогащенная
ПАВ). При нагревании разрушаются водородные связи между надмолекулярными
ассоциатами ПАВ и водой, что приводит к фазовому разделению. Это свойство ПАВ
используется в методах мицеллярной и ферментативной микробиологической
экстракций.
Цель данной работы заключалась в определении критической концентрации
мицеллообразования (ККМ), а также исследовании размера, формы и чисел агрегации
мицелл водных растворов НПАВ ОП-10 (полиэтиленгликолевые эфиры пентаэритрит
стеаратов (C17H35COOCH2)2C[CH2O(C2H4O)nH][CH2O(C2H4O)mH], n+m= 40) и АПАВ
оксифос Б (калий бис-(алкилполиоксиэтилен)-фосфат [CnH2n+1O(C2H4O)m]2POOK, n=8-
10, m=6) в зависимости от температуры, концентрации сурфактанта и неорганической
соли. Для этого визуально-политермическим методом изучены температуры фазового
перехода (температуры помутнения, cloud point temperature) в трехкомпонентных
системах ПАВ – неорганическая соль – вода. Для снижения температуры фазового
перехода (оптимизация условий проведения мицеллярной экстракции) использованы
следующие соли: NaCl, KCl, NH4Cl, MgCl2, CaCl2, AlCl3, Na2SO4, NaNO3, Na3PO4,
NaH2PO4, NaCNS.
ККМ, а также численные значения параметров n и m, отвечающих за количество
ионов ПАВ и противоионов мицеллы в приближении Хартли, определены методом
кондуктометрии. Методом динамического рассеяния света определены
гидродинамические диаметры и числа агрегации мицелл ПАВ при разных
температурах и концентрациях солей. Установлено, что в отсутствии соли размер
мицелл в широком интервале концентраций (от 10-4 до 0.05 моль) постепенно
возрастает. Введение соли приводит к резкому увеличению среднего диаметра мицеллы
до десятков мкм, а также к изменению вида распределения по размерам частиц от
мономодального (один пик с узким основанием) к би- и полимодальным, что, косвенно
свидетельствует о смене геометрии мицелл в растворе со сферической на вытянутую
эллипсоидную, сфероцилиндрическую или стержневую.
В настоящее время ведутся исследования зависимости формы и размера мицелл
ПАВ оксифос Б и ОП-10 от температуры и концентрации сурфактанта методом атомно-
силовой микроскопии, что позволит устанавливать геометрические параметры мицелл
в реальном времени.
Полученные данные будут использованы для установления связи между
эффективностью концентрирования и структурными параметрами мицелл.
ЭНЕРГЕТИЧЕСКАЯ НЕОДНОРОДНОСТЬ ПОРИСТЫХ ПОЛИМЕРОВ

ПО ДАННЫМ ГАЗОВОЙ ХРОМАТОГРАФИИ
Гуськов В.Ю., Кудашева Ф.Х.
e-mail: guscov@mail.ru
Неоднородность представляет собой одно из фундаментальных свойств любых
поверхностей. В то же время, на настоящий момент изучение энергетической
неоднородности поверхности как наличия на ней адсорбционных центров с различной
энергией адсорбции представляет собой «белое пятно» в современной термодинамике
поверхностей. Несмотря на большое число подходов к решению уравнения,
связывающего изотерму адсорбции с функцией неоднородности, на настоящий момент
не существует единого подхода, который позволил бы достоверно определить степень
энергетической неоднородности поверхностей различных сорбентов. В настоящей
работе предпринята попытка исследовать функцию неоднородности микропористых
полимеров на основе стирола и дивинилбензола.
В качестве объектов исследования были выбраны полимерные сорбенты Поролас-
Т, L-285, SD-2 и MN-200, различающиеся размером пор и удельной поверхностью.
Исследование проводилось методом обращённой газовой хроматографии на
хроматографе «Агат» с детектором по теплопроводности. Температура колонки
составляла 200 °С. Использовался режим конечной концентрации, при котором пробы
вводились в виде жидкости, объёмом от 0,02 до 70 мкл. В качестве тест-сорбатов
использовались молекулы гексана и н-бутанола.
Из экспериментальных данных были построены зависимости удерживаемого
объёма от концентрации сорбата в газовой фазе. Было установлено, что они имеют
логарифмическую форму. Исходя из этого, путём преобразования уравнения для
функции неоднородности была выведена следующая формула:
где А – предлогарифмическая константа, с – концентрация сорбата в газовой фазе,

ммоль/л, am – ёмкость монослоя, мкмоль/г, k – константа Больцмана, Т – температура,
К.
Показано, что рассчитанные функции неоднородности зависят от выбора
молекулы-зонда. Для полярной поверхности SD-2, имеющего пришитые амино-группы,
функция неоднородности по н-бутанолу лежала значительно выше, чем для гексана,
что свидетельствует о большем количестве адсорбционных центров. Установлено, что
для сорбентов с большей сорбционной активностью неоднородность поверхности
также будет больше. Обнаружено, что сверхсшитый полистирол MN-200 по своей
энергетической неоднородности близок к микропористому сополимеру стирола и
дивинилбензола L-285.
Для оценки достоверности применяемых функций неоднородности было
проведено модифицирование поверхности полимера L-285 полиэтиленгликогем ПЭГ-
4000 в количествах от 10-5% до 1% от массы полимера. Было обнаружено, что
стандартная функция неоднородности малочувствительна к изменению свойств
поверхности - только до 0,1% ПЭГ. Было предложено использовать производную от
функции неоднородности для вычисления количества адсорбционных центров только
при определённой энергии адсорбции. Обнаружено, что функция полученной
производной от степени заполнения будет чувствительной до 10-4% от массы полимера.
ПАРАДОКС ШРЁДЕРА И ПАРАДОКСЫ ТЕРМОДИНАМИКИ НАБУХАНИЯ

ПОЛИМЕРОВ В ПАРАХ И В ЖИДКОСТЯХ
Даванков В.А., Пастухов А.В., Павлова Л.А.
Институт элементоорганических соединений им. А.Н. Несмеянова РАН, Москва
e-mail: davank@ineos.ac.ru
В 1903 году немецкий химик Шрёдер показал, что пластинка желатины набухает в
жидкой воде в 25 раз сильнее, чем в насыщенных парах воды. Этот факт противоречил
общепринятому положению термодинамики, гласящему, что химические потенциалы воды
в жидкой и насыщенной паровой фазе одинаковы и потому вода и пар должны одинаково
воздействовать на третью равновесную (полимерную) фазу. Парадокс Шрёдера до сих пор
не нашел разумного термодинамического объяснения.
С применением автоматической регистрации изменяющихся размеров единичной
сферической гранулы полимера мы показали, что набухание любого (сшитого) полимера в
любой жидкой фазе всегда происходит быстрее и в большей степени, чем в насыщенных
парах растворителя над этой жидкостью. Значит, явление Шрёдера имеет всеобщий
характер и связано не с кинетикой, а с термодинамикой сорбции растворителя.
В равновесной однокомпонентной системе жидкость/пар надо рассматривать не два,
а три ансамбля молекул. (1) Молекулы паровой фазы практически не взаимодействуют
друг с другом. (2) Молекулы объёмной жидкой фазы на коротких расстояниях друг от
друга испытывают скомпенсированное всестороннее взаимное притяжение. (3) Молекулы
на границе раздела жидкость/пар испытывают притяжение только со стороны объёмной
жидкости. Последнее резко понижает способность выхода молекул воды в паровую фазу.
Структура поверхностных слоев воды вообще принципиально отличается от объёмной
воды. Важно, что только эти слои (3) находятся в равновесии с паром.
Однако наши эксперименты выявили совершенно иное, действительно
парадоксальное явление: набухший в жидкости полимер не склонен возвращать в
насыщенный пар «избыток» поглощенного растворителя. Для отторжения в насыщенный
пар этого принятого из жидкости избытка нет никаких термодинамических причин. Фаза
набухшего полимера не может генерировать более высокое давление над своей
поверхностью, т.к. в равновесии с паровой фазой здесь опять-таки участвуют только те
молекулы сорбата, которые находятся на поверхности конденсированной фазы (набухшего
полимера) и которые испытывают одностороннее притяжение только к этой фазе.
Парадоксальность ситуации заключается в том, что в равновесии с насыщенным
паром может оказаться сшитый полимер с любым содержанием сорбата, укладывающимся
в пределы от насыщения полимера паром до его насыщения жидкостью. Таким образом, в
системе пар/жидкость/полимер существует не два специфических равновесных состояния с
самостоятельными минимумами потенциальной энергии, а одна очень широкая зона
минимальной потенциальной энергии.
Тем не менее, при длительном эксперименте малейшие колебания температуры
системы или временные падения парциального давления пара приводят к медленному
необратимому уменьшению количества сорбата, хотя и не до уровня начального
«равновесного» набухания в паре. В докладе даётся рациональное объяснение и этого
парадокса в рамках рассмотрения колебаний полимерных цепей пространственной сетки с
необратимым возникновением новых прочных межцепных дисперсионных контактов.
Последние уже не могут быть разорваны воздействием насыщенного пара (хотя и
разрывались воздействием более активного жидкого сорбата).
Reference
V.A. Davankov, A.V. Pastukhov, J. Physical Chem. B. 115/51 (2011) 15188-15195.
ТЕРМОДИНАМИКА ПОЛИМОРФНЫХ ПРЕВРАЩЕНИЙ

СУПРАМОЛЕКУЛЯРНЫХ РЕЦЕПТОРОВ ПОД ДЕЙСТВИЕМ
ПАРООБРАЗНЫХ СОЕДИНЕНИЙ
Зиганшин М.А., Лучай К.В., Горбачук В.В.
Химический институт им. А.М. Бутлерова,
Казанский федеральный университет, Казань
e-mail: Marat.Ziganshin@ksu.ru
Полиморфизм супрамолекулярных рецепторов, приводящий к образованию
метастабильных структур, может существенно влиять на их сорбционную способность
по отношению к парообразным веществам и газам. Рецепторы, способных к
полиморфизму и/или псевдополиморфизму, могут быть использованы как новые
сорбционные материалы с повышенной и регулируемой селективностью, сорбционной
емкостью и термостабильностью, в качестве теплатов при получении
высокоорганизованных поверхностей для решения задач энергетики, экологии и
медицины.
В настоящей работе были определены параметры полиморфных и
псевдополиморфных переходов в фазе супрамолекулярных рецепторов совмещенным
методом термогравиметрии и дифференциальной сканирующей калориметрии с масс-
спектрометрическим анализом уходящих паров и газов. Сорбционные свойства
супрамолекулярных рецепторов, находящихся в различных модификациях, по
отношению к парообразным органическим соединениям были охарактеризованы
статическим методом парофазного газохроматографического анализа, а также с
помощью пьезоэлектрических сенсоров типа кварцевых микровесов. Изменение
морфологии поверхности наноразмерных пленок рецепторов изучалось методом
зондовой микроскопии.
В результате проведенного исследования был разработан новый подход к
молекулярному распознаванию паров ряда органических соединений, как
индивидуальных, так и находящихся в сложных смесях. Предложен подход,
позволяющий предсказывать влияние парообразных соединений на морфологию
наноразмерных пленок рецепторов, по данным сенсорного анализа.
Исследование выполнено при финансовой поддержке РФФИ в рамках научных
проектов №12-03-00590-а и 11-03-01215-a.
ПРИМЕНЕНИЕ МЕТОДА ФУНКЦИОНАЛА ПЛОТНОСТИ К ИССЛЕДОВАНИЮ

АДСОРБЦИИ ВОДОРОДА УГЛЕРОДНЫМИ АДСОРБЕНТАМИ
Зубков В.В., Гринев И.В., Самсонов В.М.
e-mail: samsonoff@inbox.ru
В связи с перспективами развития водородной энергетики, возникла
необходимость в разработке методов хранения водорода и его последующего
использования в качестве топлива. Для решения этой прикладной задачи необходимо
также развитие теоретических подходов, позволяющих надежно рассчитывать
адсорбцию водорода на твердых поверхностях и в углеродных адсорбентах различного
типа. Как показали наши предыдущие работы [1-4] метод функционала атомной
плотности (МФАП) в полной мере отвечает поставленным требованиям.
Нами проведены сравнительные расчеты величины адсорбции водорода в
пористых графитах, моделируемых как система щелевидных пор, разделенных
монослоями графена, а также в материалах, представленных молекулами фуллеренов
( C60 , C240 и C540 ). Расчеты проводился как для докритической, так и для закритической
областей температур, причем в широком интервале давлений. Показано, что оба типа
графитовых адсорбентов могут быть использованы в качестве накопителей
(аккумуляторов) водорода: графитовые нанопоры и фуллерены характеризуются
сравнимыми величинами адсорбционной емкости (массовая плотность водорода при 77
К, т.е. при низкой температуре, отвечающей температуре кипения азота, и давлении 20
МПа в щелевидной нанопоре составляет 9,4%, а на фуллерене C60 9,1%), что вполне
достаточно для использования сиротствующих аккумуляторов на автомобильном
транспорте. Применительно к молекулам C60 речь идет об адсорбции только на ее
наружной поверхности. Следует также отметить, что полученные в рамках МФАП
результаты, хорошо согласуются с экспериментальными данными и с результатами
молекулярно-динамических экспериментов. К сожалению, при высоких (комнатных)
температурах адсорбционные характеристики обычных углеродных адсорбентов
существенно снижаются.
1. Самсонов В.М., Зубков В.В., Гринев И.В. // Коллоидный журнал. 2011. Т. 73. №4. С.
520.
2. Зубков В.В., Самсонов В.М., Гринев И.В. // Известия РАН. Серия Физическая. 2012.
Т. 76. № 7. С. 926.
3. Зубков В.В., Самсонов В.М., Гринев И.В. // Поверхность. Рентгеновские,
синхротронные и нейтронные исследования. 2012. Т.1. С.56.
4. Самсонов В.М., Зубков В.В., Гринев И.В. // Письма в ЖТФ. 2011. Т. 37. №. 7.
ТЕРМОДИНАМИКА И МЕХАНИЗМ КРИСТАЛЛОГЕНЕЗИСА ИЗ ЖИДКОЙ ФАЗЫ
Кидяров Б.И.
Институт физики полупроводников СО РАН им. А.В. Ржанова, Новосибирск
e-mail: kidyarov@isp.nsc.ru
Согласно термодинамической, «капиллярной» теории нуклеации работа
образования зародыша новой фазы (ΔG(r)), включающая поверхностную (σ(r)) и
объемную энергии (h(r)), зависит от размера зародыша. Подставляя экстремальную
зависимость σ(N), полученную В.М. Самсоновым с соавторами, в уравнение для ΔG(r)
мы показали, что возникающий энергетический барьер нуклеации имеет двух-
барьерную форму, Рис. -a, b. [1]. Причиной этого является возможная структурно -
физическая двух-, или трех- стадийность формирования устойчивого микро-зародыша,
которая обуславливает несколько возможных типов нестационарности и других
особенностей в кинетике процесса нуклеации [1]. Анализ постадийности процесса
кристаллогенезиса включает до восьми возможных причин существенного изменения
формы ∆G(r), и J(t), обусловленных разнообразием свойств веществ и режимов, при
которых проводятся процессы кристаллизации [1]. В частности, в многокомпонентной
среде формирование кристаллического зародыша возможно через предварительное
образование исходного жидкого зародыша (био- органика) [2-3],
жидкокристаллического зародыша, квазикристаллического зародыша, либо через
образование ряда метастабильных кристаллических фаз [1]. Варианты последнего
случая многочисленны (до 80), но вполне перечислимы согласно таблице
сегенетоэластичных и сегнетоэлектрических фазовых переходов, составленной в 1969
году Кентимиро Аизу [1]. Знание структурно-физической специфики образования
кристаллов крайне важно для понимания закономерностей не только процесса
нуклеации, но и для прогнозирования результатов дальнейшего роста дефектных или
совершенных кристаллов, имеющих различную точечную группу симметрии, а также
различную величину сегнето- электрических или сегнето- эластичных свойств [1].
Уточнение причин этой специфики является актуальной проблемой современной
физики конденсированных сред, физической химии и молекулярной физики.
1,0
a) b)
1,5
∆G(r) / ∆G(rk2)
0,8
σ /σο
1,0 0,6
0,4
0,5
0,2
0,0 rk1 rk2
0 2 4 6 8 10 0,0
N 0 2 4 6 8 10 12 14
10r / rk
Зависимости σ(N) (a), и ∆G(r) (b) для двух-барьерной нуклеации.

1. Кидяров Б.И. Механизм, кинетика образования и выращивание нелинейных
кристаллов для оптоэлектроники // Автореферат диссертации на соискание ученой
степени д.ф.-м.н., 01.04.07 и 02.00.04. Новосибирск. 2011. – 40 с.
2. Vekilov P.G. // Nanoscale. 2010. – V.2. – P.2346 - 2357.
3. Vekilov P.G. // Nature Materials. 2012. Vol. 11. – P. 838-840.
ТЕРМОДИНАМИЧЕСКОЕ ИССЛЕДОВАНИЕ УСТОЙЧИВОСТИ МАНЖЕТЫ

ЖИДКОСТИ МЕЖДУ ДВУМЯ СФЕРИЧЕСКИМИ НАНОЧАСТИЦАМИ
Колосов А.Ю., Соколов Д.Н., Сдобняков Н.Ю., Новожилов Н.В., Антонов А.С.,
Базулев А.Н., Самсонов В.М.
Тверской государственный университет, Тверь, e-mail: nsdobnyakov@mail.ru
В природе и технике широко распространены системы, в которых дисперсные
твердые частицы или газовые пузыри соединены прослойками (манжетами) жидкости. В
рамках термодинамической теории возмущений на основе определения равновесной
формы манжеты жидкости между двумя твердыми сферическими наночастицами
исследована избыточная свободная энергия такой наносистемы с использованием
следующего соотношения:
1
Ψ = Ψ c + U 34( ss ) ( R, l ) = 2U13( ls ) ( R, l , l1 ) − U12( ll ) (r , l , l1 ) − U13( ll ) ( R, l , l1 ) + U 34( ss ) ( R, l ) , (1)
2
где фаза 1 – жидкая манжета, фаза 2 – внешняя по отношению к системе среда, фазы
3, 4 – твердые сферические частицы. Здесь Ψ c - избыточная свободная энергия манжеты,
( ss )
U 34 ( R, l ) - вклад в избыточную свободную энергию за счет взаимодействия твердых
сферических наночастиц. В наших расчетах потенциал взаимодействия твердой фазы
(алюминий) задавался в форме потенциала Шиффа [1], в то время как взаимодействия в
пленке декана задавалась потенциалом Леннард-Джонса. Методика определения
параметров потенциала Леннард-Джонса подробно изложена в [2]. Одной из проблем
рассматриваемой модели является выбор поверхности манжеты между двумя частицами. В
качестве таких поверхностей нами было рассмотрено два случая: 1. в качестве профиля
выбирается дуга окружности; 2. профилем является дуга, описываемая уравнением цепной
линии.
Нами в рамках данной работы исследовались размерные эффекты, связанные
изменением размера твердых сферических частиц при условии постоянства объема
манжеты жидкости, наличием линейных эффектов мы пренебрегали, предполагая наличие
точечного контакта между твердыми частицами и жидкостной манжетой в направлении
угла ϕ . Анализируя полученные результаты, мы приходим к выводу, что при увеличении
размера твердых сферических частиц избыточная свободная энергия постоянной по объему
манжеты нелинейно увеличивается до некоторого предельного значения соответствующего
максимальному радиусу твердых частиц. На основе зависимостей избыточной свободной
энергии манжеты для исследования стабильности такой системы, вводя в рассмотрение
«условное» расклинивающее давление
Π * ( h ) = − ∂ (Ψ / Sc ) ∂h , (2)
где= Sc π= D 2 4 π R 2 sin 2 ϕ - площадь контакта манжеты с твердыми сферическими
наночастицами, h - эффективная средняя толщина манжеты, определяемая соотношением
l

1
R2 R2  l 
h = ∫ h( y )dy =R ⋅  2 − 1 − 2 − arcsin  1   ,
−l 
1
l1 l1  R  
здесь y - вертикальная координата. Используя критерий устойчивости для манжеты
∂Π * ( h ) / ∂h < 0 (3)
можно установить область размеров, в которой подобная система должна быть устойчива [3].
Работа выполнена при поддержке РФФИ (проекты № 12-03-31593, 13-03-00119).
References
1. Schiff D. // Physical Review. 1969. V. 186, № 1, P. 151-154,
2. Сдобняков Н.Ю. и др. // Известия РАН, Серия физическая. 2009. Т. 73. № 8. С. 1198.
КОЭФФИЦИЕНТ КОНДЕНСАЦИИ ВОДЫ

Кочурова Н.Н.
Санкт-Петербургский государственный университет,
Химический факультет, Санкт-Петербург
e-mail: oleg@NK2235.spb.edu
Исследование кинетических процессов испарения и конденсации обнаруживает
влияние границы фаз на скорость фазового перехода. Интенсивность этих процессов
определяется переносом тепла и вещества в жидкой и паровой фазах, а так же
граничным термическим сопротивлением (Rгр), обусловленным молекулярными
явлениями, происходящими на границе раздела фаз. При испарении Rгр определяется
Tгр − Tn
по формуле: R гр = , гдеTn – температура пара, Tгр – температура поверхности
irm
жидкости, i – поток испаряющихся молекул, который пропорционален коэффициенту
конденсации ƒ, определяющему долю конденсированных молекул от числа всех
молекул, попавших на поверхность, r – теплота испарения, m – масса молекулы.
Модифицированное соотношение Штуке показывает, что коэффициент конденсации
зависит от поверхностного натяжения жидкости. На статической поверхности воды при
комнатной температуре коэффициент конденсации составляет 0.04, в то время, как на
свежей поверхности, например, на поверхности струи он заметно возрастает,
приближаясь к 1.
Поскольку проблема коэффициента конденсации для воды является практически
очень важной для человека, так как свойства воды определяют круговорот воды в
природе, атмосферные явления, эффективность энергетических машин и аппаратов, мы
провели целый комплекс исследований, в особенности в области динамического
поверхностного натяжения и поверхностного электрического поверхностного
потенциала (∆χ). Теоретические работы академика А.И. Русанова, посвященные
дуализму поверхностного натяжения (σ≠γ) и измерения неравновесных свойств
поверхности воды позволяют глубже понять структуру поверхности воды. В работе
представлены результаты измерений ∆ γ – ∆χ для воды и водных растворов в широком
диапазоне концентраций, проведен анализ релаксации свежей поверхности,
показывающий роль диссоциации молекул воды на границе с воздухом, который может
существенно уменьшить величину коэффициента конденсации и замедлить скорость
фазового перехода.
Работа выполнена при поддержке гранта президента РФ для поддержки
научных школ НШ-4464.2012.3.
МОДЕЛИРОВАНИЕ ПОВЕРХНОСТНОЙ ЭНЕРГИИ ГРАНИЦЫ ЗЕРНА

В ОЦК-ЖЕЛЕЗЕ
Мирзоев А.А., Верховых А.В.
Южно-Уральский государственный университет
(Национальный исследовательский университет), Челябинск
e-mail: nastena89.89@mail.ru
Благодаря своей низкой цене и превосходным механическим свойствам, сталь
является одним из наиболее важных и широко используемых металлических
материалов. Строение границ зёрен оказывает большое влияние на ее свойства:
прочность и жёсткость структуры. Прочность является одним из важнейших
функциональных свойств конструкционных материалов. Физическая природа
разрушения твёрдых тел кроется в обстоятельствах разрыва атомных связей.
Конкретизировать эти обстоятельства можно, если рассмотреть проблему на атомарном
уровне. К сожалению, экспериментально это сделать не всегда возможно. Поэтому,
целью данной работы являлось моделирование поверхностной энергии границы зерна в
ОЦК-железа, с помощью программном пакете WIEN2k.
Была исследована граница наклона ферромагнитного ОЦК-железа Σ=5 с двумя
углами разориентировки: 36.9° направления (310) и 53.1° направления (210). Эта
граница раздела обладает высокой стабильностью благодаря большому количеству
совпадающих узлов решётки в обоих зёрнах.
Все вычисления проводились в рамках теории функционала плотности методом
линейных присоединённых плоских волн с учётом обобщённого градиентного
приближения в программном пакете WIEN2k с использованием 8x4x1 k-точек в
неприводимой области зоны Бриллюэна, согласно теории Монхорста-Пака [1].
Чтобы найти оптимальную конфигурацию системы, необходимо оценить энергию
формирования границы зерна для всех конфигураций. Эта величина определяется
двумя способами: 1) согласно термодинамической теории Раиса и Ван [2]:
где Egb — полная энергия границы зерна; Еfs — полная энергия свободной поверхности.
Измеряется в электрон-вольтах.
2)В рамках подхода ab initio
где Egb — полная энергия границы зерна; Ebulk – полная энергия объёмного кристалла,
который имеет тот же объем и форму суперячейки как у границы зерна; S — площадь
поперечного сечения суперячейки. Измеряется в Дж/м2.
Таким образом, мы получили следующие результаты, для Σ5(210) −
и , а для Σ5(310) − и , что хорошо
согласуется как с результатами из других работ [3,4], так и с экспериментальми
значениями [5].
1. H. J. Monkhorst, J. D. Pack. Physical Review B, 13:5188-5192, 1976
2. J. R. Rice, J.-S Wang. Materials Science and Engineering: A, 107:23-40, 1989
3. E. Wachowicz, A. Kiejna. Computational Materials Science, 43:736-743, 2008
4. B. Hyde, D. Farkas, M. J. Caturla. Philosophical Magazine, 85: 3795-3807, 2005
5. T. Roth. Materials Science and Engineering, 18: 183-192, 1975
ГАЗОХРОМАТОГРАФИЧЕСКОЕ ИССЛЕДОВАНИЕ КАТАЛИТИЧЕСКОЙ

АКТИВНОСТИ НАНОЧАСТИЦ МЕДИ
Митина Е.Г., Шафигулин Р.В., Буланова А.В.

Самарский государственный университет, Самара
e-mail: ktyfvbn@mail.ru
Наноструктуры обладают квантоворазмерными эффектами, обусловливающими
особенности термодинамики их поверхности. С участием наноструктур можно
регулировать направление реакции и сдвигать константу равновесия в сторону
получения продуктов реакции. Особенности поверхности наноструктур обусловливают
и их каталитическую активность. кинетика реакций на поверхности наночастиц
отличается от классической. Так как размеры наночастиц сопоставимы с размером
молекул, химическая реакция проходит в ограниченном объёме и её скорость зависит
от размера частиц [1]. В гетерогенных системах размерные эффекты зависят так же от
дополнительных факторов: химической природы компонентов гетерогенной смеси,
пространственного распределения компонентов в композите и межфазного
поверхностного взаимодействия [2].
В работе были получены в лабораторных условиях наночастицы меди, изучены их
каталитические свойства в реакции гидрирования бензола, а так же исследована их
поверхность до и после использования. Образование частиц меди было доказано с
помощью энергодисперсионного рентгеновского анализа и ИК-спектроскопии, их
наноструктура установлена с помощью сканирующей электронной микроскопии.
В качестве реактора для проведения процесса гидрирования использовали
стальную трубку длинной 54 см, шириной 3 мм, заполненную наночастицами меди и
помещенную в термостат газового хроматографа Цвет-500М. Перед проведением
процесса реактор насыщали в течении 10 минут водородом для создания избытка, что
давало основания считать, что реакция гидрирования бензола проходила по псевдо
первому порядку. Кинетика гидрирования бензола на наночастицах меди была
исследована при нескольких температурах с помощью метода газовой хроматографии
на хроматографе ЛХМ-80 с детектором по теплопроводности, в качестве газа-носителя
использовали гелий. Рассчитанные кинетические параметры дают основания говорить,
что наночастицы меди обладают заметной каталитической активностью.
Для исследования поверхности наночастиц до и после проведения реакции
использовали такие метод сканирующей электронной микроскопии. Данный метод
показал, что структура данного катализатора не является стабильной, это
обусловливает снижение каталитической активности при длительном использовании.
1. Сергеев Г.Б. Нанохимия. М.: «КДУ», 2007. С 243-244.
2. Сергеев Г.Б. // Российский химический журнал. 2002. Т. ХLVI, №5. С. 22-29.
ПОЛИМОРФНЫЕ ПРЕВРАЩЕНИЯ В ВОДНЫХ РАСТВОРАХ БРОМИДОВ

АЛКИЛТРИМЕТИЛАММОНИЯ
1
Мовчан Т.Г., 2Колесникова Н.Р., 1Плотникова Е.В., 1,3Соболева И.В.,
4
Щекин А.К, 1,4Русанов А.И.
1
ИФХЭ РАН им. А.Н. Фрумкина, Москва, е-mail: movchan@phyche.ac.ru
2
РХТУ им. Д.И. Менделеева, Москва
3
МГУ им. М.В. Ломоносова, физический факультет, Москва
4
Санкт-Петербургский государственный университет, Санкт-Петербург
По результатам исследования динамического светорассеяния в водных растворах
бромидов алкил (децил-, додецил-, тетрадецил- и цетилтриметиламмония) найдены
значения коэффициентов общей диффузии мицелл, противоионов и ионов ПАВ в
широкой области концентраций, охватывающей первую и вторую критические
концентрации мицеллообразования (ККМ1 и ККМ2).
Обнаружено немонотонное и неоднозначное поведение коэффициентов общей
диффузии с ростом брутто-концентрации выше ККМ1. Рост коэффициента общей
диффузии в первой декаде брутто-концентраций бромида цетилтриметиламмония
(СТАВ) выше ККМ1 [1] согласуется с известными из литературы данными для водных
растворов ионных ПАВ [2,3]. Показано, что увеличение ионной силы раствора СТАВ
добавлением бромида калия приводит к уменьшению положительного угла наклона
зависимости коэффициентов диффузии от брутто-концентрации ПАВ, вплоть до нуля
при 0.05М KBr.
Начиная с концентрации 0.03М, в мицеллярных растворах СТАВ одновременно
наблюдались два процесса релаксации, отвечающие большим и малым значениям
коэффициента диффузии. Расчетами гидродинамического радиуса и длины мицелл и
сопоставлением с результатами измерений вязкости и литературными данными
показано, что эти процессы обусловлены сосуществованием сферических и
несферических мицелл с преимущественным содержанием в растворе асимметричных
несферических мицелл, образующихся при 0.03М СТАВ и приобретающих
цилиндрическую форму в области 0.2–0.25М.
В растворах бромидов алкил (децил-, додецил- и тетрадецил-) триметиламмония
также обнаружен рост коэффициента общей диффузии в первой декаде брутто-
концентраций, который, как и в случае растворов СТАВ, можно объяснить поведением
среднего коэффициента активности ПАВ в мицеллярной системе, связанным с
электростатическим взаимодействием всех заряженных частиц [2,3].
В растворах бромидов алкилтриметиламмония выявлены области концентраций
ПАВ, в которых наблюдается резкое снижение коэффициентов диффузии D и
повышение относительной вязкости. Расчетами гидродинамического радиуса и длины
мицелл и сопоставлением с результатами измерений вязкости показано, что снижение
D обусловлено переходом мицелл из сферической формы в цилиндрическую.
Работа выполнена при финансовой поддержке РФФИ.
1. Мовчан Т.Г., Соболева И.В, Плотникова Е.В., Щёкин А.К., Русанов А.И. // Коллоид.
журн. 2012, том 74, № 2, с. 257.
2. Weinheimer R.M., Evans D.F., and Cussler E.L. // J. Colloid Interface Sci. 1981. V. 80. №
2. P. 357.
3.Dorshow R., Briggs J., Bunton C.A., Nicoli D.F. // J. Phys. Chem. 1982. V. 86. № 13. P.
2388.
ТЕРМОДИНАМИЧЕСКИЕ СВОЙСТВА ПОРИСТОГО ПОЛИМЕРА

НА ОСНОВЕ МЕТАКРИЛОВОЙ КИСЛОТЫ
Мозговой О.С., Гуськов В.Ю., Кудашева Ф.Х.
e-mail: skill15@mail.ru
Пористые полимерные сорбенты представляют собой обширный класс
адсорбентов и широко применяются как в промышленности, так и в исследовательских
лабораториях. Основными областями применения пористых полимерных сорбентов
являются очистка промышленных выбросов от токсичных веществ, концентрирование
микропримесей из атмосферы и воды, в качестве ионообменных смол, а также в
газоадсорбционной хроматографии. Однако, на настоящий момент достаточно мало
работ посвящено изучению высокополярных пористых полимеров. Целью настоящей
работы является исследование сорбционных и термодинамических свойств пористого
полимера на основе метакриловой кислоты Diaion HP-2MG. Его удельная поверхность
составляла 1,2 м2/г, а средний размер пор 170 Ǻ.
Исследование проводилось методом обращённой газовой хроматографии в режиме
бесконечного разбавления на хроматографе «Хром-5» с пламенно-ионизационным
детектором в температурном диапазоне 140-160°С. Использовалась стальная колонка
500*3 мм. Скорость газа-носителя азота составляла 60 мл/мин. В качестве тест-
сорбатов были выбраны вещества, способные к различным типам межмолекулярных
взаимодействий. Полученные таким образом значения удельных удерживаемых
объёмов (Vg), мл/г, будут пропорциональны константам Генри, и могут служить
характеристиками свойств сорбента. Из зависимости lnVg от 1/T были рассчитаны
мольные изменения внутренней энергии (-ΔU) и энтропии сорбции (-ΔS), кДж/моль и
Дж/моль*К соответственно.
Установлено, что для поверхности изучаемого полимера характерна физическая
адсорбция и отсутствуют размерные эффекты. Удерживаемые объёмы аренов при всех
исследуемых температурах выше, чем для алканов с тем же количеством атомов
углерода. Это обусловлено сильными специфическими взаимодействиями поверхности
сорбента с π-электронной плотностью аренов. Термодинамические функции адсорбции
спиртов не зависят от поляризуемости, а зависят от дипольного момента молекулы, что
говорит о высокой полярности поверхности и о сродстве к образованию водородных
связей.
Количественно полярность исследовалась методом линейного разложения
параметров удерживания, основанном на разложении мольной энергии сорбатов в виде
суммы вкладов различных межмолекулярных взаимодействий.
Показано, что исследуемый сорбент является более полярным, чем полимерные
сорбенты на основе стирола и дивинилбензола.
Обнаружена зависимость сорбционной активности от температуры
кондиционирования. Так, удерживаемые объёмы как полярных, так и неполярных
сорбатов на колонке, прогретой при 160°С, будут существенно выше, чем на колонке,
прогретой при 200°С.
Таким образом, в настоящей работе установлено, что адсорбент Diaion HP-2MG
на основе метакриловой кислоты является более полярным, чем изученные ранее
полимерные сорбенты на основе стирола и дивинилбензола. Полученные данные
позволяют рекомендовать исследуемый полимер для эффективного
микроконцентрирования полярных загрязнителей.
ВЛИЯНИЕ ПАВ НА ДИНАМИЧЕСКИЕ ПОВЕРХНОСТНЫЕ СВОЙСТВА

РАСТВОРОВ ЛИЗОЦИМА
Носков Б.А., Тихонов М.М.
Санкт-Петербургский Государственный Университет,
Химический факультет, Санкт-Петербург
e-mail: herr-morgenstern@yandex.ru
Дилатационные поверхностные реологические свойства растворов смесей

лизоцима c додецилсульфатом натрия (ДСН) и бромидом додецилтриметиламмония
(ДТАБ) были измерены методами осциллирующего кольца и осциллирующего барьера.
Для растворов лизоцим/ДСН на начальной стадии адсорбции скорость изменения
поверхностных свойств немонотонно зависит от концентрации ПАВ, что связано с
изменением знака заряда комплекса лизоцим/ДСН при увеличении степени связывания
ПАВ [1]. Немонотонные кинетические зависимости динамической поверхностной
упругости свидетельствуют о разрушении вторичной и третичной структур белка в
поверхностном слое. Для растворов лизоцим/ДСН денатурирующее действие
межфазной границы оказывается более сильным, чем для ранее исследованных
растворов комплексов глобулярных белков и ионных ПАВ. В случае растворов
лизоцим/ДТАБ наблюдается монотонное уменьшение скорости изменения
поверхностных свойств с ростом концентрации ПАВ, связанное с увеличением
электростатического барьера адсорбции. Отсутствие локальных максимумов на
кинетических зависимостях динамической поверхностной упругости свидетельствует о
сохранении вторичной и третичной структуры лизоцима при взаимодействии с ДТАБ.
Работа выполнена при финансовой поддержке РФФИ (Проект № 11-03-00801-а).
Литература:
1. Б.A. Носков, М.М. Тихонов, Коллодн. Журн. 74, 266 (2012).
ОБРАЗОВАНИЕ И РОСТ МОНОКРИСТАЛЛОВ ТИОФЕН-ФЕНИЛЕНОВЫХ

ОЛИГОМЕРОВ НА МЕЖФАЗНОЙ ГРАНИЦЕ ЖИДКОСТЬ — ВОЗДУХ
Постников В.А. 1, Бруевич В.В.2, Иовлев А.В 2, Лупоносов Ю.Н. 2,3, Борщев О.В. 2,3,
Скоротецкий М.С.2,3, Пономаренко С.А.2,3, Иванов Д.А.2, Паращук Д.Ю.2
1
Донбасская национальная академия строительства и архитектуры,
кафедра физики и физического материаловедения, Украина
2
Московский государственный университет им. М.В. Ломоносова, международный
учебно-научный лазерный центр, физический факультет, химический факультет,
факультет фундаментальной физико-химической инженерии
e-mail: iovlev@physics.msu.ru
3
Институт синтетических и полимерных материалов им. Н.С. Ениколопова РАН
В последнее десятилетие появился новый класс π-сопряженных органических
полупроводниковых материалов – тиофен-фениленовые олигомеры ТФО, в кристаллах
которых удается сочетать высокую подвижность зарядов (~ 1 см2/(В∙с)) с эффективной
электро- и фотолюминесценцией (ФЛ). Такие материалы могут быть получены в виде
тонких монокристаллических пленок и перспективны для разработки органических
светоизлучающих полевых транзисторов и инжекционных лазеров. В настоящей работе
впервые сообщается о получении тонких монокристаллических пленок ряда ТФО с
одинаковым сопряженным ядром и различными концевыми заместителями (см. Рис.).
R
S
R = H, F, CF3, Si(CH3)3
S
R
Рис. Общая структурная формула исследованных тиофен-фениленовых олигомеров.
Разработана методика быстрого (до 3 суток) получения монокристаллических

пленок ТФО размером до 10 мм и толщиной 1÷5 мкм на межфазной границе жидкость
– воздух из смеси хорошего (слабополярного) и плохого (сильнополярного)
растворителей. Крупные монокристаллические пленки исследуемых олигомеров также
образуются при медленном охлаждении (0.1 К/час) в течение 10÷14 суток как на
поверхности, так и в объеме раствора.
Морфология и качество поверхности полученных кристаллов исследовались
методами оптической и атомно-силовой микроскопий. Установлено, что поверхность
пленки, обращенная при росте к газовой фазе – молекулярно-гладкая, с относительно
низким количеством дефектов (трещин, ступеней роста), в сравнении с нижней
поверхностью. Рост кристаллов происходит как за счет винтовых дислокаций, так и по
островковому механизму, о чем свидетельствуют пирамиды роста на нижней
поверхности.
Проанализирована термодинамика образования плоских зародышей кристаллов
ТФО на межфазной границе жидкость – воздух. Предложен механизм образования
зародышей кристаллов ТФО на межфазной границе. Предполагается, что в образование
мономолекулярных слоев на поверхности важную роль играют концевые группы
молекул. Таким образом, процесс образования и роста изученных кристаллов ТФО
можно отнести к явлению адсорбции ПАВ на межфазной границе жидкость – воздух.
Для полученных образцов кристаллов проведен анализ спектров поглощения и
ФЛ, исследована кинетика фотолюминесценции и изучена кристаллическая структура.
Работа выполнена при поддержке РФФИ (грант №12-02-90907-моб_снг_ст) и
Минобрнауки РФ (проект №11.G34.31.0055 от 19.10.2011).
ТЕРМОДИНАМИЧЕСКИЙ АСПЕКТ МИКРОФЛОТОЭКСТРАКЦИОННОГО

ИЗВЛЕЧЕНИЯ ЖИРНЫХ КИСЛОТ С ПОМОЩЬЮ
ТОНКОЭМУЛЬГИРОВАННОГО КЕРОСИНА
Сазонова В.Ф., Кожемяк М.А., Перлова О.В., Менчук Е.М.
Одесский национальный университет имени И.И. Мечникова, Одесса, Украина
e-mail: v.sazonova@onu.edu.ua
Целью данного исследования явилось выяснение возможности увеличения глубины
флотационной очистки воды от истинно растворенных жирных кислот с помощью
тонкоэмульгированного керосина. В отношении жирных кислот, в данном случае,
реализуется процесс микрофлотоэкстракции, в котором экстрагент (керосин) вводится в
раствор извлекаемого компонента (жирной кислоты) в виде высокодисперсной эмульсии, в
отличие от флотоэкстракции [1], в которой экстрагент представляет собой макрофазу.
Объектами исследования служили насыщенные растворы октановой (ОК) и
нонановой (НК) кислот, содержащие соответственно 0,68 и 0,26 г кислоты в литре.
Керосин эмульгировали непосредственно в растворах жирных кислот за 2-3 мин до
начала флотации. Флотацию осуществляли на флотационной установке
пневматического типа. Полнота микрофлотоэкстракционного извлечения жирных
кислот зависит от их поверхностной активности - способности переходить на границу
раздела фаз жидкость-жидкость и жидкость-газ. Критерием поверхностной, а
следовательно, флотационной активности жирных кислот может служить величина их
гидрофильно-олеофильного энергетического соотношения – ГОЭС [2],
представляющего собой (для любых ПАВ) отношение энергии, затрачиваемой в
процессе мицеллообразования на дегидратацию полярных групп ПАВ ( ∆GP ) и
входящих в их состав противоионов ( ∆GI ), к энергии, выделяющейся в результате
перевода в состав мицелл углеводородных радикалов ( ∆G R ):
ГОЭС = ( ∆G p + ∆G I ) / ∆G R . Величину ГОЭС ОК и НК рассчитывали по
уравнениям: ∆G миц = RT ln KKM 2 ; ∆G миц = ∆GP + ∆GI + ∆GR ; ∆GR = n ⋅ ∆GCH 2 ;
∆GCH 2 = (∆G миц )n +1 − (∆G миц )n . Расчеты показали, что ГОЭСНК (0,053)< ГОЭСОК (0,061),
поэтому она должна флотироваться лучше, чем ОК. Однако опыт показывает, что она
флотируется хуже ОК. Причиной кажущегося несоответствия может быть большая
склонность НК к мицеллообразованию в объеме фазы, чем к адсорбции на границах
раздела фаз жидкость–жидкость и жидкость-газ, т.е. для НК ∆G миц > ∆Gадс Поэтому
.
отношение указанных величин – адсорбционно-мицеллярное энергетическое
соотношение ( АМЭС = ∆Gадс
0
/ ∆G миц
0
) [3] НК меньше единицы. Представления об
АМЭС ПАВ лежат в основе термодинамического обоснования влияния длины
углеводородного радикала ПАВ на эффективность их адсорбции на границах раздела аз
жидкость-газ (флотация, пенообразование) и жидкость-жидкость (экстракция).
1. Себба Ф. Ионная флотация. М.: Металлургия, 1965. – 170с.
2. Скрылев Л.Д., Сазонова В.Ф. Оценка гидрофильно-липофильных свойств ПАВ по
величине их ККМ// Изв. вузов. Химия и хим. технология.- 1987. Т.30, №5 С.72-76.
3. Скрылев Л.Д., Стрельцова Е.А., Скрылева Т.Л. Адсорбционно-мицеллярное
энергетическое соотношение ПАВ, как критерий их пенообразующей
способности // Изв. вузов. Химия и хим. технология. -1985. Т.28, №4 С.62-66.
ИССЛЕДОВАНИЕ РАЗМЕРНЫХ ЗАВИСИМОСТЕЙ

ТЕРМОДИНАМИЧЕСКИХ ХАРАКТЕРИСТИК НАНОЧАСТИЦ МЕТАЛЛОВ
МЕТОДАМИ КОМПЬЮТЕРНОГО МОДЕЛИРОВАНИЯ
Самсонов В.М., Сдобняков Н.Ю., Комаров П.В.,
Бембель А.Г., Соколов Д.Н., Васильев С.А.
e-mail: dnsokolov@mail.ru
Применение наноразмерных рабочих элементов в электронике и других
направлениях нанотехнологий требует знания свойств наночастиц и размерных
зависимостей их термодинамических характеристик. Исследования в этом направлении
представляют большой интерес и с фундаментальной точки зрения, поскольку
приходится сталкиваться с двумя крайними методологическими подходами. С одной
стороны, многие авторы без каких-либо оговорок используют применительно к
кластерам и наночастицам такие понятия, как термодинамическая фаза, фазовый
переход, плавление и кристаллизация. В частности, в ранних работах по
компьютерному моделированию, отмеченных в [1], речь идет о плавлении кластеров,
содержащих меньше 100 атомов. С другой стороны, некоторые специалисты по
фазовым переходам и физике конденсированного состояния полностью отрицают
применимость указанных выше понятий к наночастицам и кластерам. В [2] были
получены были экспериментальные результаты, свидетельствующие о существовании
гистерезиса плавления и кристаллизации наночастиц металлов: было показано, что
температура кристаллизации заметно ниже температуры плавления, причем кривые
плавления и кристаллизации сливаются в одну точку при некотором характерном
радиусе наночастиц. Гистерезис плавления и кристаллизации был позднее предсказан
теоретически [3] и подтвержден экспериментально [4]. Отметим также, что большое
значение приобретает использование методов компьютерного моделирования фазовых
переходов в металлических нанокластерах. В [5-6] в результате молекулярно-
динамического моделирования были исследован фазовый переход
(плавление/кристаллизация) в нанокластерах никеля и меди. В [7] метод Монте-Карло
применен для исследования гистерезиса процесса плавления и кристаллизации
нанокластеров золота. С использованием метода поверхностных фаз Гиббса получена и
проанализирована размерная зависимость эффективной удельной полной
поверхностной энергии нанокластеров золота. Таким образом, прогнозирование
размерных эффектов и их влияния на термодинамические характеристики наночастиц
позволяет оценить диапазон функционирование наномасшабных устройств, который
определяется температурной стабильностью образующих их наноразмерных
функциональных элементов.
Работа выполнена при поддержке РФФИ (проекты № 12-03-31593, 13-03-00119).
1. Петров Ю.И. Физика малых частиц. − М.: Наука, 1982.
2. Жданов Гл. С. // Изв. АН СССР. Серия физическая. 1977. Т. 41. Вып. 5. С. 1004-1008.
3. Скрипов В.П., Коверда В.П. Спонтанная кристаллизация переохлажденных
жидкостей. − М.: Наука, 1984. С. 98-104.
4. Kofman R. at el. // Surface Science. 1994. V. 303. P. 231-246.
5. Самсонов В.М. и др. // Кристаллография. 2009. Т. 54. №3. С. 563-569.
6. Гафнер С.Л. и др. // Письма в ЖЭТФ. 2009. Т. 89. Вып. 7. С. 425-431.
7. Сдобняков Н.Ю. и др. // ФММ. 2011. Т. 111. № 1. С.15-22.
ПОВЕРХНОСТНЫЕ И ОБЪЕМНЫЕ СВОЙСТВА СМЕСЕЙ ТВИНОВ

С ДОДЕЦИЛСУЛЬФАТОМ НАТРИЯ
Стрельцова Е.А., Гросул А.А., Попова И.В.
Одесский национальный университет имени И.И. Мечникова, Одесса, Украина
e-mail: A-Grosul-11@yandex.ua
Изменение объемных и поверхностных свойств растворов смесей поверхностно-

активных веществ (ПАВ) по сравнению с индивидуальными растворами ПАВ и, как
следствие, проявление эффектов синергизма или антагонизма представляют как
теоретический, так и практический интерес.
В данной работе проведен количественный и термодинамический анализ
межмолекулярных взаимодействий в водных растворах и адсорбционных слоях
бинарных смесей анионного (додецилсульфат натрия (ДДСН)) и неионогенных (Твин-
20, Твин-40, Твин-60, Твин-80) ПАВ в процессе их мицеллообразования и адсорбции на
границе раздела фаз раствор ПАВ – воздух. Смешанные системы Твин-20–ДДСН,
Твин-40–ДДСН, Твин-60–ДДСН и Твин-80–ДДСН изучены в концентрационных
пределах (0,5·10-6-1,0·10-3) моль/л. Мольная доля (n) Твина в растворе составляла 0,3;
0,5; и 0,7.
В результате проведенных исследований обнаружено отрицательное отклонение
от идеальности по отношению к критической концентрации мицеллообразования
(ККМ) во всех изученных смесях при содержании Твина не более n = 0,7, т.е.
наблюдается синергетический эффект при мицеллообразовании. Это объясняется
уплотнением упаковки молекул и ионов ПАВ в мицеллах, что свидетельствует о
наличии взаимодействия и образования смешанных мицелл в системах Твин–ДДСН.
Результаты расчетов, проведенных с использованием модели Рубина-Розена показали,
что смешанные мицеллы в системах Твин–ДДСН обогащены более поверхностно-
активным ПАВ – Твином. Мольная часть (χm) Твина в смешанных мицеллах
практически не зависит от длины углеводородного радикала в их молекуле и возрастает
с увеличением его содержания в объеме раствора. Отрицательные значения параметра
межмолекулярного взаимодействия (βm) указывают на существенно более сильное
притяжение между компонентами смеси в смешанных мицеллах по сравнению с
взаимодействием между молекулами ПАВ одного типа. Экспериментальные значения
общей концентрации водных растворов смесей Твин-20–ДДСН, Твин-40–ДДСН,
необходимых для достижения значений поверхностного натяжения 48-51 мДж/м2 при
разном содержании Твинов в растворе ниже, чем значения общей концентрации,
рассчитанной теоретически, что указывает на образование смешанного адсорбционного
слоя на границе раздела фаз раствор ПАВ – воздух. В данном случае синергетический
эффект для смесей Твин-20–ДДСН, Твин-40–ДДСН проявляется в снижении общей
концентрации ПАВ, необходимой для достижения максимальной адсорбции на границе
раздела фаз раствор ПАВ – воздух. Для смесей Твин-60–ДДСН и Твин-80–ДДСН
наблюдается антагонизм поверхностного натяжения.
Сопоставление значений стандартных свободных энергий Гиббса адсорбции
∆
( G адс) индивидуальных ПАВ и их смесей со значениями стандартных свободных
0
энергий Гиббса мицеллообразования ( ∆ G0миц) показало, что процесс адсорбции

индивидуальных ПАВ и их смесей является термодинамически более выгодным по
сравнению с процессом их мицеллообразования.
ТЕРМОДИНАМИКА АДСОРБЦИИ ОРГАНИЧЕСКИХ СОЕДИНЕНИЙ

НА ПОВЕРХНОСТИ УГЛЕРОДНЫХ ВОЛОКОН.
Султанова А.Х, Валинурова Э.Р, Кудашева Ф.Х.
e-mail: aic_c@mail.ru
Методом инверсионной газовой хроматографии изучены актированное
углеродное волокно и его модифицированные образцы. Модифицирование волокна
осуществляли жидкофазным окислением в концентрированной азотной кислоте и
обработкой волокна раствором наночастиц серебра. Исследования проводили на
газовом хроматографе в интервале температур 200-300 оС с пламенно-ионизационным
детектором и стеклянной 0,5 м колонкой. Для моделирования различных типов
межмолекулярных взаимодействий в колонку с исследуемым образцом - адсорбентом
вводили тест-сорбаты. По построенным изотермам сорбции рассчитали константы
сорбционного равновесия, емкости монослоя, По изостерам сорбции тест-сорбатов
рассчитали изостерические теплоты сорбции.
Для расчёта полярности поверхности адсорбентов применили метод линейного
разложения параметров удерживания, основанный на разложении индексов Ковача или
теплот сорбции сорбатов в виде суммы вкладов различных межмолекулярных
взаимодействий.
Рассчитаны вклады различных видов межмолекулярных взаимодействий в общую
энергию сорбции.
Установлено, что адсорбция органических соединений на поверхности
углеродных волокон определяется в основном дисперсионной составляющей, которая
вносит вклад в межмолекулярные взаимодействия сорбент–сорбат от 71 до 99%, а
вклады индукционно-ориентационного, электронодонорного, электроноакцепторного
взаимодействий составляет 0,5-12,5%, 0-19,1%,0-13,9% соответственно.
По полученным экспериментальным данным можно рекомендовать дальнейшее
использование данных адсорбентов для избирательного извлечения различных
токсикантов из объектов окружающей среды.
ВЛИЯНИЕ КОНФОРМАЦИОННОЙ ПОДВИЖНОСТИ КАЛИКС[4]АРЕНОВ

НА ФОРМИРОВАНИЕ ПОРИСТЫХ КРИСТАЛЛИЧЕСКИХ СТРУКТУР
Суров О.В., Крестьянинов М.А., Воронова М.И.
Институт химии растворов им. Г.А. Крестова Российской академии наук, Иваново
e-mail: ovs@isc-ras.ru
Каликс[n]арены – макроциклические рецепторы, которые наряду с краун-эфирами
и циклодекстринами образуют один из основных классов супрамолекулярных
соединений – «хозяев». Каликс[n]арены представляют собой циклические продукты
конденсации фенолов с альдегидами и относятся к классу [ln]-метациклофанов. Интерес
к широкому спектру производных, получаемых химической модификацией переферии,
дополняется интересными конформационными свойствами каликсаренов. В растворе
может существовать динамическое равновесие между стереоизомерами в различной
конформации, вызванное возможностью вращения ароматических колец макроцикла.
При кристаллизации из соответствующих растворителей, например,
метоксипроизводные каликс[4]арена образуют молекулярные кристаллы, в
кристаллических решетках которых одновременно находятся различные конформеры.
Особенность молекулярной упаковки этих кристаллов такова, что образуется хорошо
развитая сеть сквозных каналов, напоминающая транспортные поры цеолитов.
В работе проводится оптимизация структуры и расчет электронных спектров
поглощения (ЭСП) возможных конформеров некоторых производных каликс[4]аренов
методом теории функционала плотности с использованием гибридного функционала
B3LYP в пакете программ Gaussian 09.
Сравнение расчетных ЭСП с экспериментальными в различных растворителях, а
также анализ ЭСП пленок, полученных при упаривании растворов, позволяет выявить
условия одновременной кристаллизации различных конформеров с целью получения
пористых цеолитоподобных структур.
Органическим и металлорганическим материалам, чьи свойства по поглощению
«гостей» напоминают традиционные цеолиты, в настоящее время уделяется большое
внимание. Особый интерес в этой связи представляет катализ, а также хранение,
разделение и транспортировка газов с целью их дальнейшего использования. В
противоположность клатратам, пористая структура которых поддерживается наличием
в них молекул-«гостей», цеолитоподобные сорбенты-«хозяева» способны обратимо
поглощать небольшие молекулы «гостей» с относительно свободным их перемещением
через транспортные поры в кристаллическую решетку, обладающую устойчивой
системой полостей.
ИССЛЕДОВАНИЕ СВОЙСТВ МЕЗОСТРУКТУРИРОВАННОГО

СИЛИКАТА МСМ-41
Сухарева Д.А., Гуськов В.Ю.
e-mail: soulsMirror@yandex.ru
Мезопористые материалы обладают высокой адсорбционной емкостью и
развитой поверхностью. Они играют важную роль в различных отраслях
промышленности, медицине, защите окружающей среды. Силикатные материалы типа
МСМ-41 обладают регулярным каркасом в форме пчелиных сот с диаметром пор около
35Å и толщиной стенки между порами порядка 8Å. Удельная поверхность составляет
около 1100 м2/г. Характерное отличие мезоструктурированных силикатов от других
кремнеземов состоит в узком распределении пор по диаметру. Их высокая
однородность в настоящий момент представляет существенный интерес для изучения.
В настоящей работе исследованы сорбционные и термодинамические свойства МСМ-
41.
Исследование проводилось на хроматографе «Агат» с детектором по
теплопроводности в интервале температур 140-2000С. В качестве адсорбатов были
выбраны органические вещества различной природы. Из значений удерживаемых
объёмов были рассчитаны мольные изменения внутренней энергии (-ΔU) и энтропии (-
ΔS) адсорбции.
В гомологических рядах тест-сорбатов наблюдается инверсия зависимости –ΔU
от количества атомов углерода. Наибольшее значение в ряду спиртов соответствует
наиболее полярной молекуле этанола. Это говорит о значительных донорно-
акцепторных взаимодействиях на поверхности сорбента.
Полярность поверхности исследовалась методом линейного разложения
параметров удерживания (ЛРПУ). Рассчитан вклад различных типов взаимодействий в
удерживание.
Так для пар гексан-бензол и гептан-толуол значения удерживаемых объемов для
бензола и толуола значительно больше алканов. Это объясняется вкладом
специфических взаимодействий за счет π – электронной плотности бензольных колец и
положительного заряда на поверхности сорбента.
Соединения близкие по температурам кипения, такие как гексан – пропанол
также имеют сильно отличающиеся значения удерживания. Было обнаружено, что если
на всех неполярных сорбентах гексан удерживается лучше, чем спирты, то на данном
сорбенте удерживание пропанола больше, и даже молекула этанола удерживается
лучше. Это связано со значительными донорно-акцепторными взаимодействиями
между гидроксильными группами. По данным исследования дисперсионные
взаимодействия для этанола и бензола составляют 30 и 71 %, соответственно, а вклад
специфических 70 и 29 %. Таким образом установлено, что специфические
взаимодействия вносят существенный вклад в свободную энергию адсорбции, и
сорбент МСМ-41 имеет полярную поверхность.
Неоднородность поверхности исследовалась на примере двух соединений: н-
бутанола и гексана. Было обнаружено, что если для н-бутанола параметры удерживания
зависели от концентрации сорбата в газовой фазе, то для гексана удерживаемые
объёмы оставались постоянными. Это говорит о том, что поверхность МСМ-41
абсолютно геометрически однородна.
О ТЕМПЕРАТУРНЫХ ГРАНИЦАХ СУЩЕСТВОВАНИЯ МИЦЕЛЛ

ОКСИЭТИЛИРОВАННЫХ НЕИОНОГЕННЫХ ПОВЕРХНОСТНО-АКТИВНЫХ
ВЕЩЕСТВ В ВОДНЫХ РАСТВОРАХ
Тихова А.А., Глухарева Н.А., Гермашева И.И.
Белгородский государственный национальный
исследовательский университет, Белгород
e-mail: glukhareva@bsu.edu.ru
Несмотря на всестороннее изучение поведения оксиэтилированных неионогенных
поверхностно-активных веществ (НПАВ) в связи с их широким практическим
применением, вопрос о температурной зависимости растворимости этого класса
веществ и соответствующих фазовых переходах до сих пор остается дискуссионным.
Обычно НПАВ характеризуются наличием верхней температурной границы
растворимости – точкой помутнения, выше которой в системе ПАВ-растворитель
происходит дегидратация молекул ПАВ с последующим выделением их в отдельную
фазу. Однако для НПАВ с линейным алкильным радикалом существует также аналог
нижней температурной границы мицеллообразования ионогенных ПАВ – точки
Крафта. Целью настоящей работы являлось изучение поведения дисперсии НПАВ,
имеющего верхнюю и нижнюю температурные границы растворимости. В работе был
использован образец оксиэтилированного нонилфенола с разветвленным алкильным
радикалом Неонол АФ9-10 (средняя степень оксиэтилирования n=10), а также
оксиэтилированный нонилфенол с преимущественно линейным алкильным радикалом
АФ9-15 (средняя степень оксиэтилирования n=15).
Сочетанием тензиометрического и визуального методов получены фазовые
диаграммы водных растворов изученных НПАВ. Установлено сходство фазовой
диаграммы для нонилфенола с линейным алкильным радикалом с диаграммами
растворов ионогенных ПАВ, характеризующихся наличием точки и границы Крафта,
которая соответствует переходу гетерогенной системы в мицеллярный раствор.
Фазовая диаграмма водных растворов Неонола АФ9-10 имеет вид, характерный для
большинства НПАВ с верхней температурной границей растворимости,
мицеллообразование в которых начинается практически от 0°С. Для АФ9-15 визуально
наблюдаемая область существования мицеллярного раствора лежит при более высоких
температурах (54-84°С), и нижняя температура растворения для него выше, чем для
разветвленного аналога, подобно тому как температуры плавления линейных
соединений выше, чем температуры разветвленных изомеров.
С использованием метода динамического светорассеяния определены
гидродинамические радиусы, числа агрегации и форма присутствующих в растворе
частиц при различных температурах. В растворе Неонола АФ9-10 с нагреванием
зафиксировано значительное укрупнение мицелл, сопровождающееся их
асимметризацией, в области температуры помутнения (66°С). АФ-15 даже при
невысоких концентрациях (несколько ККМ) при низких температурах находится в виде
крупных агрегатов (~200 нм), которые в узком температурном интервале переходят в
сферические мицеллы (~7-8 нм). Процесс подобен фазовому переходу.
Таким образом, растворение АФ9-15 с образованием мицеллярного раствора
происходит при некоторой температуре, аналогичной точке Крафта для ионогенных
ПАВ.
Работа выполнена в рамках НИР по государственному заданию,
регистрационный номер 38532011.
КОЛЛОИДНЫЕ И РЕОЛОГИЧЕСКИЕ СВОЙСТВА ОКИСЛЕННЫХ БИТУМОВ,

ПОЛУЧЕННЫХ ИЗ МОДИФИЦИРОВАННОГО СЫРЬЯ
Шрубок А. О.
Белорусский государственный технологический университет, Минск
e-mail: rala@tut.by
Для прогнозирования эксплуатационных свойств и поведения битумов в условиях
хранения, нагревания, приготовления на их основе вяжущих материалов необходимо
знать из основные физико-химические и механические свойства, которые определяют
строение, размеры и свойства структурных элементов битумов как коллоидных систем.
Объектами исследования в данной работе служили образцы окисленных битумов,
полученные из гудрона остаточного нефтепродукта атмосферно-вакуумной перегонки
нефти, перерабатываемого в ОАО «Нафтан» (г. Новополоцк), модифицированного
пиролизной смолой и ее компонентами.
На ротационном вискозиметре Brookfield DV-II+IV Pro (шпиндель SC4-21/13R,
объем пробы 7,1 мл) проводили измерение динамической вязкости образцов битумов в
интервале температур 50-120°С. На основании экспериментальных данных по
динамической вязкости получены вязкостно-температурные кривые исследуемых
образцов битумов. Установлено, что для каждого исследуемого образца вязкостно-
температурные кривые описываются двумя температурными интервалами. Это
свидетельствует о том, что битум может находиться в различных фазовых состояниях:
связанно-структурированном и свободно-структурированном состоянии. Анализ
полученных результатов позволил рассчитать значения энергии активации вязкого
течения для связанно-структурированного и свободно-структурированного состояния
исследуемых образцов в соответствии с теорией Эйринга. Она составляет 75-170
кДж/моль.
Показано, что ведение модификатора в сырье процесса окисления изменяет состав
и структуру компонентов нефтяной дисперсной системы за счет адсорбции
компонентов дисперсионной среды на частицах дисперсной фазы и увеличения
концентрации дисперсной фазы, обусловленной участием углеводородов в процессах
конденсации и деструкции. Указанные изменения в испытуемых образцах приводят к
возрастанию энергии активации вязкого течения.
На основе анализа полученных результатов исследования разработаны
рекомендации по их практической реализации.
Работа выполнена при финансовой поддержке БРФФИ (грант № Х12М-051).
FOR NOTES
Section 5
Applied aspects
of chemical
thermodynamics
THE EFFECT FROM METHANOL ADMIX TO ADSORPTION HEATS OF HYDROGEN

BY THE PARTIALLY DEACTIVATED NICKEL CATALYST
FROM AQUEOUS-ALKALINE MEDIUM
Afineevskiy A.V., Lukin M.V.
Scientific Research Institute of Thermodynamics and Kinetics of Chemical Processes,
Ivanovo, e-mail: luckmv@mail.ru
It is known that on the surface of a catalyst such as the skeletal nickel, hydrogen exists
as a specific adsorption nanocomplexes, called individual forms of hydrogen. Purposeful
change of the surface concentrations of adsorbed hydrogen individual forms allows to fine-
tune the activity and selectivity of catalytic systems based on nickel catalysts. However, the
parameters of the adsorbed hydrogen individual forms reactivity are not published, and
conclusions of the fine-tune possibility are made only from a general point. Experimental
basis for the calculation of the thermodynamic parameters of the adsorption nanocomplexes
hydrogen-metal is the hydrogen adsorption heat by the catalyst surface.
The aim of this work was to determine the effect of methanol admix to the adsorption
heat of hydrogen by porous nickel catalyst from solutions of sodium hydroxide - water.
We used a porous nickel, which had a specific surface by BET 89±5 m2/g Ni. As the
liquid phases were used 0,01, 0,1 and 1 M sodium hydroxide solutions with the addition of
methanol up to 0,11 mole fraction. The partial deactivation of the nickel catalyst nickel was
carried out by treated varying amounts (0,05 M and 0,1 M) of aqueous solution of sodium
sulfide; sodium hydroxide had concentration corresponding to used solvent [1].
The research resulted in determination of the adsorption heat of hydrogen on a partially
deactivated porous nickel catalyst from multicomponent solvent water-methanol-sodium
hydroxide. Found that the degree of the nickel catalyst deactivation has a significant influence
on the patterns of hydrogen adsorption by surface of the porous nickel catalyst. It is shown
that reactions on the surface of partially deactivated porous nickel catalyst as well as in the
absence of sodium sulfide takes place dehydrogenation of methanol [2], leading to a
significant for increase adsorbed hydrogen. Comparison of the dependency with [3] illustrated
the differentiation of obtained dependences form; it is facilitating the determination of the
adsorbed hydrogen reactivity parameters in liquid phase hydrogenation reactions. Besides the
formation of the adsorption nanocomplexes: metal - methanol and metal - alkoxide-ion
decreased the adsorption amount of sodium maleate as an organic substrate by the competitive
nature of the adsorption.
References
[1] Prozorov D.A., Lukin M.V., Ulitin M.V. Chemistry and Chemical Technology Research-
Engineering Journal. 2010. V.53. № 2. P. 125-128.
[2] Lukin M.V., Barbov A.V., Ulitin M.V. Russian Journal of Physical Chemistry A. 2001. V.
75. № 9. P. 1528-1532.
[3] Prozorov D.A., Afineevskiy A.V., Ulitin M.V., Lukin M.V. Chemistry and Chemical
Technology Research-Engineering Journal. 2010. V. 53. № 9. P. 18-21.
Section 5 — Applied aspects of chemical thermodynamics ♦ 399
KINETIC DECOMPOSITION TERT-BUTYL HYDROPEROXIDE IN THE PRESENCE

OF DIBENZO-18-CROWN-6
Anisimova V.I., Suvorova I.A., Batyrshin N.N.
Kazan National Research Technological University, Kazan, e-mail: sia_1976@mail.ru
Decomposition of hydroperoxides is one of the most important stages of the radical-

chain degenerate-branching process the oxidation of hydrocarbons, on the kinetics of which
have a great influence education hydrogen-bonded self-associates. The presence of crown
ether oxygen atoms provides the possibility of formation of associates with hydroperoxides.
The objective of the study was to determine the association and its contribution to the
overall rate of decomposition. In this study, we investigated the kinetics of catalytic
decomposition of tert-butyl hydroperoxide (TBHP) in chlorobenzene at 90-120oC ([TBHP]0 =
0,2÷2,0 mol/l) in the presence of crown ether: dibenzo-18-crown-6 ( [DB18CR6]0 = 5∙10-3
mol/l).
It was found that the rate of catalytic decomposition first increases with increasing
concentration of hydroperoxide, and then, reaching a maximum value, no longer dependent on
the concentration of TBHP. This dependence suggests the formation of an intermediate
complex between TBHP and crown ether.
Consequently, we can make the following formal – kinetic scheme:
DB18CR6 + nGPTB ⇆ DB18CR6 · nTBHP
DB18CR6∙nGPTB → DB18CR6 + products
according to the Michaelis-Menten equation rate of decomposition:
k ⋅ K ⋅ [ DB18CR 6]0 [TBHP ]0
W = ,
1 + K ⋅ [TBHP]0
where k – rate constant of the decomposition of the complex TBHP with DB18CR6, K –
equilibrium constant of the complex formation.
There is a method to determine the stoichiometry of the complex, i.e. number of
molecules involved in the complex. For this we find the difference between reverse rates and
reverse maximum rate, construct a graph of their dependence on the concentration of TBHP.
1 1 1
ln( − ) = ln( ) − n ⋅ ln[S ]0
W Wmax K ⋅ Wmax
From the tangent of the slope found that n = 3 - number of molecules TBHP related to
the complex. At the same time, on the order of TBHP close to unity. Consequently, not
decompose all three molecules TBHP related to the complex, but only one. Thus the
decomposition of hydroperoxide obeys bimolecular law and kinetic equation describing the
reaction rate:
W = k·[TBHP]·[DB18CR6].
CHARACTERIZATION OF HYDROGEN AND METHANE ADSORPTION

ON BASOLITE MOF’s USING THE COUPLING OF MANOMETRIC
AND CALORIMETRIC MEASUREMENTS
Rémi André , Pierre Le Parlouër1, Fabrice Bancell, Svetlana Sinyova2, Stanislav Belyaev3
1
1
SETARAM Instrumentation, Caluire, France
2
SETARAM Instrumentation Russia, Saint-Petersburg
e-mail: svetlana.sinyova@setaram.com
3
KOMEF, Moscow, e-mail: komef@komef.ru
Metal-organic frameworks (MOFs) offer an advantage over classical other porous

materials (activated carbon, zeolites) because their properties can be tailored due to the vast
available choices of metal clusters and organic linkers. Nowadays these structures are foreseen
to multiple applications in gas adsorption, like hydrogen storage, selective adsorption of CO2
against CH4, CO2 against H2…
The gas sorption Sievert’s technique has proven to have many advantages over the
other techniques for the evaluation of the ad/ab-sorbed amount of gas by the materials in a
wide range of temperature and pressure. In addition, there is a total freedom in the size and
shape of the sample holder in the volumetric technique, enabling the coupling of techniques
and in-situ measurements of various chemical and physical parameters. The coupling with a
low temperature calorimeter will be described in this presentation.
The thermodynamic of the adsorption is essential for the practical application and
among all the enthalpy of adsorption (or desorption) is a key parameters.
Practically there are two ways to determine this enthalpy. The first one is an indirect
method, where the enthalpy is derived from adsorption isotherms at different temperatures.
The second one is a direct method, where the enthalpy is measured via calorimetric technique.
The paper will present some new results using a combination of calorimetric and
volumetric technique with the adsorption of methane and hydrogen on different Basolite
MOF’s samples. The temperature and pressure conditions ranged between 87K and 303K and
between 0 and 80 bar (50 bar in the case of H2). Both heat effects and pressure drops are
measurable and the recorded data allowed plotting sorption isotherms and calculating the total
heat of adsorption.
THERMODYNAMIC APPROACH TO A QUANTITATIVE ASSESSMENT

OF GLASS-FORMING ABILITY OF Fe-Zr-B MELT
Arutyunyan N.A.1, Zaitsev A.I.1,2, Dunaev S.F.1, Knyazev A.V.2
1
Chemistry Department of M.V. Lomonosov Moscow State University, Moscow
2
I.P. Bardin Central Research Institute of Ferrous Metallurgy, Moscow
e-mail: naarutyunyan@rambler.ru
The field of application of amorphous materials has been expanded significantly due to
their use as a precursor for nanocrystalline or mixed amorphous-crystalline compositions. This
is especially true in regard to the iron-based alloys, including those containing zirconium and
boron. At the same time the search for alloy compositions, which are prone to amorphization,
is carried out mainly by the trial-and-error method. It is caused by the lack of direct criteria for
prediction the possibilities and conditions for transformation of metal melts into an
amorphous state. The purpose of this report is to perform the correlation between the
thermodynamic properties of Fe-Zr-B liquid alloys and their glass-forming ability. Particular
attention has been paid to the specificity of chemical short-range order and the type of
chemical bond between the components. The features have been determined by means of
analysis of the temperature and concentration dependences of the thermodynamic and other
structure-sensitive physico-chemical properties. Analytical representation of the temperature
and concentration dependences of the thermodynamic properties of Fe-Zr-B liquid alloys and
binary subsystems was based on the statistical thermodynamic theory of ideal associated
solutions. This approach allows taking into account various types of chemical bonds between
the components. The covalent interaction is responsible for the formation of molecule-like
associates. Metallic and other types of chemical bonds can be treated as excess interaction. To
determine the type, quantity, and thermodynamic functions of formation of associates as well
as the number and values of coefficients in the expression, which describes the excess
interaction, the method of self-consistent analysis of all available data on the thermodynamic
functions and equilibrium phases has been carried out. The performed calculations resulted in
the conclusion that besides monomer Fe1, Zr1, and B1 particles the associative FeZr2, Fe4Zr,
Fe3B, FeB, ZrB, and ZrB2 groups are present in binary Fe-Zr, Fe-B and Zr-B melts,
respectively. The key features that predetermine the thermodynamic and kinetic stimuli of
amorphization have been determined, viz. excess entropy and heat capacity of the liquid.
Extreme values of these functions correlate with the experimental intervals of amorphization
of Fe-Zr and Fe-B alloys and coincide with the concentration ranges where associative
complexes with the considerable negative entropy of formation prevail, namely FeZr2, Fe4Zr
and Fe3B, respectively. The entropies of formation of ZrB and ZrB2 groups are an order in
magnitudes less. At the same time there is no any available information about amorphization
of Zr-B alloys. Ternary Fe-Zr-B melt is characterized by existence of not only all binary
associates, but also the ternary Fe8ZrB2 complexes with a large negative value of entropy of
formation. The region of maximum presence of complexes of this type coincides with the
interval of amorphization. These results suggest that glass-forming ability of Fe-Zr-B alloys is
determined by rapid increase in the degree of short-range order in the melt during cooling,
which is controlled by the entropy of formation of associative complexes.
This work was supported by the RFBR (grant 10-03-00506).
EXTRACTION AND EQUILIBRIUM PROPERTIES OF SYSTEM INCLUDING

SUPERCRITICAL FLUIDS OF CO2 AND OIL COMPONENTS
1
Asadov М.М., 2Ramazanova E.E., 2Aliyev E.N.,2Shabanov A.L.
1
Institute of Chemical Problems, National Academy of Sciences of Azerbaijan, Baku
2
Scientific-Research Institute of Geotechnological Problems Oil, Gas and Chemistry, Baku
e-mail: mirasadov@gmail.com
Oil and its products are dominant pollutants of the environment. The extraction of
useful components from natural and technogenic materials by various fluid solvents is a very
important process.
In the present work, for extraction of oil-containing substances from soil, we have used
accessible and inexpensive CO2, which can be easily converted into SCF state. CO2 is not
toxic, is non-inflammable and it is a part of atmospheric air and does not pollute the
environment.
The extraction of oil from oil-contaminated soils using SCF CO2 is achieved by using
the following method. In the metal extractor, connected to CO2 gas cylinder, condenser and
pump, we loaded 100 g of oil-bearing soil. The oil content in soil was 3,5 g. From gas cylinder
CO2 was fed into extractor. Using condenser and high-pressure pump CO2 was converted into
SCF state by changing temperature and pressure (251-252 K and 7.1-7.5 MPa). In separator
gas is separated from the extraction products and re-routed to extraction stage.
3,395 g of oil was separated by extraction. The treated soil was removed from the
extractor. In one-period extraction 97 % result achieved in 60 minutes (see Fig).
Figure. Dependence of the extraction

degree of oil and its products from oil-
contaminated soil on the duration of
the SCF CO2 extraction.
Т = 251 K and р = 7,4 MPa.
Thus, it is established that the

fluid extraction process can improve
the extraction degree of oil and its
products from oil-contaminated soil.
This ensures the safety of the process
through the creation of environmentally friendly waste technology. The behavior of critical
lines in systems, containing carbon dioxide and n-alkanes is analyzed.
ANALYTICAL PARAMETRS OF DND AS REVEALD BY DSC

Avramenko N.V., Korobov M.V., Ivanova N.I., Parfenova A.M.,
Senyavin V.M., Beljaeva L.A.
e-mal: natali@td.chem.msu.ru
Physicochemical investigation of the material consisting of disaggregated
nanodiamonds of detonation synthesis (DND) was carried out. It was for the first time when
three forms of the material (liquid dispersion, paste and dry powder) were studied within one
experiment. The material made of disaggregated nanodiamonds in the form of a dry powder
and a paste is not a chaotic mixture of primary nanoparticles but rather a stable secondary
structure containing voids. The structure of this kind can be described by the two parameters –
mean size voids rnano and their total volume Vnano. Parameters rnano and Vnano are the same for
powders and pastes, pastes do not swell; rnano is bigger than that of the primary nanodiamond,
rnano and Vnano are well reproducible and are independent of disintegration method, methods of
powder and paste obtaining.
Differential Scanning Calorimetry (DSC) method was suggested to be able to
distinguish pastes of disaggregated and aggregated nanodiamond materials. DSC curve make
it possible to distinguish disaggregated from non disaggregated samples. One can suggest that
characteristic size and total volume are parameters of nanodiamonds themselves while the
paste is a secondary structure made by primary crystals of nanodiamonds. The structure is
rather stable and is characterized by a narrow size distribution of voids and stable total volume
of voids. Isopiestic and sorption experiments confirm this suggestion.
ΔТ parameter is the most effective (difference in nanophase melting temperature and
volume phase of water). The parameter is determined for aqueous and non aqueous DND
pastes and is a characteristic of the degree of sample disaggregation in pastes and dry
powders. Using benzene instead of water allows to characterize DND by a low degree of
aggregation. The parameter ΔТ allows to control fractionation of materials from disaggregated
DND. Thermogravimetric method TG also used for the first time for DND, supplements DSC
in those cases when kinetic difficulties arise on solvent melting. Thus, in DND pastes formed
by N-methyl-pyrrolidone (NMP) NMP nanophase was detected by TG method only.
Disaggregated DND samples were simultaneously treated by high pressure (80 Kb) and
temperature (800-1500 K). After processing the samples studied by DSC, X-ray diffraction
patterns (XRD), Transmission Electron Microscopic (TEM), Scanning Electron Microscopic
(SEM) methods. DSC method revealed the absence of any secondary structure at all
temperatures. The other methods are allowed to observe the beginning of samples
graphitization at temperatures above 1000 K. The results obtained confirm an earlier
suggestion that nanophase of water fills voids in a secondary structure formed by diamond
nanocrystals. Compression of samples leads to voids disappearance. Ultrasound treatment and
centrifugation does not change the secondary structure of disintegrated DND.
It has been shown that the combination of DSC, adsorption and Dynamic Light
Scattering (DLS) methods allow to obtain reproducible characteristics of three forms of the
material.
This work was supported by RFBR (grant 12-03-00653).
THE CONNECTION BETWEEN THERMODYNAMIC AND QUANTUM PROPERTIES

OF N-ALKANES
Dezortsev S.V., Dolomatov M.Yu., Podyacheva K.I.
Ufa State Academy of Economics and Service, Ufa
e-mail: dezortsev@rambler.ru, dolomatov@gmail.com
The estimation of thermodynamic properties (ThPs) of n-alkanes is essential in the

theory of chemical structure of substance and engineering practice. Classic ThPs of n-alkanes
are most extensively studied.
The purpose of this work is to find the connection between the basic ThPs of n-alkanes
and their electronic structure. It is the continuation of previous investigations in Ref. [1, 2].
Data on ThPs of n-alkanes was taken from [3]. Values of EHOMO and ELUMO were computed by
ab-initio 6-31**G method [4]. All of the compared values were obtained by partition of current
value on the value for the lower paraffin hydrocarbon (С1).
We have ascertained nonlinear quantitative appropriateness between ThPs of n-alkanes
in Gibbs expression for free energy of the system and characteristics of their electronic
structure:
Z = α i ⋅ e β ⋅E , (1), Z = α i + β i ⋅ E + γ i ⋅ (E ) 2 ,
i (2)
where αi, βi and γi – relevant empirical coefficients; Z – thermodynamic property; ЕHOMO and
ЕLUMO – calculated values of the highest occupied molecular orbital (EHOMO) and the lowest
unoccupied molecular orbital (ELUMO) energies, eV, ∆Е – forbidden gap (difference between
the HOMO and LUMO values), eV, IP – ionization potential, eV.
Among ThPs for the n-alkanes С1-С10 homologous series standard enthalpy, entropy and
its change, and free energy by the temperature 298,16 K were examined.
For the expression (1) and (2) best correlations between thermodynamic and quantum
properties of n-alkanes С1-С10 may be observed for calculated values of highest occupied
molecular orbitals energy, the width of conducting band and IP values, confirmed by outcome
of experiment by photoelectron spectroscopy (PES). Correlation coefficients for most of all
determined empirical dependences for ThPs from boundary molecular orbits energies have
values higher, then 0,9. Connection with the forbidden gap and EHOMO clarify itself mostly
neatly. For ELUMO connection with PCP is less then accurate. May be, it can be explained, that
available experimental methods for substance IP determination are better developed and have
higher resolution, then methods of electron affinity determination. Computation programs
correction is making by experiment.
The existence of such correlations means the availability of the concept of
thermodynamic properties forecasting direct from quantum computations and photoelectron
spectroscopy data.
References
[1] Dezortsev S.V., Dolomatov M.Yu., Shutkova S.A., Shuyakovskaya D.V. XVIII
International Conference on Chemical Thermodynamics in Russia, Samara, October 3-7,
2011. V. 1. P 71-73.
[2] Dezortsev S.V., Dolomatov M. Yu. 4th EuCheMS Chemistry Congress, Czech Republic,
Prague, August 26-30, 2012. S. 864.
[3] Physical-chemical properties of individual hydrocarbons /Red.: prof. Tatevsky V.M. / М.:
Gostoptechisdat. 1960. 412 p.
[4] Jensen F. John Wiley&Sons, 2007. 599 p.
THERMODYNAMICS OF FUEL CELL WITH ANODE

BASED ON DOUBLE PEROVSKITE Sr2NiMoO6
Dmitriev A.S., Zhernov I.V., Vylkov A.I., Filonova E.A.
Ural Federal University named after the first President of Russia B.N. Yeltsin, Ekaterinburg
e-mail: dmitriev.vaughn@gmail.com
The solid oxide fuel cell (SOFC) is an electrochemical device that can be used for
stationary or mobile generation of electrical energy from gaseous fuel. The conventional
SOFC, which uses Y2xZr1-2xO2-x(YSZ) as the electrolyte and porous Ni-YSZ cermet anode is
commercially viable with pure H2 or syngas as the fuel. But this anode is fouled by carbon
deposition and sulfur poisoning when operated on natural gas. Development of an anode
material that can operate on natural gas would provide a cheaper, more convenient SOFC. For
this application double perovskite Sr2NiMoO6 have been under investigation due to excellent
tolerance to sulfur.
In present work fuel cell based on Sr2NiMoO6 (as anode material) and
La0.88Sr0.12Ga0.82Mg0.18O2.85 (as electrolyte) has been assembled and investigated. The samples
were obtained by self-propagating synthesis via wet-chemical route. The phase purity was
investigated by means of X-ray diffraction on an Inel Equinox 3000 diffractometer using Cu
Кα-radiation.
Chemical compatibility between electrolyte and anode materials was studied by means
of contact annealing method in temperature range of 1073 ≤ T, K ≤1373. No interaction was
found in the mentioned temperature interval.
The pellet of electrolyte material was polished with flint-paper carefully and anode paste
was deposited by staining method. Then annealing followed by cooling to room temperature
was carried out. After that, the pellet with anode layer was fixed on alundum tube. For that
purpose, a mixture of organic glue with fine high-temperature glass was prepared. The
mixture was applied to the joint of the pellet and the tube. The cell was heat-treated in order to
sealing. The pasteous cathode material (La0.7Sr0.3Co0.9Fe0.1O3) was deposited by staining
method. During the next step, platinum contact leads were connected. The cell was annealed,
cooled to 1123 K and then tested. According to cell design, the top side of the pellet (cathode)
is in air and the bottom side (anode) is in the fuel gas. In order to stabilize the contacts, an
extra hold-down tool was constructed.
The current-voltage characteristic was investigated in temperature range of
823 ≤ T, K ≤1123 with constant flow of the fuel gas. The measurements were carried out by
means of an Agilent 34401A multimeter and a MCP-63 resistance box. It has been found that
the equilibrium value of the electromotive force equals 1179 mV at 1123 K which is 99.3% of
theoretically calculated value. The largest value of maximum power was measured to be 38.39
mW/cm2 at the same temperature.
This work was supported by RFBR (grant 11-03-00282-а).
Reference
Eriksson A.K., Eriksson S.-G., Ivanov S. A. Mat. Res. Bull. 2006. V. 41. P. 144-157.
THE CONNECTIONS BETWEEN MACROSCOPIC AND QUANTUM

PROPERTIES OF N-ALKANES C1-C10
Dolomatov M.Yu., Dezortsev S.V.
e-mail: dolomatov@gmail.com, dezortsev@rambler.ru
The purpose of this work is to find the patterns, connecting the basic physical properties
of n-alkanes and their quantum features from the point of view of thermodynamics and
electrodynamics. Integrated oscillator strength (IOS) in UV, VIS and NIR area is connected
with PCPs of the individual and complex substances by simple empirical dependences [1]:
∆Z = γ ⋅ exp(∆θ ) and ∆Z = γ 0 + γ 1 ⋅ (∆θ ) + γ 2 ⋅ (∆θ ) 2 + γ 3 ⋅ (∆θ ) 3 , (1)
where Z – the equilibrium physical-chemical property of the radiation absorbing system, in the
unit of suitable properties; ∆θ - the change of integral oscillator strength, litre·nm·mole-1·sm-
1
; γ – coefficients, depends on the used substance, which have the dimension
[(property)·107·m-3·mole].
On the one hand, IOS is connected with ionization energy and electron affinity [1]. The
ionization potential (IP) is proportional to the area under absorbance curve:
IP = IP0 + A1 ⋅ θ , (2)
where IP – ionization potential, eV; IP0 – ionization potential of the first term of the
homologous series, eV.
Consequently, present dependences between PCP, optical properties and IP may be used
in practice for prediction of different PCPs. The connections of PCP and corresponded
characteristics of electronic structure can be described by exponential (3) and quadratic
polynomial (4) dependences [2]:
Z = α1 ⋅ e β1⋅EHOMO , Z = α 2 ⋅ e β 2 ⋅ELUMO , Z = α 3 ⋅ e β3 ⋅∆E , (3)
Z = α 1 + β1 ⋅ E HOMO + γ 1 ⋅ ( E HOMO ) 2 , Z = α 2 + β 2 ⋅ E LUMO + γ 2 ⋅ ( E LUMO ) 2 ,
Z = α 3 + β 3 ⋅ ∆E + γ 3 ⋅ (∆E ) 2 , (4)
where αi, βi and γi – relevant empirical coefficients; Z – PCP; ЕHOMO and ЕLUMO – calculated
values of the highest occupied molecular orbital (EHOMO) and the lowest unoccupied
molecular orbital (ELUMO) energies, eV; ∆Е – forbidden gap (difference between the HOMO
and LUMO values), eV.
So, electronic structure of the substance is connected not only with such chemical
properties as reactivity, but with the most of physical properties. Furthermore, it is important
to note, that intermolecular interactions in gas and liquid phase of n-alkanes are connected
with electron transition process and molecular boundary orbitals interactions of condensed
phase particles. Established regularities enlarge the facilities of quantum mechanics and
indicate the common nature of macroscopic and quantum properties of the substance.
References
[1] Dolomatov M.Yu.. Baskirskii khimicheskii zhurnal. 2010. V. 17. № 3. P. 75-80.
[2] Dezortsev S.V., Dolomatov M.Yu., Shutkova S.A., Shulyakovskaya D.V. XVIII
International Conference on Chemical Thermodynamics in Russia. Samara. Russia. October
3-7. 2011. V. 1. P. 71-73.
THERMODYNAMIC AND EXTRACTION PROPERTIES FROM EXPERIMENTAL

STUDY ON INFINITE DILUTION ACTIVITY COEFFICIENTS
OF VAROUS SOLUTES IN IONIC LIQUID
Domańska U.
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology,
Warsaw, e-mail: Ula@ch.pw.edu.pl
The aim of this work is to summarize our systematic studies on activity coefficients at
infinite dilution (γ12∞) of various organic compounds and water in imidazolium-, pyridinium-,
isoqionolinium-, pyrrolidynium-, piperidinium-based ionic liquids (ILs) with different anions
as bis{(trifluoromethyl)sulfonyl}imide, thiocyanate, tosylate, tetracyanoborate and others [1-3].
All sets of experimental data, measured by gas-liquid chromatography, are reported for many
different solutes in IL, for example piperidinium-based ILs [C5C1Pip][NTf2] and
[C6C1Pip][NTf2] in temperature range T = (308.15-358.15) K [4]. Moreover, ambient pressure
liquid densities of those ionic liquids are presented at different temperatures. The results are
discussed in terms of an influence of structure of both solute and ionic liquid on γ12∞.
Capabilities of the studied ionic liquids in liquid-liquid extraction of aromatics or sulphur
compounds from aliphatic hydrocarbons are demonstrated in terms of infinite dilution
selectivity and capacity.
Finally, linear solvation energy relationship (LSER) theory and regular solution theory
(RST) were used to analyze the obtained experimental data. In particular, correlative and
predictive power of the most current version of the LSER is demonstrated and the
Hildebrand’s solubility parameters are calculated as a function of temperature by using the
RST [4].
References
[1] Domańska U. Królikowski M., Acree W.E. J. Chem. Thermodyn., 2011, 43, 1810-1817.
[2] Domańska U. Królikowska M. J. Chem. Eng. Data, 2011, 56, 124-129.
[3] Domańska U., Królikowski M. J. Chem. Eng. Data, 2010, 55, 4817-4822.
[4] Paduszyński K., Domańska U. J. Chem. Thermodyn. (2012) submitted.
ASSESSMENT OF PHASE DIAGRAMS OF THE SYSTEMS

BASED ON UREA AND AMMONIUM NITRATE
Dzuban A.V., Aitekenov S.K., Voskov A.L., Uspenskaya I.A., Voronin G.F.
e-mail: alex.dzuban@gmail.com
Urea and ammonium nitrate are the most popular solid nitrogen fertilizers and their
water solutions (UAN) are widely used liquid fertilizers. Addition of salts containing sulphur,
potassium, calcium and other elements to solid urea or its solutions allows to develop new
complex fertilizers. However a lot of thermodynamic properties of such multicomponent
mixtures should be studied before such development including its physico-chemical and
thermodynamic properties. The possibility of phase transformations under temperature
variations, interaction with water and atmospheric gases can lead either to destruction of solid
fertilizers pellets or to solution decomposition with a precipitation of solid phase; also
relatively high freezing temperatures impose constraints on conditions of shipping and storage
of liquid fertilizers. These and many other problems can be solved by investigating
corresponding phase diagrams.
Usually the systems presenting a practical interest are multicomponent. In this case
phase equilibria calculation is a reasonable alternative to direct experimental investigations. A
choice of suitable thermodynamic models and optimization of their parameters for binary
systems followed by transition to a system of higher order allows decreasing time required for
investigation of new compositions. By means of such approach experiments for validation of
calculation results or for model parameters refinement can be conducted selectively.
In this work we present calculation results of iso- and polythermal sections of phase
diagrams for systems consisted of urea, water, sulphate, thiosulphate, ammonium nitrate and
potassium formate. As an example calculated liquidus surface and isothermal section of H2O
– (NH2)2CO – HCOOK phase diagram at 270 K are shown in the figure.
This work was supported by RFBR (grants 11-03-00499-a and 12-03-31069-mol-a) and
the URALCHEM OJSC.
THERMAL PROPERTIES OF VOLATILE RHENIUM COMPOUNDS

AND COATING OBTAINING BY MOCVD
Gelfond N.V., Zherikova K.V., Morozova N.B., Semyannikov P.P., Sysoev S.V., Igumenov I.K.
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, e-mail: gel@niic.nsc.ru
Rhenium has a unique combination of physical and chemical properties which makes it
and its alloys and compounds ideal for use in electronics, electrical and instrument
engineering, and as catalysts in various chemical processes. Rhenium coatings are used to
improve the heat and wear resistance of the details and protect them against corrosion. In
recent years chemical vapor deposition by the thermal decomposition of initial metal
compound (precursor) vapors on the product’s surface (MOCVD) became widespread to
obtain rhenium layers. In present study we selected the following precursors for formation of
rhenium coatings by MOCVD: dirhenium decacarbonyl Re2(CO)10 and cyclopentadienyl
rhenium tricarbonyl Re(CO)3(Cp).
To select the parameters of MOCVD process of rhenium coating deposition we
undertook the investigations aimed at obtaining the information about the thermal behaviour
of the complexes in the condensed and gas phases, temperatures of decomposition beginning
and products of thermal decomposition of compound’s vapours, temperature dependencies of
the saturated vapour pressure for the complexes.
The thermal behaviour of Re(CO)3(C5H5) in the condensed phase is studied by means of
thermogravimetry and differential scanning calorimetry. Thermal decomposition of the vapour
of Re2(CO)10 and Re(CO)3(C5H5) is investigated in vacuum and in the presence of hydrogen
and water vapours by means of in situ high-temperature mass spectrometry. The routes of
vapour decomposition on a heated surface are proposed. Using Knudsen's effusion method
with mass spectrometric registration of the gas phase composition and the flow method,
temperature dependences of saturated vapour pressure were measured; thermodynamic
parameters of the sublimation of complexes were calculated. For Re2(CO)10 we specified the
data on the saturated vapour pressure using two independent methods within the temperature
range below the phase transformations of the compound and the start of decomposition of
complex vapour: ∆Н°Т aver. = (95,5 ± 2,3) kJ·mol-1, ∆S°Т aver. = (188,3 ± 7,0) J·mol-1·K-1
(effusion method), ∆Н°Т aver. = (93,6 ± 1,7) kJ·mol-1, ∆S°Т aver. = (187,5 ± 5,0) J·mol-1·K-1
(flow method). For Re(CO)3(C5H5) the thermodynamic characteristics were determined for
the first time: ∆Н°Т aver. = (85,2 ± 1,0) kJ·mol-1, ∆S°Т aver. = (173,6 ± 2,7) J·mol-1·K-1 (flow
method).
Based on this research the deposition conditions were defined for performing MOCVD
experiments. As a result rhenium coatings with an average thickness of 3-13 microns and 2-8
microns using Re2(CO)10 and Re(CO)3(Cp), respectively, were obtained in an atmosphere of
hydrogen on steel and ceramic (C/SiC) substrates. The coatings were investigated by X-ray
diffraction and scanning electron microscopy. The growth mechanism proved to rather vary in
case of using different precursors.
THE STUDY OF THE THERMODYNAMIC PROPERTIES OF MATERIALS BASED

ON CALCIUM PHOSPHATES ACCORDING TO ATOMIC FORCE MICROSCOPY
Golovanova O.A., Galashova S.A., Lobov I.A.
F.M. Dostoevsky Omsk State University, Omsk, e-mail: galashovasa@mail.ru
In recent years much attention is paid to improving the quality and duration of human
life. Lesions and joint diseases are a problem for people of all ages. The most effective way to
treat and restore the integrity of the tissue paid in this case is a joint replacement. It was the
creation of implants and materials that can replace the last tissue is an important task for
today’s materials scientists, chemist and etc. One possible solution to this problem is to create
a bioactive coating on metal implants.
One of the subjects of extensive research as the coating material and the implant is
hydroxyapatite which is a natural mineral as well as the main mineral component of bone
tissue.
In thermodynamic calculation as a prototype of a biological fluid model solution was
taken mineral composition (inorganic macro components), temperature, ionic force and pH,
which correspond those of healthy adult body fluids of an average person. To perform the
calculation we used the values of the thermodynamics
products solubility K0s of sparinglysoluble compounds,
which may occur in the study of hypothetical
solutions. To assess the possible formation of poorly
soluble compound using the calculated values of the
indices of supersaturation SI; (quantitatively)
supersaturation (S) in solution generated relatively
poorly soluble compound (Mp+Aq-). Overall, the results
f thermodynamic calculations showed that
hydroxyapatite is the most thermodynamically stably
phase as fizioge and pathogens minerals which
confirms a special role in their formation.
It is known that the energy of the solid phase of
the embryo depends on the degree of supersaturation
of it also depends on the size of the critical radius of
the embryo. The study of the thermodynamic parameters Fig. The atomic force image of the
of hydroxyapatite crystallization will enable to clarify the crystal hydroxyapatite.
mechanism of its crystals.
We attempted to determine the Gibbs energy of formation of aggregates of the solid
phase on the basic on data obtained from the study of the synthesized hydroxyapatite samples
by atomic force microscopy.
THERMODYNAMIC PARTICULARITY OF Al2O3-SiO2-C

Grishin N.N., Belogurova O.A.
I.V. Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Raw
Materials, Kola Science Centre of RAS, Apatity, Murmansk region
e-mail: grishin@chemy.kolasc.net.ru
The thermodynamics of the processes occurring in the system Al2O3–SiO2–C, for

products mullitization of kyanite 3(Al2O3·SiO2) → 3Al2O3·2SiO2 + SiO2 was observed. We
were shown that the investigated system behaves as two formally independent subsystems
SiO2–C and Al2O3–C.
Carbothermal reduction in psevdo close system for products of mullitization
thermodynamically most probable are the reactions leading to the formation of silicon carbide.
It may be formed during the firing of materials at the interface of carbon with SiO2 on the
reaction of SiO2 + 3С → SiC + 2СО. Moreover the capture of gaseous silicon monoxide,
emerging in the reaction zone, and link it to the carbide on the surface of the carbon particles
according to the equation SiО + 2С = SiС + СO is occured. Carbidization of aluminosilicate
matrix was allowed to get high temperature mullite-graphite refractory and insulating
materials.
Creation of conditions preventing the formation of a direct contact of grains of mullite,
SiO2 and Al2O3 with carbon and thus blocking of thermodynamically most probable reactions
of carbidization and ensure removal from the reaction zone of gaseous reaction products, will
direct reduction reaction towards the formation of gaseous silicon monoxide. In the pseudo
open system, the carbon presenting in the charge is not directly involved in the recovery
process SiO2 free or bound into mullite by direct contact with him, but shifts the equilibrium
reaction SiO2 → SiO + 0,5О2 towards the formation of silicon monoxide.
Due to this side effect of carbon, silica generated during mullitization of kyanite
effectively dissociates at high temperature to form a gaseous SiO, which diffuses out of the
sample, transfering the silicon in carbon backfill where it is reduced and disproportionates in
reactions (SiOг + 2Ств = SiCтв + СОг and 2SiOг → SiO2 + Si) to form SiC, SiO2 and Si. As a
result, in the remaining solid phase was concentrated alumina. High-alumina precursor Al2O3
(95%) with the ratio Al2O3/SiO2 = 10-60 were received. Chemical beneficiation leads to the
formation of product which use as perspective raw material for getting of aluminum metal.
Chemical beneficiation leads to the formation of product which use as perspective raw
material for getting of aluminum metal.
POLYMER COMPOSITES BASED ON THERMALLY STABLE POLYAMIDEIMIDE

AND POLYVINYLPYRROLIDONE FOR MEMBRANE TECHNOLOGIES:
STRUCTURE AND THERMAL PROPERTIES
Gubanova G.N., Smirnova V.E., Popova E.N., Romashkova K.A., Kononova S.V.
Institute of Macromolecular Compounds, Russian Academy of Sciences, Saint-Petersburg
e-mail: gubanovagn@yandex.ru
Nonporous films based on compositions of polyamideimide (PAI) and

polyvinylpyrrolidone (PVP) perspective for pervaporation membrane were investigated by
differential scanning calorimetry (DSC) and dynamical mechanical analysis (DMA). PAI was
synthesized by the low-temperature polycondensation of dicarboxyphenyl-phthalimide
dichloride with 4,4’-diaminodiphenyl ether (M 68000). PVP with molecular weight MM
24000 was used. Compositions PAI (100 wt%), PVP (100 wt%), PAI/PVP (50:50 wt%) and
PAI/PVP (33:67 wt%) were prepared by stirring PAI and PVP in N-methylpyrrolidone
solution at room temperature.
The glass transition temperature of PVP was registered on DSC curve at 152˚C. After
heat treatment of sample near the glass transition temperature diffused endothermic peak,
connected with the destruction of mesomorphic structure of PVP, was registered. At the
second scan endothermic peak under discussion does not observed. On the DSC curve PAI-
PVP (50:50 %) and PAI-PVP (33:67 %) glass transition temperatures are observed at 190 and
189˚C correspondingly. Having been compared this value with values of the glass transition
temperature of neat PVP (152˚) and neat PAI - 270˚C, one can conclude that this temperature
characterizes composition PAI-PVP, being compatible on the molecular level.
Glass transitions temperatures of neat PAI and neat PVP expected at least for
composition PAI/PVP (33,3 wt%: 66,7 wt%) did not observed, which is contrary to the
assumption about appearance of micro-heterogeneity with the increasing of PVP contents.
This result led to necessity of investigations of PAI/PVP composition films by dynamical
mechanical analysis.
According to DMA data only one maximum at 196°C is observed on tg δ (T) curve for
composition PAI/PVP(50:50 wt%), that confirms good compatibility of polymer components.
During further heating at 270°C sharp increasing of tg δ is observed owing to plastic yielding
of polymer. Partially incompatibility of components of this composition (concerning PVP)
was observed as shoulder at 150˚C on the tg δ (T) curve. Consequently, composition PAI/PVP
(50:50 wt%) may be regarded as homogenous system. More complex temperature dependence
was observed for composition PAI/PVP (33,3 wt% : 66,7 wt%). Three maximums were
observed on tg δ curve: more intensive peak at 150°C, corresponding to pure PVP, the peak at
200°C, corresponding to PAI/PVP system and peak at 270°C, corresponding to the separate
phase of PAI. Consequently, this composition is heterogenous system with three separate
polymer phases.
The obtained results are in a good agreement with DSC and WAXS data.
INVESTIGATION OF THE MELTING OF THE METALLIC POWDER PR-N77Х15С3R2

Ilinykh A.S., Zamyatin V.M., Barbin N.M., Krivorogov M.V.
Ural Institute of the State Fire Service EMERCOM of Russia, Yekaterinburg
e-mail: asi85@yandex.ru
To obtain a high wear resistance, corrosion resistance and heat resistance of steel
components of machines and mechanisms the metallic powders are melted on their surfaces.
When plasma heating takes place, powder materials are melted and thin layer is formed
on the surface of component. Then crystallization process takes place and powder coating is
formed [1-3].
To choose the rational parameters of putting of coatings and regime of the plasma
treatment of the surface of components it is necessary to improve our notions about the
process of melting of the powder material and the properties of the formed alloy. So,
presented work is devoted to investigation of these questions.
As a material for the study the metallic powder on the basis of nickel (PR-
N77Х15С3R2) of fraction 20-100 mkm was taken. Chemical composition (in masses. %) of
investigated material is following: Ni -0.5C - 15Cr - 3.2Si – 2B.
The process of melting of the alloy was studied by the method of thermal analysis.
The thermogram of heating of the
investigated pattern is presented on the Fig.1.
As we can see, this curve has five
characteristic fractures. The first fracture at
T=931ºC shows the beginning of melting of
pattern (the temperature of the solidus line of
alloy). Last fracture at T=1028ºC corresponds
to the end of melting (the temperature of the
liquidus of alloy).
Between these boundary values of
temperature interval three additional fractures
are discovered, that testify about the phase
transformations in the two-phase region of
alloy according to the peritectic reaction. Fig. 1. The thermogram of heating of alloy.
References
[1] Antsiferov V.N., Shmakov A.M., Ageev, S.S., Bulanov V.Ya. Gas-thermal coatings.
Ekaterinburg: «Science», 1994.
[2] Borisov Yu.S., Kharlamov Yu.A., Sidorenko S.L. Kiev: Naukova Dumka, 1987. 544 p.
[3] Shevchenko O. Nizhny Tagil: NTI (f) of the USTU – UPI. 2006. 290 p.
EXTENSION OF THE CUBIC-PLUS-ASSOCIATION (CPA) EQUATION OF STATE

TO NFM-BENZENE DERIVATIVES
Izadpanah A.A., Osfouri S., Mahmoudjanlo H.
Department of Chemical Engineering, Faculty of Gas and Petrochemical Engineering,
Khalij Fars University, Bushehr, e-mail: hmjanlo@gmail.com
Vapor-liquid phase equilibrium in the distillation operations are very important.

Therefore using a thermodynamic model for estimating these types of experimental data at
different pressure and temperatures and or extrapolation of new points according to
experimental data is very much desired. In this work, we study the vapor-liquid phase
equilibria of systems containing N-formylmorpholine (NFM) and benzene derivatives using
Cubic-plus-Association (CPA) Equation of State. CPA EoS that was presented by
Kontogeorgis et al.2 in 1996 has used a lot in recent years. Benzene derivatives include 1,3,5-
trimethylbenzene, 1,2,4-trimethylbenzene, buthylbenzene, ethylbenzene and
isopropylbenzene.
First, the CPA EoS parameters for NFM with 5 association schemes are obtained using
vapor pressure and saturated liquid density data. Then for determining the best parameters, the
vapor-liquid phase equilibrium for systems containing NFM and aromatics is investigated. As
the vapor-liquid phase equilibrium description depends on the EoS parameters, a discussion is
also presented about the best set of parameters and the method to estimate them. Also the best
parameters of the SRK EoS for 1, 2, 4- trimethylbenzene are obtained and the 2B, 4C
association scheme has chosen as the good association scheme for NFM solvent.
THERMODYNAMIC CHARACTERISTICS OF CALCIUM PHOSPHATE ADHESION

ON THE TITANIUM ALLOYS
Izmailov R.R., Golovanova O.A.
F.M. Dostoevsky Omsk State University, Omsk, e-mail: izmailov_87@mail.ru
One of the actual problems of modern science (chemistry, physics, medicine) is the
synthesis and study of bioactive substances for medical use. Most effective among coatings
with bioactive properties are calcium phosphates coatings. In this paper we identified
adhesion characteristics of carbonate hydroxylapatite (CHA) on titanium, using the
measurement of contact angle and surface tension of CHA suspensions. Found that surface
tension and contact angle increase with the growth of carbonate hydroxylapatite concentration.
In our opinion, this fact may be related to the partial dissolution of calcium phosphate and
formation of inorganic surface inactive substances. At a concentration of CHA in a suspension
of more than 10%, the surface of titanium alloy is not wetted. One of the main and important
characteristics of the coating is ratio of the energy of adhesion (Wa) and cohesion (Wc). This
ratio may be obtained from the Young-Dupré equation:
Wa Wa 1 + cos Θ
= 1 + cos Θ, (1) = , (2)
σ 01 2σ 01 2
Wa 1 + cos Θ
Wc = 2σ 01 , (3) = . (4)
Wc 2
In this case, it was found that the growth of the CHA concentration of suspension causes
decrease of the adhesion energy which characterizes the interaction of the dispersed system
with a titanium surface. So with a doubling of the amount of carbonate hydroxylapatite the
adhesion energy decreases of 0.7 and more (fig. 1).
140
120
Adhesion energy, MJ
100
80
60
40
20
0
5% 10 % 20 %
Fig. 1. Dependence of the adhesion energy
Сalcium phosphate concentration, % mass.
of calcium phosphate concentration.
Also, there is an increase the cohesive energy, which characterize the interaction in the
dispersion system. In our opinion, this fact may be explained by the formation of the thick
coating. The degree of wetting is determined by a balance between adhesive and cohesive
energies, in addition, when its ratio is close to 1 and then there is wet, etc. Found that at the
concentration of calcium phosphate over 10% there is a transition to a nonwettability.
As a result of research the adhesion characteristics that allow to control the quality of
the bioactive calcium phosphate coatings on titanium alloys obtained by using the
thermodynamic parameters.
This work was supported by the RFBR (grants 12-03-98011-r_sibir_a).
COMPUTATIONAL SEARCH FOR NEW REFRIGERANTS

Kazakov A.1, McLinden M.O.1, Domanski P.A.2, Heo J.2, Brown J.S.3, Frenkel M.1
1
Applied Chemicals and Materials Division, National Institute of Standards and Technology,
Boulder, CO, USA, e-mail: andrei.kazakov@nist.gov
2
Energy and Environment Division. National Institute of Standards and Technology,
Gaithersburg, MD, USA
3
Department of Mechanical Engineering. Catholic University of America,
Washington, DC, USA
Recently, the concerns of climate change have initiated a search for new refrigerants
with low Global Warming Potential (GWP). Specifically, the use of hydrofluoroolefins
(HFOs) is presently considered. Due to the presence of double bond(s) and, consequently,
high reaction rates with atmospheric OH, HFOs have much lower atmospheric lifetimes than
the HFC-based refrigerants presently in use. However, a more systematic search for new
classes of refrigerants that, in addition to having low GWP, would also satisfy thermodynamic
performance and safety requirements has not been attempted. We explore the possibilities for
refrigerants having low global warming potential (GWP) using two distinct, but
complimentary, approaches. In the first approach, we evaluate the effect of a refrigerant’s
fundamental thermodynamic parameters on its performance in the simple vapor compression
cycle and several variations on the simple cycle; this defines the limits of what is
thermodynamically possible for a refrigerant. The analysis employs evolutionary algorithms,
and it identifies the critical temperature and ideal-gas heat capacity as the most significant
fluid parameters. There is a fundamental tradeoff between high efficiency and high volumetric
capacity, especially for the simple vapor compression cycle. Differences between refrigerants
in the simple cycle can be reduced by proper cycle modifications. In the second approach, we
examine more than 56000 chemical compounds from a public domain database of chemical
structures. A subset of about 1200 candidate fluids is identified by applying screening criteria
to estimates for GWP, flammability, stability, toxicity, and critical temperature. The fluids
with critical temperatures below 400 K (i.e., those which could be used in current equipment
with minor modifications), are dominated by halogenated olefins. Additional chemical
families, including ethers and cyclic compounds, are represented among the fluids having
critical temperatures above 400 K. Combination of the results of the two approaches allows
further reduction of the candidate pool. Finally, the performance of the remaining fluids was
tested in different cycle simulations.
DYNAMICS OF THE ENTROPY CHANGING FOR THE PROCESS OF CATALYSTS

POLYMERIZATION SYNTHESIS
Kerbaliyev R.A., Seyidov N.M.
Institute of Petrochemical Processes of National Academy Sciences of Azerbaijan, Baku
e-mail: rask1@rambler.ru
Thermo-physical characteristics of the process have been studied [1]. Meanwhile such an
important part of chemical thermodynamics as a tend of chemical reaction has not been yet
considered. According to the second law of thermodynamics the transformation is spontaneously
going only for processes which is accompanied by on entropy increasing.
The entropy is determined by the following way:
∆S 298 = Σ∆S 298
0
( prod .) − Σ∆S 298
0
(read .) (1)
The relationship (1) shows the mode of determination of the chemical reaction entropy at
reference temperature (298 K) chosen. It should be noted that the relationship does not reflect
peculiarities of the process because of relevancy for the reference temperature. However in reality
this process is conducted within the interval 348-363 K. The relationship characterizing the
entropy change on temperature is given as follows [2].
T2
S t = S0298 + ∫ CpdT/T (2)

T1
Mechanism of reaction of the catalyst synthesis has been studied in details it consists of 6 stages:
1) CCl4 + 2H2O → 4HCl + CO2 ↑
2) 6HCl + 2Al → AlCl3 + 3H2 ↑
3) CCl4 → CĊl3+ Ċl
4) CĊl3 + CĊl3 → C2Cl6
5) 2Al + 6Ċl → Al2Cl6
6) 2Al + CĊl3 → Al2Cl6 + 2С
The dependence of heat capacity on temperature can be expressed as follows:

Cp = a+ bT + cT2 (3)
Submitting Cp from (3) value into (2) we can obtain:
S t = S0298 + ∫ (ν 3 a 3 + ν 4 a 4 ) - (ν 1a 1 + ν 2 a 2 )dT + ∫ (ν 3 b 3 + ν 4 b 4 ) − (ν 1b1 + ν 2 b 2 )TdT +

1
(4)
+ ∫ (ν 3 c 3 + ν 4 c 4 ) − (ν 1c1 + ν 2 c 2 )dT/T 2
Denote: (ν 3 a 3 + ν 4 a 4 ) - (ν 1a 1 + ν 2 a 2 ) → α
(ν 3 b 3 + ν 4 b 4 ) − (ν 1 b1 + ν 2 b 2 ) → в (5)
(ν 3 c 3 + ν 4 c 4 ) − (ν 1c1 + ν 2 c 2 ) → γ
Integrating expression (4) with assumption for (5) one can obtain:
 T2 T 2   1 1 
S t = S0298 + α (T2 - T1 ) + β  2 − 1  +  − 
 2 2   T2 T1 
The results of entropies temperature dependences of for each of 6 stages are obtained.
[1] Seyidov N.M., Dahlin M.A. and others. A.S. № 732229 USSR. Byull. № 17. 1980.
CALORIMETRY OF ACRILYC GLUE COMPOSITION HARDENING BY UNDER

ACTION THE COMPLEXES OF AMINE AND TRIALKYLBORANE
Kir’yanov K.V., Gulenova M.V., Dodonov V.A.
N.I. Lobachevsky Nizhny Novgorod State University, Nizhny Novgorod
e-mail: kvkiryanov@yandex.ru
The thermal effect accompanying by glue composition hardening leads to uncontrollable

uneven heating of a glue joint. Under certain conditions the glue composition cracks will
appear, and at high temperatures the destruction of the polymer material is possible. This
process leads with the change of structure and violation of quality appropriate gluing material.
The influence of trialkylborane, amines and small additives – quinones (n-quinone,
anthraquinone), peroxides (dibenzoil-, dilauroil- and t-BuOOH) on the heat evolution in the
process of hardening the adhesive compositions was experimentally studied with using a
DAK1-1A microcalorimeter of Kalve type. We selected the optimum ratio the components of
acrilyc composition. The acrilyc base (AB) consists of methylmethacrylate (36 mas.%),
buthylacrylate (24,5 mas.%), hydroquinone (1,5 mas.%), acrylic acid (6 mas.%) and PMMA
(29 mas.%, Dacryl 90). We used the complex of trialkylborane (R = Et, Pr) and amine
(NH2(CH2)6NH2 (GMDA) or CH3O(CH2)3NH2) (MOPA) as a hardener with concentration of
3-5 mas.%.
This recipe is applicable for bonding of thermoplastics with low surface energy, such as:
polyethylene (PE), PVC, PTFE-4, and its components are easily available in the Russian
chemical market. The specified glue system hardened at the room temperature and showed
high adhesive strength with good stability over time.
We carried out of hardening reaction at 298,15 K and pressure of 101,325 kPas in the
dry argon atmosphere. It was established, that in case of the specified systems thermo-kinetic
curves of the process of hardening depend only on the type of entered amine and have two
fields of heat evolution. In the first field we observed sharp increase in thermal capacity,
which in the first 10 min of composition hardening reached values 0,15 for complexes with
GMDA, and 0,07 W / (of AB) – with MOPA. This is due, apparently, the interaction of
trialkylborane with dissolved monomer oxygen, resulting in the generated oxygen - and
carbon-centered radicals. The subsequent increase and decline of heat evolution was due to
the classical polymerization acrylic monomers. Optimal initiating system Et3B-
NH2(CH2)6NH2 has ratio B:N equal to 1:1.5.
At the introduction of small additives in the second field of heat evolution we observed
two maxima. The last, about 1-3 mW / (g AB), may occur at the expense of additional radical
formation through the course of diffusion processes in the interaction between trialkylborane
and peroxides, and, mainly, with p-quinones. This is especially pronounced in the case of
dibenzoilperoxide and nafthoquinone. Additives of nafthoquinone, p-quinone and
dilauroilperoxide are activators of process of composition hardening. The other studied
additives play a role of destabilizers in these process.
The study of the influence of small additions of quinones providing a high degree of
conversion monomer acrilyc composition allowed to determine of the optimal glue
composition structure.
KINETICS OF REDUCTION AND THERMODYNAMICS OF SUBLIMATION

OF ALKALINE PROMOTOR IN К2О⋅nFe2O3 SYSTEM
Kiselev A.E., Kudin L.S.
Ivanovo State University of Chemistry and Technology, Ivanovo, e-mail: fulleren@inbox.ru
The processes, which occur at reduction (activation) of catalytic agent, determine the
finite composition of catalyst and the distribution of the active centers on the surface with the
definite free energy. In this report a high temperature mass spectrometry method is used to
study the process activation of the catalyst precursor К2О⋅nFe2O3 for the steam conversion
reaction of CO.
Three processes take place in the temperature range 750-1200 K. The sublimation in the
form of К2О molecules from the surface Fe2O3 occurs up to temperature 1010-1050 K. In this
case the partial vapor pressures of К2О molecules over К2О⋅nFe2O3 about two and more times
less than over pure К2О. The effective values of sublimation enthalpies of the alkaline
promoter depend on its concentration in solid phase and are given in Table.
In the temperature range 910-990 K Fe2O3 dissociates with forming of the homogeneous
solid solution Fe3O4 in Fe2O3. In turn, in the temperature range 1030-1200 K the
heterogeneous system Fe3O4-Fe2O3 dissociates with formation of Fe3O4. It should be noted
that, the effect of changing of mass spectra and hence the vapor composition over the system
under study in the activation process, has been observed during the reduction period of a
heterogeneous system. To interpret this phenomenon has been hypothesized on the
restructuring of the lattice of the catalyst during its reduction, controlled by the chemical
promoter. As results of this rearrangement, the interaction of the potassium oxide with the
catalyst precursor changes radically: with the hematite K2O forms a number of chemical
compounds (ferrites K2O∙nFe2O3), but with the magnetite K2O forms the system Fe3O4-
K2O∙mFe2O3 (where m is a residue of the hematite, which does not reduce during the process
activation of catalyst precursor). Presumably, the regulation of the finite ratio Fe2+:Fe3+ is
directly related to the amount of K2O:the ion Fe3+, which is located near an alkali metal,
reduces more difficult, namely, when the ratio in the residue mFe2O3:K2O becomes equal m:1,
K2O prevents from the further reduction. The rate of reduction is decreased with increasing of
the amount of potassium oxide in the solid phase.
After the reduction of catalyst precursor only the atoms K become the products of
sublimation of Fe3O4-K2O∙mFe2O3 system. The effective values of sublimation enthalpies of
potassium are listed in the Table. The magnetite formed, apparently, because of the
peculiarities of its crystal structure promotes the lengthening of К—О bond, which leads to it
rupture and sublimation of atoms K. This fact, according to authors, predetermines the
property of alkali metal atoms to activate the work the active centers on the surface, while
being in inert form of the oxide.
Table. Effective enthalpies of sublimation ∆sHо(Т) components of the alkaline promoter
(kJ/mol)
Vapor component \\ mass.% К2О 2 8,89 16,37 37,01
К2 О 253±27 172±12 126,8±9 171±15
К 217±15 223±12 412±36 325±32
Thus, mass spectrometric study of the dynamics change of the partial vapor pressures of
atoms K and molecules К2О under reducing conditions at a constant temperature allows
determining the kinetic characteristic of the reduction process of the catalyst.
THERMODYNAMIC ANALYSIS OF REACTIONS OF SODIUM-THERMAL

REDUCTION OF COMPLEX TANTALUM OXOFLUORIDE COMPOUNDS
Kolosov V.N., Orlov V.N., Prokhorova T.Yu., Miroshnichenko M.N.
I.V. Tananaev Institute of Chemistry and technology of Rare Elements and Mineral Raw
Materials, Kola Science Centre of RAS, Apatity, е-mail: tantal@chemy.kolasc.net.ru
Tantalum powders are widely used as precursors in the production of capacitors with
porous anodes. Commonly, they are produced by sodium-thermal reduction of potassium
heptafluorotantalate (K2TaF7) from a melt with a composition corrected by a flux represented
by an alkali metal halide. In view of the trend to miniaturization, it is necessary for
radioelectronics to have higher capacity per one unit of capacitor volume, which means
employing tantalum powders with increasing specific surfaces. The specific surface can be
extended by employing melts in which the K2TaF7 is, either partly or entirely, displaced by
complex tantalum oxofluoride compounds. To select compounds for oxygen-containing
admixtures in sodium-thermal reduction of finely dispersed tantalum powder, there has been
performed a thermodynamic analysis of sodium-thermal reduction of oxofluoride tantalum
compounds.
Calculations were carried out with regard for the aggregate state of reagents and
products, in the first approximation (without taking into account the temperature dependence
of the reagents’ thermal capacity). Some of the thermal characteristics (enthalpy, entropy),
lacking in the literature for certain oxofluoride compounds, were calculated using the
Sokolov-Belyaev method. Below are presented the results of thermodynamic analysis of
reactions of tantalum oxofluoride compounds reduction by sodium.
Thermodynamic data of reactions of sodium reduction of complex oxofluoride tantalum
compounds
ΔH0, ΔS0, ΔG973, ΔG1073,
Reduction reaction
kJ·mole-1 J·mole-1·K-1 kJ·mole-1 kJ·mole-1
K2TaO2F3+5Na=
-242.0 69.3 -309.3 -316.3
Ta+2KF+NaF+2Na2O
KTaOF4+5Na=
-699.4 86.3 -783.4 -792.0
Ta+KF+3NaF+Na2O
K3TaOF6+5Na=
-529.8 134.6 -660.8 -674.2
Ta+3KF+3NaF+Na2O
K2Ta2O3F6+10Na=
-812.9 198.0 -1005.5 -1025.3
2Ta+2KF+4NaF+3Na2O
The experiments have proved the possibility of sodium reduction of the above
mentioned compounds.
This work was supported by the RFFR (grant 12-03-98803 - р_sever_а).
PHASE EQUILIBRIA AND CONVERSION OF SALTS IN THE MULTICOMPONENT

WATER-SALT SYSTEMS CONTAINING POTASSIUM NITRATE
Kudryashova O.S., Matveeva K.R., Kistanova N.S.
Natural Science Institute of the Perm State University National Research,
Perm, e-mail: oskud@psu.ru
Double decomposition reaction of salts aimed on potassium nitrate production can be

carried out between alkaline, alkaline-earth metals or ammonium nitrates and potassium
chloride, sulfate or carbonate, for example:
NaNO3 + KСl = NaCl + KNO3
Magnesium or calcium nitrate can be used in the process instead of sodium salt.
Reaction with sodium nitrate only is used in industry though there are a number of patents for
a conversion method of potassium nitrate from calcium nitrate and potassium chloride
receiving. Technological process of potassium nitrate receiving based on double
decomposition reaction which was given above include a stage of solution evaporation with
the subsequent polythermal crystallization of salt, is well studied and based on solubility
diagram of the system NaNO3 + KСl = NaCl + KNO3 – H2O.
On purpose of optimum temperature and concentration parameters determination of
potassium nitrate from magnesium or calcium nitrate receiving processes the solubility in
four-component mutual water-salt systems Mg(NO3)2 + 2KСl = MgCl2 + 2KNO3 – H2O and
Ca(NO3)2 + 2KСl = CaCl2 + 2KNO3 – H2O at 25 and 50ºС was studied for the first time.
On the basis of 2KCl + Mg(NO3)2 ↔ 2KNO3 + MgCl2 – H2O system solubility diagram
the scheme of magnesium chloride and potassium nitrate crystallization process in a closed
cycle with two stages was offered. Potassium nitrate crystallization is carried out at 20±2ºС.
Magnesium chloride dihydrate can be received by mother liquor evaporation. In Ca(NO3)2 +
2KСl = CaCl2 + 2KNO3 – H2O system crystalline potassium nitrate receiving at 20±2ºС is
also feasible. However possibility of calcium chloride receiving in a crystalline state or in the
form of solution requires additional treatment at mother liquor and use of low temperatures.
Comparison of the three systems listed above showed that the maximum potassium
nitrate yield virtually is not depends on crystallization temperature and happens to be in
system with magnesium salt. The solubility diagram topology of this system is such that the
mother liquor remaining after crystallization and separation of potassium nitrate contains
1,5% of potassium salt at 25ºС, thus losses of potassium ion will be minimal.
Carrying out double decomposition reaction of salts in isohydric conditions allows to
significantly reduce a water and energy consumption in the processes of potassium nitrate
receiving. Cyclic isohydric processes with additional salts involvement include salting-out and
polythermal crystallization stage with slight temperature drop. Temperature and concentration
isohydric cycles parameters of potassium nitrate from sodium nitrate and potassium chloride
receiving were determined on the basis of the first time studied solubility diagrams of five-
component mutual systems K+, Na+/NO3-, CO32-, Cl- - H2O и K+, Na+, NH4+/NO3-, Cl- - H2O.
Isohydric cyclic processes usage expedience in the industry was confirmed with kinetic
researches. Basic quantities of cyclic isohydric processes were calculated on the basis of
enlarged laboratory experiment. The received data were compared with real manufacture
characteristics.
Li,Na,K,Rb,Cs,La,Pu||F AND Na,Mg,Pt,U||Cl SYSTEMS FOR GENERATION IV

NUCLEAR TECHNOLOGY: 3D MODELS OF T-X-Y_DIAGRAMS
Lamueva M.V., Lutsyk V.I., Zelenaya A.E., Malygina E.N., Mogloeva S.N.
Institute of Physical Materials Science (Siberian Branch, Russian Academy of Sciences),
Ulan-Ude, e-mail: vluts@pres.bscnet.ru
Multicomponent fluoride systems with small thermal-neutron capture cross-section form
a basis for the fuel composition of molten salt reactor (MSR). As formation of solid phases in
the fuel circuit causes a change in neutron-energy balance in nuclear reactor, investigation of
fluoride systems determines successful realization of MSR project.
LaF3
Fig. Field AeABFS (a) of diagram with binary incongruently melting compound and mass
balances on isopleth UH at TQ+S (b) and TQ_S (c). 3D model of Li,K,La||F T-x-y diagram (d).
A computer model of LiF-KF-LaF3 system as one of the bounding systems of LiF- NaF-
RbF-LaF3 system can be made as the modification of T-x-y diagram with binary compound
with decomposition before melting and appearing within the ternary liquidus and T-x-y
diagram with incongruently melting binary compound.
The kinematical method is used for the unruled and ruled surfaces simulation (Fig. d). In
this case, a surface is presented as the pseudo-ruled one, that is, a space curve, given by the
interpolation polynomial, moves along the analogously given directing curves. As solid phase
solubility in this system doesn’t exist, the solidus and solvus surfaces are absent. As a result a
phase diagram includes eight two-phase regions and eight three-phase regions.
Computer model simplifies a problem of microstructure design. The field AeABFS is
divided by lines KeAB and KA into the fragments eABFK, AeABK and ASK (Fig. a). The
microstructure of fragment eABFK includes a matrix M=RQ+BQ+Be and crystals Ае, the
microstructure of fragment ASK includes matrix М and crystals A1. Microstructure of
fragment AeABK contains both type of crystals A: M+A1+Ae. A competition of primary (1) and
eutectical (e) crystals can be observed on the diagram of horizontal material balance. On the
fragment UH^(A-Q)(eABQ) of the isopleth, that belongs a ray BV, the diagrams of horizontal
materials balances have been constructed before and after reaction L+AQ=BQ+RQ (Fig. b-c).
They illustrate that the dividing of portion of crystals A on Ae, A1 and Ar on Are, Ar1 takes
place ("r'' is the remains after reaction L+AQ=BQ+RQ).
References
[1] Benes O., Konings R.J.M. J. Nucl. Mater. 2008. V. 375. P. 202-208 & V. 377. P. 449-
457.
[2] O. Benes, R. J. M. Konings. Calphad. 2008. V. 32. P. 121-128.
THERMODYNAMIC MODELING OF PHASE EQUILIBRIUM

IN METAL ALLOYS, CONTAINING NITROGEN AND CARBON
Leonovich B.I., Trofimov E.A., Nikonova O.V.
South Ural State University, Chelyabinsk, e-mail: splav.zlat@mail.ru
Nickel, iron and chromium are the base of heat-resistant alloys. The specific properties
of these alloys are largely determined by nitrogen and carbon content. These elements in the
melt form carbide, nitride and carbonitride inclusions, which may have a significant effect on
the grain size, oxidation resistance, ductility and durability of alloys, and in case of their unfit
form and location it can be cause of metal brittle fracture. Therefore, the theoretical study of
equilibrium phases formation in these alloys, and in particular, the definition of the mutual
components solubility is essential.
In the present study for the thermodynamic research of the metal alloys containing
carbon and nitrogen was used Hillert-Staffanson regular solution model that can be applied to
M1–M2–M3–X systems, containing the solvent metal (M1, M2 and M3) forming a
substituttional solution, and one substance (X), forming an interstitial solution. The vacancies
(v) in the interstitial sublattice are considered as an additional component of the system. The
system, where the major elements M1, substitute additives M2 and M3 (if the system is a four-
component) and the addition X, forming an interstitial solution, can be defined as
stoichiometric phase (M1, M2, M3)a(X, v)c.
Calculations of phase equilibrium were carried out by the data presented in relevant
scientific papers [1-3] using the values of Gibbs energies for phase formation and
temperature-dependent parameters. The calculation results for the systems Ni–Cr–C, Ni–Cr–
N, Fe–Cr–N, Fe–Cr–C, Fe–Ni–C, Fe–Ni–N, Fe–Ni–Cr and Fe–Cr–Ni–N are presented
graphically in the form of isothermal and polythermal phase diagrams sections for
temperatures from 900 to 1600°C. The concentration limits of formation carbide and nitride
phases in equilibrium with the metal were found. Constructed diagrams allow to determine the
sequence of phase conversions and the equilibrium phases proportions under the conditions
typical for technological processes of superalloys industry [4, 5].
This work was supported by the RFBR (grants 08-08-00416, 07-08-12092 and 11-08-
12046-ofi-m-2011).
References
[1] Hillert M., Qiu C. Metllurg. Trans. A. 1991. V. 22 A. № 9. P. 2187-2198.
[2] Raghavan V. Journal of Phase Equilibria. 1997. V. 18, № 2. P. 158-172.
[3] Frisk K. Z. Metallkunde. 1991. Bd. 82. H. 2. S. 108-117.
[4] Leonovich B.I. Izvestia vuzov. Chiornaia metallurgia. 2011. № 5. P. 3-6 (in Russian).
[5] Leonovich B.I., Kuznetsov Yu.S., Trofimov E.A. Vestnik YuUrGU. Seria "Metallurgia".
Issue №18 – 2012. – № 15 (274). P. 50 – 52 (in Russian).
THE EFFECT OF CONCENTRATION OF CATALYTIC POISON

ON THE THERMODYNAMIC CHARACTERISTICS OF THE HYDROGENATION
PROCESS OF SODIUM MALEATE WITH ADSORBED HYDROGEN
Lukin M.V., Prozorov D.A.
Institute of Thermodynamics and Kinetics of Chemical Processes,
The aim of this work was to evaluate the effect of the concentration of catalytic poison
on the thermodynamic characteristics of such a heat of hydrogenation maleta sodium, and of
the maximum absorption and adsorption coefficients of hydrogen adsorbed catalyst surface.
Determination of the heat of hydrogenation of sodium maleate conducted adsorption
calorimetry on the liquid isothermal calorimeter shell designed for liquid-phase studies of
heterogeneous catalytic processes. All experiments were performed at 303 K. For the
experiment using a porous nickel catalyst, which was prepared by treatment with cyclic
skeletal nickel hydrogen peroxide to remove residual aluminum, which prevents the correct
interpretation of the results of the adsorption-calorimetric experiment. Active catalyst has a
surface area 90±2 m2/g and a porosity sm3/sm3 0,5±0,05. Experiment and catalyst deactivation
process was carried out in aqueous solutions of different concentrations of sodium hydroxide
to the previously developed technique. S2- ion concentration in the solution was determined by
direct potentiometry.
The dependence of the heat of hydrogenation of the number of injected sodium maleate
was linear and depended on the concentration of decontaminant. Increasing the concentration
of sodium maleate led to a drop in the heats of hydrogenation, indicating significant
heterogeneity heterogeneous catalyst. Simultaneous increase in the degree of deactivation
associated with the initial content of sodium sulfide in the system leads to a drop in the heat of
hydrogenation of the same number of injected sodium maleate. However, the range of heats of
hydrogenation of sodium maleate adsorbed hydrogen remains constant from -140 to -30 kJ
/mol, which indicates the absence of side reactions. In addition, the data obtained in this work
can reasonably be argued that deactivation of the catalyst does not change the nature of the
elementary chemical acts on the surface. Proof of this are the constant values of the heats of
hydrogenation of sodium hydrogen maleate from the gas phase, and data of additional kinetic
experiments.
Reduction of the maximum hydrogen adsorption and from 17,7 to 3,9 cm3 of hydrogen
per gram of catalyst, in particular, with the degree of deactivation shows that the sulfur atoms
of the active centers of the surface of the block. At the same time there is a growth of
adsorption equilibrium constants, which indicates an increase of the binding energy of
hydrogen to the surface of the porous nickel shifts, which are the equilibrium toward
prochnosvyazannyh forms of adsorbed hydrogen.
Reduction of the maximum hydrogen adsorption and from 17,7 to 3,9 cm3 of hydrogen
per gram of catalyst, in particular, with the degree of deactivation shows that the sulfur atoms
of the active centers of the surface of the block. At the same time there is a growth of
adsorption equilibrium constants, which indicates an increase of the binding energy of
hydrogen to the surface of the porous nickel shifts, which are the equilibrium toward forms of
adsorbed hydrogen with a high heat of adsorption.
Thus determined the thermodynamic characteristics are the basis for calculating the
constant reactivity of adsorbed hydrogen and are the theoretical basis for predicting the
catalytic action of the porous nickel, and create optimal catalytic systems based on it.
TERNARY LIQUID – LIQUID EQUILIBRIA OF 1-BUTYL-1-METHYLPYRROLIDINIUM

BASED IONIC LIQUIDS
Lukoshko E., Domańska U.
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology,
Warsaw, e-mail: elukoshko@ch.pw.edu.pl
The object of our work is the measurements of three ionic liquids as follows: 1-butyl-1-
methylpyrrolidinium tetracyanoborate [BMPYR][TCB], 1-butyl-1-methylpyrrolidinium
tris(pentafluorethyl)trifluorphosphat [BMPYR][FAP] and 1-butyl-1-methylpyrrolidinium
dicyanamide [BMPYR][N(CN)2] in ternary systems. Thiophene forms with n-heptane
azeotropic mixture at 0.832 mass fraction of thiophene at T = 356.3 K, therefore the
separation of this mixture is not possible using rectification. Alternative method is liquid-
liquid extraction and in this case the information about ternary liquid-liquid equlibria is
necessary. Previous works indicated that ionic liquids can be used in separation of thiophene –
alkane mixtures successfully. The experimental tie-lines in liquid−liquid phase equilibria
(LLE) of submitted ionic liquid + n-heptane + thiophene have been determined at T = 298.15
K by gas–liquid chromatography. The solute distribution coefficient and the selectivity were
calculated for all systems. The experimental results have been correlated using NRTL model.
The influence of anion structure on phase equilibria and separation of thiophene and heptane
are discussed.
THERMODYNAMICS OF HYDRODEN–VACANCY INTERACTIONS IN ALPHA IRON

Mirzaev D.A., Mirzoev A.A., Ursaeva A.V., Ruzanova G.E., Shaburov A.D., Okishev K.Yu.
South Ural State University, Chelyabinsk, e-mail: mirzayev@mail.ru
In the last 15 years a number of experimental works was published showing that strong
attraction exists between vacancies and solute atoms of hydrogen in α iron. Hydrogen atoms
can be accumulated in vacancies, which in turn leads to the increase of vacancy concentration
(J. Alloys and Compounds 356–357 (2003) 263 and others).
In order to evaluate quantitatively this interaction ab initio calculations of the energy of
formation of VHn (n = 1...5) complexes were performed in WIEN2k package. Decrease of
energy on successive increasing n from 0 to 5 was found to be 0,60; 0,61; 0,39; 0,34 and 0,30
eV, which agrees with other works (PRB 67 (2003) 174105; 85 (2012) 094102). According to
those works, adding the sixth hydrogen atom to the VH5 complex almost does not change the
energy.
Based on these results an improved version of A.A. Smirnov’s statistical and
thermodynamic theory of VHn complex formation was developed taking into account the
features found in ab initio calculations. Estimates made by this theory show that the fraction
of vacancies containing 1, 2, 3 and more hydrogen atoms is much greater than that of single
vacancies, and a competition exists between vacancies with different neighbourhood. With
decreasing temperature the VH2, VH3 complexes become successively predominant, and
below 350...450 K almost all vacancies are bound with five hydrogen atoms (VH5). Interaction
with hydrogen must really increase the equilibrium vacancy concentration, especially at low
temperatures. At 500 K this increase may be 3...6 orders of magnitude. At still lower
temperatures the decrease of vacancy concentration may be changed by growth. This effect
becomes much stronger with increasing overall concentration of hydrogen in the solution.
However, despite the great increase of vacancy concentration due to interaction with hydrogen
atoms, it remains much smaller than the concentration of the latter, and vacancies are probably
not very effective as hydrogen traps.
Diffusion of vacancies in iron below 500...600 K becomes almost ceased, so the
described changes in vacancy concentration in grain volume may not be realized. But
hydrogen atoms are rather mobile at low temperatures, and since vacancies emerge at grain
boundaries, then the fast diffusion of hydrogen atoms may cause the formation of complexes
like VH4 or VH5 near the boundaries. Coalescence of such complexes may lead to formation
of vacancy discs filled with hydrogen, that are actually the nuclei of flakes. They may continue
to grow by the same mechanism intensified by the internal pressure of gaseous hydrogen
within the discs. Such mechanism is very similar to that proposed by R.A.Ryabov and
P.V.Geld (Metally (1975) 6, 114).
THERMODYNAMIC MODELLING POSSIBILITIES OF PHASE-CHEMICAL

TRANSFORMATIONS FOR SYNTHESIS AND OPERATING CONDITIONS OF SOME
CHEMICAL-TECHNOLOGICAL MATERIALS, SYSTEMS AND PROCESSES
Mischenko G.A., Najmushin A.B., Kacher E.B., Zubkova M.Yu., Slobodov A.A.
St.Petersburg Research National University ITMO,
St.Petersburg State Institute of Technology, St.Petersburg, e-mail: aslobd@gmail.com
On the basis of minimization principle for characteristic thermodynamic functions the

complex of methods and databases (realized in computer program-information system),
intended for description, modeling and calculation of phase-chemical transformations is
developed. The complex has no restrictions on componentity, number of potentially possible
phases and chemical forms (reactions) in a system.
On this basis the calculation of chemical and phase transformations occurring in
different inorganic systems is carried out, f.e. МgO - C - Al – H2O – air at 298 - 2400 K. It
describes and simulates processes occurring in thicker and cells of corresponding refractory
with antioxidant on the basis of aluminium and without one. Multiplane picture of
temperature and composition influence on phase and chemical transformations in a system is
received. These dependencies have allowed to reveal fields of stability for main components
composing the composite. Also the process of evolution for gas phase composition depending
on temperature is investigated, and the efficiency of the antioxidizing addition (suppressing
ability of gas phase to oxidize carbon) is quantitatively investigated.
The developed methodology has allowed also to investigate and reveal mechanisms of
phase-chemical transformations occurring at sialons SixAlyOzNt synthesis by means of
carbothermy kaoline nitration. The influence of reagents on character and amount of
impurities, on areas of thermal stability for sialon phases are investigated, on their
thermomechanical and chemical resistance are studied. The essential influence of temperature
on realization of one or another scheme of sialons synthesis is revealed. The conditions of
phases recrystallization, mainly gas-phase synthesis process, etc. are determined.
Also this methodology is used for thermodynamic research of synthesis (from binary
compounds) process for another composite - complex carbonitride of titanum, tantalum, and
tungsten. The correspond system: TiC - TiN - TaC - TaN - WC is investigated in wide area of
compositions and temperatures (298 - 3000 K). Qualitative and quantitative regularities on
influence of temperature and components ratio on character of phase transformations running
during synthesis are revealed, on course of homo- and heterogeneous reactions, on formation
of intermediate and by- products. The areas and fields of phases stability, their ratio depending
on state variables are determined. The conditions promoting and preventing formation of
"harmful" product – W2C (forming at input cobalt into alloy, complex carbide (W,Co)3C, that
leads to the alloy embrittlement).
Realization of the method has allowed correctly and effectively to solve the put
problems for various classes of catalytic materials. On this basis the calculation of chemical
and phase transformations occurring in systems Fe2O3-MnxOy, ZnO-Al2O3-CuO etc. is carried
out. It describes and simulates processes occurring in thicker and cells of corresponding
catalysts. Multiplane picture of temperature and composition influence on phase and chemical
transformations in the systems is received. Received theoretically and by calculation way the
results for all investigated multicomponent systems not only well will agreed with known
(truth, by virtue of considered systems complexity, quite often rather fragmentary and limited)
experimental data, but also give qualitatively and quantitatively more rich information on
mechanisms of running processes (both nature and chemical-technological ones).
STUDY OF CHEMICAL COMPATIBILITY AND PHYSICOCHEMICAL STABILITY

OF PYROTECHNIC COMPOSITIONS BY CALVET ISOTHERMAL/DIFFERENTIAL
SCANNING CALORIMETRY AND SIMULTANEOUS THERMAL ANALYSIS
Nazarov M.S., Mozgunov N.E., Emelianov M.V.
Applied Chemistry R & D Institute JSC, Sergiev Posad, e-mail: niiph@niiph.ru
Calvet isothermal microcalorimetry/differential scanning calorimetry and simultaneous

thermal analysis (thermogravimetry, differential thermogravimetry and differential thermal
analysis) are used to investigate chemical compatibility of pyrotechnic composition
components and physical and chemical stability of pyrotechnic compositions.
Instrumentation and methodological support of this research include DAС-1-1 and
DAC-7M Calvet isothermal microcalorimeters developed at the Institute of Chemical Physics
of the USSR Academy of Sciences, Calvet TG-DSC111 SETARAM calorimeter (France) and
Q-1500D derivatograph by «MOM» company (Hungary) with specialized «ACTest» software
and SETSOFT 2000 SETARAM (France) software inside. These devices automated and
combined into a «Stability» innovative cluster stand to investigate physical and chemical
properties of pyrotechnic compositions and pyrotechnic products.
Pyrotechnics for various purposes are studied including the newly developed
compositions based on high-energy materials, nanomaterials, black powders, smokeless
powders, ultrafine and nano-oxidants and nano-fuels powders, explosives, solid rocket
propellants.
Experiments were carried out under adiabatic conditions in two modes. In the
isothermal mode temperatures were 60°C, 80°C, 100°C and 120°C, the sample weighed 1-2 g
and the experiment lasted up to 10-15 days. In the scanning mode the temperature range was
from 25°C to 300°C, the sample weighed 10-50 mg and was heated at a rate of l K/min-5
K/min. Experiments were conducted in an inert atmosphere of argon and an oxidizing
atmosphere of air, including the atmosphere with a relative humidity of 65%, 80% and 95%,
or at a controlled moisture sample, the maximum weight of water amounts up to 2% by
weight of the sample specimen.
Using the recommendations of the current national standards, ASTM international
standards, specialized SETSOFT 2000 SETARAM (France) software the criteria of chemical
compatibility and physical and chemical stability of pyrotechnic compositions have been
quantitative developed of the reactivity of high-energy components and materials, including
nanomaterials, thermal effects of complex physical and chemical processes of thermohumidity
aging of pyrotechnic compositions have been quantitative assessed. Kinetic analysis of
differential thermogravimetry and heat flow calorimetry using Ozawa-Kissinger and Freeman-
Carroll methods is also performed.
Test results obtained are used to develop new pyrotechnic compositions and pyrotechnic
products for various purposes, to establish and confirm the warranty storage period of
fireworks.
THERMODYNAMIC EXERGY METHOD FOR DESIGNING OF WATER-USE

ENERGY-RESOURCE-SAVING INTEGRATED CHEMICAL PROCESSES
Nevsky A.V., Kashina O.V., Bushuev M.V.
Ivanovo State University оf Chemistry and Technology, Ivanovo, e-mail: nevsky@isuct.ru
In this work the features of the method of exergy analysis of energy-resource-saving

chemical processes of industrial enterprises water management systems have been considered.
For this purpose, the methodology for designing of energy-resource-saving water-
consumption and water-disposal systems of various fields industrial plants, developed by us
earlier, has been evolved. In the course of study, the numerical experiment, the task of which
was to form the base of experimental data, consisting of a set of parameters of multiple-choice
of the structure of designed Integrated Chemical Processes (ICP) has been carried out. The
calculation of ICP parameters was performed by means of information system developed,
which include a software package.
The analysis of the effect of pollutant mass load change on the value of exergy loss
change of the process of technological water streams mixing of various manufactures has been
carried out.
The observed exponential growth regularity of the relative change of exergy loss values
vs. the reduction of the ratio of component (contaminant) mass fraction at the output of
chemical chemical processes to the component mass fraction at the input to it, i.e. with
increasing of pollutant dilution in the process of individual water streams mixing has been
studied. According to methodology applied, the increase of the relative change of exergy loss
at water streams mixing process indicates thermodynamically less effective variant choice of
organization of energy-resource-saving water management systems of industrial plants.
The established regularities allow to identify the factors that contribute to finding the
best environmental and technological solutions at the designing of ICP of industrial plants
water management systems. The most important of these factors are: the greatest possible at
the conditions of given manufacture separation of technological water streams on the basis of
thermodynamic exergy analysis of given processes; the decrease of raw materials consumption
rates on the basis of innovative technological solutions on more efficient interaction between
the raw materials to produce the final product; the repeatedly-serial use of technological water
in manufacturing on the basis of modern high technologies of using water as solvent,
extractant, rinsing medium.
The data obtained in the work received approval at the designing of ICP of water
management systems of large chemical, textile, food, machinery construction, glass-
production, motor-transport and other industrial enterprises of the Central, Volga and
Southern Federal districts of Russia.
This work was supported by Russian Ministry of Education and Science (project
01.03.005) and by RFBR (grant 04-05-78035).
COMPENSATION EFFECT OF VISCOSITY

IN MULTICOMPONENT HYDROCARBON SYSTEMS
Nigmatullina I.E., Dolomatov M.Yu., Dezortsev S.V.
In the regions of kinetic phase transitions of the second order (process of softening-
vitrification) and viscous flow, a variation in the properties of multicomponent organic
systems is relaxation in nature and is related to the change in the energy of intermolecular
interactions with composition [1]. From the kinetic theory of liquid state, it is known, that
dynamic viscosity of a Newtonian incompressible fluid is related to activation energy of
viscous flow and is described by the Frenkel-Eyring equation [2, 3]:
η=η0·exp(Ea/RT), (1), η=σ0·exp(ΔGa/RT), (2).
The free energy is described by well-known Gibbs equation:
ΔGa=Ea-T·ΔS. (3)
The preexponent σ0 in expression (2) is usually assumed to be dependent on temperature
and molecular weight M [3] and is calculated from the expression:
σ0=T·(6,6-2,25·logM)·10-8 . (4)
From expressions (2) and (3) we can obtain
η=σ0·exp(-ΔS/R)·exp(Ea/RT), (5) and ΔS=(lnσ0-lnη0)·R, (6).
Where Ea – activation energy of viscous flow, J/mole; average number molecular weight
of the substance at the temperature T=273oC, g/mole; R – universal gas constant equal to 8,31
J/(mole·K); T – temperature, K; ΔS – viscous flow activation entropy, J/(mole·K); ΔGa – free
activation energy of viscous flow in the Eyring equation, J/mole; η – dynamic viscosity, Pa·s;
η0 – preexponent of dynamic viscosity, Pa·s; σ0 – viscosity of the substance in the state of
ideal gas, Pa·s.
It has been shown, that the compensation effect of dynamic viscosity exists in natural
and synthetic multicomponent hydrocarbon systems [1, 4]. The present work seeks to study
the compensation effect of dynamic viscosity in multicomponent high-molecular-weight
hydrocarbon systems on the base of high-boiling hydrocarbon fractions (HHF) – polyolefin
systems (oil tar and low-density polyethylene (PE)). For the HHF-PE systems investigated, the
dependence of the characteristic viscosity on the activation energy of viscous flow is
described by the linear equation (coefficient of linear correlation is larger than 0,9). Using the
knowledge of the compensation effect of dynamic viscosity, we can obtain materials with pre-
scribed strength, plastic and rheological properties, which is of importance in their production
and operation.
References
[1] Dolomatov M.Yu., Dezortsev S.V.. Bashkir. Khim. Zh. 2010. V. 17, №. 3. P. 67-71.
[2] Frenkel’ Ya.I. [In Russian]. M.: Nauka. Leningrad. 1975.
[3] Bartenev K.M., Frenkel’ Ya.I. [in Russian]. M.: Khimiya. Leningrade. 1990.
[4] Dolomatov M.Yu., Ishkinin A.A. Inzh.-Fiz. Zh. 2011. V. 84. №. 6. P 1325-1328.
[5] Dolomatov M.Yu., Dezortsev S.V. Inzh.-Fiz. Zh. 2012. V. 85. №. 6. P. 1352-1356.
THERMODYNAMIC ANALYSIS OF MAGNESIUM-THERMAL REDUCTION

OF MgTa2O6, Mg4Ta2O9, LiTaO3
Orlov V.M., Kryzhanov M.V.
I.V.Tananaev Institute of Chemistry and technology of Rare Elements and Mineral Raw
Materials, Kola Science Centre of RAS, Apatity, e-mail: orlov@chemy.kolasc.net.ru
The magnesium-thermal reduction of tantalates is a popular method of producing

tantalum powders with a great specific surface [1].
The reduction reactions were analyzed on a TERRA bundled software providing
simulation of chemical and phase equilibrium. The standard database of thermodynamic
properties of substances was supplemented with calculated characteristics of Mg4Ta2O9,
MgTa2O6 [2] and LiTaO3.
Systems of stoichiometric composition (MgTa2O6-Mg-Ar, Mg4Ta2O9-Mg-Ar и LiTaO3-
Mg-Ar) were examined in the temperature range of 300-3000 К under the argon pressure of
0.101 МPа without taking into account ionized substances. The temperature range of initial
reagents was 300-1300 К, with a measurement pitch of 100 K. The equilibrium temperature of
reaction products was determined by the method described in work [2].
The equilibrium temperature in the MgTa2O6-Mg-Ar system was practically
independent of the reagent temperature and at the room temperature of the charge it equaled
2581 К. In the Mg4Ta2O9-Mg-Ar system the equilibrium temperature at the reagent room
temperature was 2148 К, increasing to 2590 К in response to charge temperature increasing to
1300 К. At the reagent temperature in
excess of 1000 K, the difference
between equilibrium temperatures in
the systems did not exceed 10 degrees.
In the LiTaO3-Mg-Ar system,
increasing of the reagent temperature
from 300 to 1300 К has led to an
increase of equilibrium temperature
from 1960 К to 2196 К. According to
the data on equilibrium phase
composition presented in the Figure,
lithium does not form at the reaction
temperature of 1800 K. This was
experimentally confirmed in the course
of lithium tantalate reduction by
magnesium vapors at 830°C.
This work was supported by RFFR (grant № 12-03-98802 р_sever_а).
References
[1] Orlov V.M., Kryzhanov M.V. A method of tantalum powder production. RF patent
2465097, МПК B22F 9/22 (2006.01), publ. 27.10.2012, Bull. № 30.
[2] М.V. Kryzhanov, V.M.Orlov, V.V.Sukhorukov. Zhurnal Prikladnoy Khimii. 2010. V.83.
Is. 3.
CRYSTALLIZATION SIMULATION OF TELLURITE GLASSES

Plehovich A.D., Kut’in A.M.
Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod
e-mail: plehovich@gmail.com
Actual problems on control of crystallization in multicomponent glassy materials

contribute to its prevention in obtaining fibers, and at an accelerated, often catalytic
crystallization provides unique glass nanocrystalline materials with wide range of properties.
Due to the important technological applications the development of a mathematical model for
crystallization of a multicomponent glass in the device is required.
The report presents the results of the development and computerized implementation
starting from the Kolmogorov theory of the mathematical model of crystallization of glasses
in the DSC instrument. The model consistently used the thermodynamic functions of the
liquid (viscous-flow), vitreous and crystalline states both at nucleation of the crystalline phase
and determination of the thermodynamic factor in the diffusion-limited speed of its growth.
Developed to provide the necessary model input data
a. thermodynamic functions for tellurite glass were preliminarily found by the results on
processing of calorimetric data.
b. thermal conductivity of glass was determined by Netzsch 409 PC Luxx instrument
using DSC method.
Crystallization thermograms were processed on the basis of DSC measurements in a
series of samples of crystallizing tellurite glasses with different composition from the
standpoint of mathematical models. A predominantly heterogeneous crystallization
mechanism was found and fundamental characteristics of crystallization were defined.
Universal principles of the model provide its predicting abilities while scaling the
process to the set-ups for production of optical fibers.
CONNECTIONS BETWEEN MAGNETIC SUSCEPTIBILITY AND BASIC

PHYSICAL-CHEMICAL PROPERTIES OF N-ALKANES
Podyacheva K.I., Dezortsev S.V., Dolomatov M.Yu.
A lot of experimental data about physical-chemical properties (PCP) of individual

hydrocarbons make it possible to model different technological processes in chemical and
nanotechnologies. Thermo-physical properties of hydrocarbon systems are known very well.
Much less attention is paid to their electro-magnetic properties. Accurate correlations between
electronic characteristics and the PCP of n-alkanes like molecular weight, temperature of
ebullition, density and so on were found [1].
The aim of this work is the development of the estimation and prediction methods of
PCP for hydrocarbons and materials on their basis. The task is to expose interconnection
character between fundamental physical-chemical and magnetic properties of n-alkanes as a
well known test subject with a lot of PCP data. Methane is an exception from general series.
Thus, it is necessary to investigate interconnection between basic physical-chemistry and
magnetic properties in n-alkanes homologue series C2-C10. While data analysis we supposed
that connections between magnetic susceptibility and basic physical-chemical properties of n-
alkanes С2-С10 can be approximate by exponential dependence on the analogy with [1, 2]:
Z = α1 ⋅ e β1⋅χ , where Z – physical-chemical property from the table; αi and βi – empirical
coefficients, obtained by least-squares method; χ – сoefficient of magnetization.
Table. Values of empirical coefficients for dependences of n-alkanes С2-С10 PCPs

from coefficient of magnetization
Physical-chemical property (PCP) Coefficient of magnetization, χ, х10-6, 1/g

α1 β1 Correlation coefficient
Molecular weight, g/mole 3·1013 -30,98 0,99
Boiling-point, К 109 -17,707 0,99
Relative density. 293 K, g/ml 107,86 -5,9582 0,96
Critical temperature, К 8·107 -14,067 0,99
Dynamic viscosity. 293 K (С5-С10), cPs 8·1021 -60,227 0,99
Crystallization temperature, К 3·103 -22,022 0,95
Critical pressure has polynomial type of dependence from SMR: Pcr=-
3246,2·χ2+6188,6·χ-2887,1 with correlation coefficient R=0,99.
The obtained characters of relations between critical and magnetic properties of n-
alkanes C2-C10 allow us to suppose the collective character of electrons interactions in
substance and its influence on the basic PCPs.
References
[1] Dezortsev S.V., Dolomatov M.Yu., Shutkova S.A., Shulyakovskaya D.O. XVIII
International Conference on Chemical Thermodynamics in Russia. Samara. Russia. October
3-7. 2011. V. 1. P. 71-73.
[2] Dezortsev S.V., Dolomatov M.Yu. 4th EuCheMS Chemistry Congress. Czech Republic.
Prague. August 26-30. 2012. Chem Listy 106. S. 864.
THE EQUILIBRIUM OF THE PALLADIUM AND COPPER COMPLEXES

IN THE CATALYTIC SOLUTIONS USED IN THE CARBONYLATION PROCESSES
OF UNSATURATED COMPOUNDS
Putin A.Yu., Bruk L.G., Katsman E.A., Temkin O.N.
e-mail: putinalekse@yandex.ru
Homogeneous catalytic carbonylation of alkenes and alkynes in the catalytic systems

based on palladium complexes is of great interest for the past 50 years [1]. These processes
allow to obtain valuable products: carboxylic acids and their derivatives under mild
conditions.
So, in the PdBr2–CuBr2–THF–H2O catalyst system the reaction (1) is coupled with the
reaction (2) (30°C and atmospheric pressure):
СО + 0,5 О2 = СО2 (1)
RCH=CH2 + СО + Н2О = RCH(СООН)CH3 + RCH2CH2COOH (2)
The acetylene carbonylation proceeds to succinic and maleic anhydrides in the PdBr2 –
LiBr – AN catalyst system (3).
С2Н2 + 2СО + Н2О → succinic anhydride + maleic anhydride (3)
This study deals with the mechanism of these conjugated processes. The aim of this
research is to study the equilibrium of palladium and copper complexation in mentioned
catalytic solutions. The information on equilibrium of the copper and palladium complexes in
these systems is essential for the discrimination of hypotheses about the mechanism of
catalytic reactions (1-3). The model solutions containing components of catalytic systems in
various combinations, as well as the catalytic solutions in situ were studied by electron and
infrared spectroscopy. The assignment of the absorption bands to different palladium and
copper complexes has been carried out.
The equilibrium of complexation in CuBr2–LiBr–THF system has been investigated (the
concentration of lithium bromide was varied). The formation of several copper(II) complexes
has been registered in tetrahydrofuran (CuBr2, CuBr3-, CuBr42- are the dominating
complexes). The equilibrium constants and the extinction coefficients of corresponding
complexes were calculated.
The equilibrium of complexation in PdBr2–LiBr–THF, PdBr2–LiBr–AN systems has
been studied after contact with carbon monoxide. It has been shown that the palladium(II)
carbonyl complexes dominate in PdBr2–LiBr–THF system under carbon monoxide treatment
(the band at 2104 cm-1) and the palladium(II) carbonyl complexes (the band at 2120 cm-1) and
the palladium(I) carbonyl complexes (the band at 1908 cm-1) present in acetonitrile system.
During the coupled process of carbon monoxide oxidation and alkene
hydrocarboxylation (1, 2), copper exists in the form of copper(I) compounds, and palladium is
present in the form of palladium(II) carbonyl complex and probably in the form of the
complex with the corresponding alkene. In the course of the acetylene carbonylation
palladium is probably present in the form of palladium(I) complexes with carbon monoxide
and maleic anhydride.
Reference
[1] Bruk L.G., Oshanina I.V., Gorodsky S.N., Temkin O.N. Russian chemical journal. 2006.
V. 50. № 4. Р 103-114.
THE ANOMALOUS BEHAVIOR OF CESIUM IN PLUTONIUM MICROFUEL

Rusinkevich A.A., Ivanov A.S.
National Research Centre “Kurchatov Institute”, Moscow
e-mail: rusinkevich_andr@mail.ru
During the burnout part of any fission product can bind in stable chemical compounds
with other system components and is excluded from the process of diffusion. This part is
called the trapped fraction.
This paper presents the results of thermodynamic research of two types of microfuels
(with oxygen getter and without) with plutonium kernels at different burnups. The behavior of
trapped fraction of such elements as Ag, Ce, Cd, Cs, La, Mo, Pu, Pd, Ru, Sr, Te, Y was
studied. The influence of oxygen getter on the trapped fraction and release of fission products
is shown.
In microfuels without the oxygen getter it was found a sharp increase of cesium trapped
fraction and respectively decrease of free cesium at burnup ~ 26% FIMA and more. This leads
to a significant nonlinear dependence of trapped fraction on burnup and should cause a sharp
decrease of cesium release from microfuel. Apparently, the observed effect is due to the
formation of carbonate Cs2CO3 in plutonium fuel. In case of microfuel with oxygen getter
carbonate formation does not occur and cesium trapped fraction does not depend on burnup.
THERMODYNAMIC ARGUMENTATION OF REACTION PROGRESS

WHILE SULFATE REE AND HYDROGEN INTERACTING
Salnikova E.I., Andreev O.V., Kachalova G.S.
Tyumen State University of Architecture and Civil Engineering, Tyumen
e-mail: elenasalnikova213@gmail.com
Compound La2O2S alloyed by ions Nd3+ is a perspective laser material [1]. There are
more than 8 ways of Ln2O2S compounds preparation. One of them is a method of sulfate
process in hydrogen streaming. The method is processible, productive and ecological [2,3].
Data on kinetic and thermodynamic reaction characteristics are the base for processing of
technological parameters of compounds Ln2O2S powders preparation. There is no evidence
about thermodynamic processes which take part during sulfate REE and hydrogen interacting
in literature. Some data on thermodynamic oxo compounds REE quantities can be found [5].
Let us consider thermodynamic of processes while sulfate rare earth elements and
hydrogen interacting 600oС – 1150oС by the example of oxolantan sulfate. We offer the
following chemical reactions:
La2(SO4)3 + 7H2 = Ln2O2SO4 + H2S + S + 6H2O ( Ι)
La2O2SO4 + 4H2 = La2O2S + 4H2O ( ΙΙ )
La2O2SO4 + H2 = La2O3 + SO2 + H2O ( ΙΙΙ ).
Standard enthalpy reaction ( ∆Н 0 ) is calculated by standard enthalpy cyclization
( ∆Н 0 298 ) considering the first inference of Gess law for the last stage ( ΙΙΙ ) . Standard enthalpy
value (+2347kJ/mol) endoenergic reaction takes place with energy consumption.
Experimental data are given.
Standard entropy value of the reaction ( ∆S 0 ) which is equal to (-7,9 J/mol.К) is
calculated by the third law of thermodynamic. Negative value of standard reaction entropy
means thermodynamic impossibility of spontaneous reaction in standard conditions which
deals with reality.
As the paper deals with thermodynamic of processes while sulfate rare earth elements
and hydrogen interacting 600oС – 1150oС by the example of oxolantan sulfate, enthalpy value
calculations are done. Enthalpy ( ∆Н ) in the condition of 898 К which is equal to (+7094,2
кJ) and in condition of 1448К which is equal to (+11439,3 kJ) are calculated. Enthalpy value
increasing is determined by main laws of kinetics and chemical equilibrium. It is the
temperature diapason where processes carry with a nigh speed.
Analyzing data obtained using energy Gibbs expressing ∆G = ∆H − T ⋅ ∆S we can come
to the conclusion that reaction possibility is maximum in high temperature. Enthalpy and
entropy values are presented. Gibbs energy value is minimum.
Further analysis of thermodynamic value of the given compounds will present detailed
results.
References
[1] Kirillovich A.A. Synopsis of a thesis PhD (physics and maths): 01.04.03, 01.04.07. М.
1989. 22 p.
[2] Suponitsky U.L. A thesis of Doctor in chemistry: 02.00.04. Moscow. 2002. 248 p.
FLORY-HUGGINS PARAMETERS OF SYSTEMS:

PHOTOPOLYMERS – LOW-MOLECULAR LIQUIDS
Shpineva M.A., Konyukhov V.Yu.
D.I. Mendeleev University of Chemical Technology of Russia, Moscow
e-mail:volkon_1@mail.ru
Flexographic plates (photopolymers) during production and operation processes interact

with a variety of low-molecular liquids, as a result of such interaction they absorb solutions
i.e. swell to a varying degree. Plates’ swelling ultimately reduces print quality, so the study of
this process is highly relevant.
Process of polymer swelling is a superposition of two co-occurring processes. On the
one hand, it is a diffusion of the solvent into polymer matrix, on the other hand it is a
deformation of polymer matrix (grid) caused by absorption of liquid. As the swelling goes
grid stretches increasingly, causing tension in the material. The process stops when further
solvent diffusion is constrained by grid tension. The value of maximal polymer matrix
deformation depends on thermodynamic quality of the solvent, characterized by the value of c.
A mathematical model describing diffusion of the solvent into the polymer and deformation of
the polymer matrix was proposed in [1].
Studies of photopolymers swelling were conducted in ethyl acetate, butyl acetate, ethyl
cellosolve, n-heptane, n-butanol, isopropanol and water. In chromatographic experiments
ethyl acetate, butyl acetate, heptane, isopropanol, n-butanol were used. the highest
thermodynamic affinity (minimum value of c) towards flexographic plates have butyl acetate
and ethyl acetate as for them c has the minimum value. For these solvents c<0,5 and without
the grid polymers under consideration would dissolve to form a true solution. In the case of
heptane c=0,55, and its properties are close to q-solvent.
Flory-Huggins criteria can also be determined from the chromatographic data. the
equation for calculating c out of chromatographic data is:
Here P1° is the vapor pressure of the solvent (sorbate) at a column temperature, Vg is a
specific retention volume (corrected retention volume, divided by the weight of the polymer in
the column), M2 is the molar mass of the polymer (phase), B11 is the second virial coefficient
of the sorbate, V1 is the molar volume of the liquid sorbate [2].
For n-butanol, isopropanol and butyl acetate c decreased with increasing T, for n-
heptane and ethyl acetate dependence with a maximum was observed.
It was interesting to compare the values of c obtained by the two methods described at
close temperatures (T = 30°C). It is evident that there is a good correlation between c values
which shows the correctness of used methods for c determining.
References
[1] Denisyuk E.Ya., Volkov E.R. Vysokomolekularnie Soedineniya Seriya A. 2003. № 45. P.
1160-1168.
[2] Dzhvarsheyshvili A.I., Sherstneva M.K., Konyukhov V.Yu. XVI International conference
on chemical thermodynamics in Russia. Suzdal. July 1-6. 2007. V 1. P 260.
THERMODYNAMIC MODELING OF PHASE EQUIBRIUM IN SYSTEMS Me-B-C-O

(Me = Ti, Zr, V, W) IN VACUUM AND SYNTHESIS OF BORIDES/CARBIDES LAYERS
UNDER INLUENCE INTENSIVE ELECTRON BEAMS
Smirnyagina N.N., Khaltanova V.M.
Institute of Physical Materials Science SB RAS, Buryat State University,
Ulan-Ude, e-mail: ionbeam@ipms.bscnet.ru
We have presented results of the thermodynamic calculations simulating the interaction
between transition metal oxides with carbon and various boron compounds in the equilibrium
conditions. The thermodynamic investigation of equilibrium in systems Ti-B-C-O, Zr-B-C-O
and V-B-C-O is carried out with the purpose of formation conditions optimization of
functional layers on a surface of iron-carbon alloys as a result of electron beam boriding in
vacuum. Originally the boriding component choice and the determination of optimum
conditions for the boriding on temperature and pressure are main purposes of thermodynamic
consideration. The interaction of oxide with carbon and various boriding components (boron
carbide В4С, boron B, boron oxide В2О3) is investigated.
The thermodynamic calculations were executed with the computer systems ASTRA-
4/pc or TERRA. The calculations were carried out in a temperature of 673 - 1813 K (melting
temperature of pure iron Fe 1812 К) and in pressure range 105-10-4 Pa.
As a result of thermodynamic modeling is fixed, that at borides synthesis in quality
various boriding components the use of a B or a В4С, instead of a В2О3 is most much
preferable. Greatest power expenditures were observed for compositions with participation of
B2O3, then В4С. The difference reached 550-600 kJ/kg (B2O3) and 2-3 kJ/kg (B4C) [Ti-B-C-
O].
The sequence of the chemical transformations at borides synthesis, namely, the oxides
→ the carbides→ the lowest borides→ the supreme borides is established. First temperature
of borides formation depends on total pressure in system. So in system Ti B-C-O at pressure
105 Pa the TiO2 interaction with various boron components (B2O3, B4C, В) begins at
temperatures 1900-2100 K but at pressure 10-2-10-3 Pa the formation beginning temperature is
reduced up to 850-900К. It is established, that in mixes with participation B4C and B
originally there should be a phase transformation into the condensed condition with formation
of liquid phase В2О3.
It is submitted, that investigated systems MeO2-B (B4C, B2O3)-C [Me = Ti, Zr] and
V2O3-B (B4C,B2O3)-C are not ternary. In all investigated ternary systems, at least, two sides of
a concentration triangle are not binary sections of systems Me-B-O2. The special attention is
given to ternary system B-C-O2 as interaction В2О3-C determines behavior of all quaternary
system as a whole. Thermal properties and character dissociation of В2О3 are shown
depending on the common pressure in system. Fields of crystallization of all possible phases,
and also influence of temperature and pressure upon their behavior are established.
Preliminary results of electron beam boriding of carbon steels are presented. The
thickness of TiB2 layer was of the order of 80-100 µm, ZrB2 – 100-150 µm, VB2 - 150 µm and
WC – 200-300 µm. Layers will consist from TiB2, ZrB2, VB2 and WC (X-ray analysis (D8
ADVANCE, Cu Kα- radiation)). Research by means of a scanning microscope (LEO 1430VP)
has shown, that borides layers formation is difficult physical and chemical process. Their
formation is difficult physical and chemical process. The structure, phase structure and
strength characteristics are investigated.
This work was supported by the RFBR (grant 12-08-98036-р-sibir-а).
USING OF THERMODYNAMIC TOPOLOGICAL ANALISYS FOR REACTION

PROCESSES INTENSIFICATIONON EXAMPLE: OF 2-METHOXYPROPENE
PRODUCTION
Solokhin A.V., Nazanskiy S.L., Kiyko A.V.
Lomonosov Mocow State University of Fine Chemical Technologies, Moscow
e-mail: nazanski@yandex.ru
Reaction process of the 2-methoxypropene (MTP) production is considered. Reaction is

situated in liquid as 2,2-dimethoxypropane (DMP) destruction with methanol (MET) and 2-
methoxypropene formation. Side reaction of the intermolecular dehydration of methanol is
situated also.
Numerical calculation of ideal plug flow reactor, that was carried out previously, has
shown that with the flow of 2,2-dimethoxypropane (DMP) by 100 kmol/h and reactor volume
by 12 m3 conversion of reaction is 37%, selectivity is 84%. In connection with this, the using
of recycled flow sheet, synthesized by using thermodynamic-topological analysis method, for
given process intensification was suggested. It was established that side reaction is reversible
under process holding conditions and due to that one can use recycling of side products for its
suppression.
Mathematical model of recycled flow sheet of given process were made on the basis of
reaction kinetics data. By means of that, values of recycle streams, that theoretically can
produce 100% conversion and selectivity of DMP, were found.
Estimation of the parameters of the NRTL equation was held on the basis of liquid-
vapor equilibrium data of reaction mixture. Vapor-liquid equilibrium calculations were
carried out by using the given equation. Also distillation diagrams structures were drawn
under different pressure as well. It was shown that formed azeotropes DMP-MET and MTP-
MET greatly change their composition with pressure changing. Due to that fact one can use
principle of redistribution of concentration fields [1] for separation of reaction mixture.
Synthesized process flow diagram of the process includes reactor, separator and 4 rectification
columns working under different pressures.
At the final stage numerical simulation of process flow diagram was carried out. The
influence of different parameters on conversion of DMP and selectivity were investigated
during the simulation. As a result the general constructive and regime parameters, that
produce practically 100% conversion and selectivity, were picked up.
Reference
[1] Serafimov L.A., Frolkova A.K. Theoretical Foundations of Chemical Engineering. 1997.
V. 31. № 2. P. 159-166.
THE USE OF CHEMICAL THERMODYNAMICS FOR ANALYSIS PLASMA

CHEMICAL TECHNOLOGY SYNTHESIS RARE-EARTH MATERIALS
Sosnowski S.A., Sachkov V.I., Obkhodskaya E.V.
Siberian Physical-Technical Institute of Tomsk State University, Tomsk
e-mail: ssa777@mail.ru
This paper presents the results of chemical and thermodynamic analysis of plasma-
process for nanopowder materials from aqueous metal salt solutions. To this end, A
thermodynamic calculation of equilibrium composition in a system containing, in general, rare
earth elements in various combinations, with respect to the process of plasma-practical for
nanopowder materials from a mixture of dispersed aqueous salt solutions (nitric, hydrochloric
acid, fluoride, etc.). Calculation of equilibrium compositions was carried out on a computer
with P = 0.1-0.01 MPa, in the temperature range 300-5000 K, the total initial concentrations
of the metal salts in the system under 10 - 200 g/l.
Compounds of rare earth metals (REM) have a wide range of applications. In particular,
oxides play an important role, along with metallurgy, nuclear technology, the production of
materials for high-tech areas of consumption, such as the production of phosphors, industrial
ceramics, high-quality glass, fiber optics, lasers, film and photographic equipment. Obtaining
nanopowders by REM is one of the most important areas of nanotechnology. Along with the
development of basic scientific aspects of this school, is crucial to the development of
practical methods of production of nanoscale materials. For the ever-increasing consumer
sphere REM oxides possessing unique properties, the problem of their production is
particularly acute.
Plasma-process for nanopowder materials from aqueous metal salt solution reduces the
number of process steps, reduce their duration, to reduce the overall energy consumption. The
resulting powders reduce the temperature and duration of sintering of ceramics, which
eliminates the loss of oxide sintered mass and improve sustainability of production. The initial
solutions can be used reextract obtained at the operating plant.
When considering the process of plasma processing fluorine or chlorine-containing
solutions of metals, highlighting their unique feature: an education oxides occurs in response
pyrohydrolysis, and if fluoride or metal chloride is highly volatile, the reaction occurs in the
gas phase. It should be noted that other solutions transition plasma chemical reactions in the
gas phase have not celebrated.
THERMODYNAMIC AND KINETIC MODELLING OF CARBIDE DISSOLUTION

ON HEATING OF HIGH-CHROMIUM IRON ALLOYS
Sozykina A.S., Okishev K.Yu.
South Ural State University, Chelyabinsk, e-mail: k.okishev@inbox.ru
Iron alloys with high content of chromium (12...30 wt. %) and carbon (1...3 wt. %) are
widely used in industry as tool and wear-resistant materials. For increasing hardness they are
quenched from high temperatures (900...1200 C), where a partial dissolution of chromium
carbides (Cr, Fe)7C3 occurs. The amount of dissolved carbide phase determines the chemical
composition of γ solid solution and therefore the structural composition and properties of the
alloy after quenching. According to available experimental data, equilibrium composition of
γ phase is achieved in 1...10 hours at the temperatures mentioned. However, in experiments
and in industrial heat treatment smaller holdings are often used. Thus a model of carbide
dissolution kinetics is necessary for prognosticating the results of heat treatment.
To develop such a model we used literary experimental data for 15 alloys with various
content of chromium and carbon. The kinetic model is based on Zener-Hillert equation for the
growth/dissolution controlled by volume diffusion, while the limiting amount of carbide phase
being in equilibrium at given temperature was calculated by thermodynamic model of Lee
(Calphad 16 (1992) 121). Application of model equations to experimental data showed that
the activation energy of dissolution depends significantly on the atomic fraction of chromium
in metal sublattice of the carbide yCr: it has a minimum at yCr = 0,57 and equals 200 kJ/mole at
yCr = 1/2. It is much less than the activation energy of chromium diffusion in austenite, which
may be a result of a great difference in specific volumes of M7C3 carbide and the γ solid
solution. The second model parameter, i.e. the factor determining the “time scale” of the
process, decreases linearly with increasing equilibrium amount of carbide phase. Comparison
with experimental data showed that calculation results provide the composition of γ solid
solution composition with the error of ±0,25 %Cr and ±0,05 %C, and the position of
martensitic point that was evaluated by empirical formula Ms = 475 – 275·(%C) – 12·(%Cr) –
10·(%Cr)·(%C), °C with the error within 9 °C. In combination with previously developed
model for calculation the hardness of the alloy as a function of chemical composition of the γ
phase (and martensite formed on quenching) and the position of Ms this permits to
prognosticate the structural composition and hardness of alloys depending not only on their
chemical composition and heating temperature before quenching, but also on holding time at
that temperature. The model can thus be applied for selection of optimal heat treatment for an
alloy with any given content of chromium and carbon.
THERMODYNAMICS OF MELTS COMPONENTS INTERACTION,

FORMING NON-METALLIC AND INTERMETALLIC PHASES
Trofimov E.A.
South Ural State University, Chelyabinsk, e-mail: tea7510@gmail.com
Information about thermodynamics of the components interaction in metal melts,

forming a complex equilibrium phases is important, but to the present day the full
systematization of all experimental date of this interaction type in the systems based on the
main used metals was not realized.
The approach commonly used to analyze heterogeneous interactions in non-ferrous
metal melts is based on consideration of some chemical reactions taken place in the test
system. This approach does not absolutely permit to include the mutual influence of the
complex chemical composition of the interacting phases on the nature of interaction products.
System development of thermodynamic analysis of processes in liquid metal is the
purpose of this work. It allows full enough and thermodynamically correctly describe the
phenomena occurring for the interaction process in metal melts with complex composition
and complex equilibrium (non-metallic and intermetallic) phases for various states of matter.
The developed analysis system is based on calculating coordinates of the surface of
components solubility in the metal melts (SCSM). These are special multicomponent phase
diagram, which allows to tie the microchanges in the metal alloy in accordance with the
qualitative change in the composition of the complex phases.
The general principles of the constructing method of SCSM for different groups of
metals were formulated and SCSM of systems based on copper, cobalt, nickel, aluminum,
lead, bismuth, indium and tin for a wide range of composition and temperatures is plotted.
Simultaneously with the thermodynamic modeling the extensive experimental study of
the results interaction between the components of metallic melts was carried out. A
modification method based on a study of the composition, size and shape of inclusions
substances formed in the liquid metal in a concentration gradient of impurities was used.
Regimes implementation options proposed methodology of the study have been substantiated.
Their applicability and adequacy of the results obtained by other methods was shown. The
composition, shape and size of inclusions formed in the metal melts of these systems under
various conditions were studied. The compositions of the metal, located next to the inclusions
are found.
With the SCSM a number of different processes related to the existence of complex
metallic melts in equilibrium with the various condensed phases and gas was analyzed. Thus,
the effectiveness of the method of analysis, its prospects and its productivity to improve the
processes of non-ferrous metallurgy was demonstrated.
Some parts of the research relating to the investigation of systems based on nickel, was
supported by RFBR (grant 11-08-12046-ofi-m-2011).
PHASE EQUILIBRIUMS IN THE Cu–Al–Mg–O SYSTEM

UNDER THE CONDITIONS OF COPPER MELT EXISTENCE
Trofimov E.A., Nikonova O.V.
South Ural State University, Zlatoust, e-mail: tea7510@gmail.com
The synthesis realization results for corundum particles in copper-aluminum melt [1, 2]
depend on many factors and some of them are difficult to control. The central problem is
prevention of aluminum oxide film formation, significantly reduced the mechanical
characteristics of the metal samples.
A possible solution of this problem could be adding magnesium in the metal compound.
It is assumed that magnesium addition eases the oxygen diffusion in the metal, as it will
prevent Al2O3 film formation. The results of previously thermodynamic analysis of the Al–
Mg–O system can be used for approval this approach [3]. However, the experimental results
attained in the course of this approach, are ambiguous and does not allow confidently
recommend this approach to obtain metal matrix composite.
It has been tasked to carry out a thermodynamic analysis of the Cu–Al–Mg–O system
with more than 90% copper in the system at temperature 1100 ... 1300°C by building surfaces
of components solubility in metal melt (SCSM) for this system.
To calculate the activity of components in nonmetallic melts the absolute ionic solution
theory has been used. For calculating the activity of components in metallic melts first order
Wagner's interaction parameters were used. The result of the calculations is the isothermal
sections SCSM for the Cu–Al–Mg–O system at temperatures 1100 ... 1300°C.
The results of calculating the surfaces of components solubility in metal melt have been
compared with the data presented in relevant scientific papers and the results of our own
experiments, namely the X-ray microanalysis of nonmetallic inclusions formed in the copper
melts, with different contents of magnesium, aluminum and oxygen in metal structure.
This work was supported by the RBBR (grant 12-08-31055 mol_a).
References
[1] Trofimov E.A., Mikhailov G.G., Alexeev V.A. Nanotechnologies of functional materials
(NFM’10): proceeding of the international scientific and technical conference. Saint
Peterburg. 2010. P. 278-279 (in Russian).
[2] Trofimov E.A., Alexeev V.A. Nanotechnologies of functional materials (NFM’12):
proceeding of the international scientific and technical conference. Saint Peterburg.. 2012. P.
549-552 (in Russian).
[3] Trofimov E.A., Kadochnikov Yu.G. Russian Metallurgy (Metally). 2006. V. 2006. № 4. P.
297-302.
CRYSTALLIZATION PATHS WITHIN THE TERNARY SYSTEM WITH TWO

COMPOUNDS (INCONGRUENTLY MELTING AND DECOMPOSING)
Tsyngeev B.V., Lutsyk V.I., Zelenaya A.E., Sungrapova I.D.-S., Maiorova M.K.
Institute of Physical Materials Science SB RAS, Ulan-Ude, e-mail: vluts@pres.bscnet.ru
In a system (Fig. a) with incongruently melting compounds: ternary one and a binary
compound with decomposition in 4-phase reaction of liquid formation, the phase regions
projection to the Gibbs triangle divide the latter into 75 concentration fields. Twelve of them
are zero-dimensional, 37 – one-dimensional and 26 – two-dimensional fields.
Investigation of these fields by the vertical mass-balances (Fig. d, e, f, g) and imitation
of their DTA spectra (Fig. b, c) have shown, that some of them have no their own set of
microstructure elements. They are: 16 one-dimensional fields APA (coincides with 3), BQ
(19), QCQ (7), CPC (16), ERRC (13), RPR (9), PAPR (8), QP (20), PRP (10), ERP (12 & 22), PCP
(21), PE (20), BU (18), R1U (23), pBCU (25), CU (17) and 6 zero-dimensional ones Q (QE), P
(20), PC (EPC), PA (PAQA), PR (PRQ), ER (ERE). Besides 2 two-dimensional fields resemble
each other: 22 and 12. Mass balances for the invariant reactions have been artificial
widespread in a temperature axis to demonstrate the regrouping of masses for the material
points.
Two-dimensional fields 23, 24, 25, 26 may be used for the design of the
microconstituents of the phases assemblages only in the non-equilibrium processes, as below
the temperature of point U a binary compound R1 doesn’t exist.
Fig. Crystallization fields and isopleth MN – a); DTA spectra simulation for the 2-dimensional field
24 & 1-dimensional field pBCU – b-c); mass balances for the fields 24, pBCU, 25, eBCU – d),e),f),g);
L+B+C 3-phase region model for prototyping by 3D-printer –h).
Computer model of T-x-y diagram has been used for its phase regions prototyping by a
3D-printer (Fig. h). Nothing conveys an idea better then holding it in your hand. 3D Printing is
an effective way to enrich learning and research in virtually any faculty. Proficiency in
prototyping and 3D modeling has become an essential requirement for design, science and
engineering students and researchers.
PHASE EQUILIBRIUM RESEARCH, REALIZED IN NICKEL-BASE SUPERALLOYS

Vakhitova E.R., Trofimov E.A.
South Ural State University, Chelyabinsk, e-mail: tea7510@gmail.com
Such properties of heat-resistant alloys as high-temperature strength up 1000°С, thermal

stability and high resistance to corrosion have allowed widely using them in the aerospace
industry to produce parts of the rocket and gas-turbine engines.
The main requirement to such alloys is the stability of the phase structure – stability of
solid solution on nickel-base, strengthening γ′-phase and carbide phases. The special features
of this type alloys are the complexity of matrix γ-phase composition for nickel-chromium
system and structure instability (variability) while heat treatment and high-temperature
operation, the reason for it is the interaction of the matrix and carbide strengthening and
intermetallide phases.
There are known some methods to assess the phase composition of nickel superalloys
basing on their composition data and notion of their electronic structure, it permits to predict
tendency for formation harmful (topologically close-packed) phase in these alloys. Method
PHACOMP is one of these methods, which take into account inhomogeneity of the alloying
elements distribution in microstructure, the alloying elements bonding in carbide and other
phases, etc. (there are some similar methods: New-PHACOMP, Solubility index, the method
of alloying imbalance calculation described by G.I. Morozova). In spite of these advances in
the phase instability prediction in nickel-base superalloys there are still many unsolved
problems in this area.
In the present work using modeling tools such as Mathcad different algorithms of phase
stability evaluation in nickel-base superalloys were realized. Developed tools allow to find for
complex multicomponent alloys (characterized variations in the concentrations of alloying
elements) such compositions, which correspond with the optimal values special parameters of
valuation methodologies. The results of this work have allowed to estimate the phase structure
stability of nickel-base superalloys typically used in the Russian Federation industry.
At the same time in this work electron structure metallography of concerned nickel-base
alloys experimental and industrial specimens was made.
The results of the phase composition estimation were compared with the equilibrium
diagrams presented in relevant scientific papers, with the results of electron microscopic
analysis and also with data of the mechanical characteristics testing.
The obtained results can be used to formulate recommendations for methods
improvement of computer aided design for nickel-base superalloys and also computer
optimization techniques of these alloys composition.
The work was supported by the RFBR (grant № 11-08-12046-ofi-m-2011).
THE IMPROVEMENT OF THE ELECTRODE NANOMATERIALS

ON THE BASIS OF POLYMER FILMS OBTAINING METHODS
Yashtulov N.A.1, Lebedeva M.V.1, Revina A.A.2, Flid V.R.1
1
e-mail: lebedevamv221087@mail.ru
2
A.N. Frumkin Institute of Physical Chemistry and Electrochemistry
The development of management composition methods, structure, nanoparticles (NP)

properties, revealing of the nanostructured composites controlled formation and stabilization
conditions, peculiarities of mechanisms current forming reactions in the NP presence, the
influence of nanomaterials morphology, structure, phase composition on the reactivity, are a
fundamental objective of physical chemistry and fine chemical technologies for the decision
of modern power engineering problems. The nanomaterials using, the elucidation of their
functioning peculiarities, as well as improvement and optimization of the obtaining
technology through the modern methods using and chemical thermodynamics approaches can
serve as a basis for the development of the new generation energy sources.
Modified polymer membranes Nafion with a thickness of less than 0,2 mm were applied
as nano-structured matrix-substrates. Polymer membranes are widely used in the energy
sources due to their high unipolar proton conductivity [1]. The diffusion coefficient of water
in the membrane (D), was found to increase from about 10-6 to 10-4 cm2/s with increasing
temperature, and the activation energy was estimated to be 15-20 kJ/mol [2]. The membrane
ion conductivity is provided by the hydrated protons transfer on the system of fixed
sulfogroups by the equation:
RSO3H + nH2O ↔ RSO3- + H+nH2O,
where R is a fragment of the polymer, SO3H - functional group.
Modification of electrode-metallic composites was performed by metal nanoparticles,
received with radiation-chemical reduction of metal ions in water-organic reverse-micellar
solutions [3]. The application of reverse micelles as nanoreactrs in the synthesis allows to
obtain stable metal NP with controlled size and shape [4].
The thin-film metal-polymer Pt and Pd nanocomposites can be used as the basis of high
performance miniature flexible generators of energy [4]. Optimization of the metal
nanoparticles formation conditions in polymer matrix allows improving the functional
characteristics of the energy sources membrane-electrode blocks. In addition, the metal-
polymer nanocomposites promote additional catalytic oxidation of fuel, preventing its
penetration through the polymer membrane (crossover).
References
[1] Sahu A.K., Pitchumani S., Sridhar P., Shukla A.K. Bull. Mater. Sci. 2009. V. 32, № 3.
P. 285-294.
[2] Yeo S.C., Eisenberg A. J. Appl. Polym. Sci. 1997. V. 21. № 4. P. 875-898.
[3] Patent of RF no. 2322327-2008, Byull. Izobret. 2008. 11.
[4] Yashtulov N.A., Bolshakova A.N., Revina A.A., Flid V.R. Russ. Chem. Bull. 2011. V. 60.
№ 8. Р. 1581-1585.
DEVELOPING OF NEW GENERATION OF STEELS, BIMETALS, AND OTHER

PERSPECTIVE MATERIALS BASED ON THE RESEARCH AND MODELLING
OF THERMODYNAMIC PROPERTIES OF METALLIC AND SLAG SYSTEMS
Zaitsev A.I.
I.P. Bardin Central Research Institute of Ferrous Metallurgy, Moscow
e-mail: izaitsev@mtu-net.ru
The detailed study of the thermodynamic properties of a large number of practically

important metallic and slag systems of different nature and complexity have been carried out
using the most informative methods of chemical thermodynamics - Knudsen mass
spectrometry and integral variant of the effusion method. Based on the obtained results the
new concept has been formulated for the structure and physico-chemical behavior of liquid
mixtures of inorganic compounds, silicates, slags, and fluxes. It starts from the assumption
that molecule-like partly ionized associates or complexes exist in the melt. Development of
this approach has allowed the adequate interpretation of the thermodynamic behavior,
structure state, nature of the chemical interaction between the components, and the most
important physico-chemical properties (viscosity, surface tension, density, heat conductivity,
and electroconductivity) from the unified point of view over the whole concentration range. It
was found that this approach is also applicable for liquid metallic alloys with intensive
interparticle interaction between the components. Based on the analysis of the phenomenon of
association the adequate methods have been developed for describing the temperature and
concentration dependences of the thermodynamic and important physico-chemical properties
of metallic melts including glass-forming ability.
With the use of the obtained database and formulated theoretical principles the models
of processing of the liquid and solid steel have been developed, including refining, alloying,
formation and evolution of non-metallic inclusions, the interaction with the lining during ladle
treatment, continuous casting of steel, precipitation of non-metallic excessive phases during
the temperature-deformation treatment of metal. These results for the first time allowed us to
develop effective methods for prediction and control of the type, quantity, size, and
morphology of non-metallic inclusions, non-metallic excessive phases, and forms the
impurities are present.
Based on established fundamental principles the advanced energy-saving technologies
have been developed for mass production of high quality steels, including automobile, pipe
and other steels with extremely high level of properties, which are difficult to combine, e.g.
strength, ductility, corrosion resistance; bimetallic materials with a unique combination of
properties for the chemical, petrochemical engineering, road, mining, agricultural, and other
machinery; special alloys for various purposes. Many of the developed technologies have been
implemented at the domestic steel plants resulted in a significant economic effect.
This work was supported by the RFBR (grants 10-03-00506-a, 11-08-00526-a, 11-08-
12128-ofi-m-2011).
ТЕРМОДИНАМИЧЕСКИЙ АНАЛИЗ ПРОЦЕССОВ ПЕРЕРАБОТКИ

ГАББРО-БАЗАЛЬТОВОГО СЫРЬЯ
Бабиевская И.З., Дергачева Н.П., Дробот Н.Ф., Кренев В.А., Фомичев С.В.
Институт общей и неорганической химии им. Н.С.Курнакова РАН, Москва
e-mail: fomichev@igic.ras.ru
Габбро-базальтовые породы используются с древнейших времен в качестве

строительного материала, штучного камня для облицовки зданий, получения щебня. В
наши дни – это сырье для петрургии, производства теплоизоляционных и композитных
материалов.
Габбро-базальты – это магматические горные породы, состоящие из силикатов и
алюмосиликатов. По минеральному и химическому составу это сложное,
многокомпонентное сырье. Для производства из него современных материалов
обязательной технологической операцией является процесс получения расплава.
Изучение физико-химических свойств таких расплавов экспериментальными методами
затруднительно, поэтому зачастую единственно возможным выходом из этого
положения является использование термодинамических методов расчета равновесий в
сложных гетерогенных системах с химическим взаимодействием компонентов.
Экспериментальное изучение фазового состава расплавов системы Si-Al-Ti-Fe-Ca-
Mg-Na-K-O представляет собой трудную задачу в связи с высокими температурами
(1000-15000С) и одновременной кристаллизацией из расплава трех-четырех фаз со
значительным перекрыванием областей их образования. В таких случаях
целесообразно привлечение возможностей химической термодинамики, позволяющей
давать оценку фазового состава и вероятного направления преобразования веществ,
исходя из величин свободной энергии начального и конечного состояния системы.
Нами был предложен метод расчета минеральных составов габбро-базальтов по
данным их химического анализа. Расчеты выполнялись с помощью программного
комплекса СЕЛЕКТОР-С, который позволяет включать жидкую фазу расплава, твердые
растворы минералов, составляющих габбро-базальтовое сырье и газовую фазу
(атмосферу плавления).
С целью определения возможности и целесообразности применения подобных
расчетов было проведено сопоставление полученных результатов с
экспериментальными данными. Для этого были рассчитаны минеральные составы
базальтов из различных месторождений, в том числе и лунных океанических
оливиновых базальтов, доставленных экспедицией Appolo-12. Обязательным условием
отбора образцов было наличие надёжных экспериментальных данных об их
химическом и минеральном составе, определенных современными инструментальными
методами.
Результаты расчетов показали хорошую сходимость с соответствующими
экспериментальными значениями.
Предложенный способ может найти применение для оценки минерального
состава сырья и методов его модификации, а также для рекомендаций по условиям
проведения процессов в технологии получения базальтовых волокон, керамики и
изделий каменного литья.
РАСЧЕТ ТЕРМОДИНАМИЧЕСКИХ ФУНКЦИЙ УГЛЕВОДОРОДНОГО СОСТАВА

КАМЕННОУГОЛЬНОЙ СМОЛЫ И ЕЕ ШИРОКОЙ ФРАКЦИИ
С ТЕМПЕРАТУРОЙ КИПЕНИЯ <270°С
1
Байкенов М.И., 2Гюльмалиев А.М., 1Амерханова Ш.К., 3Байкенова Г.Г.
1
Карагандинский государственный университет им. Е. А. Букетова, Караганда
e-mail: murzabek_b@mail.ru
2
Институт нефтехимического синтеза им. А.В.Топчиева РАН, Москва
3
Карагандинский экономический университет Казпотребсоюза, Караганда
В процессе гидрогенизации ТТУС самая главная задача – это увеличение выхода

жидких продуктов за счет передачи водорода соединениями, которые легко частично
отдают свои атомы водорода в реакционную смесь [1]. Авторами в работе [1] показано,
что содержание водорода в составе донора сильно влияет на значения его
термодинамических функций и сделан вывод, что эффективность Н-донора
определяется не количеством водорода в его составе, а значениями термодинамических
функций.
Для термодинамических исследований углехимических процессов, в частности,
гидрогенизационной переработки угля, каменноугольной смолы в широком
температурном диапазоне, необходимо иметь данные по значению термодинамических
функций, таких как теплоемкость, энтальпия, энтропия, свободная энергия Гиббса. В
настоящее время соответствующие экспериментальные данные по термодинамическим
функциям углеводородного состава первичной каменноугольной смолы и ее фракций
отсутствуют, поэтому исследователи уделяют большое внимание разработке
теоретических и практических методов их расчета [2-3].
В основе метода расчета термодинамических функций углеводородного состава
лежит аддитивная схема для исследования реакционной способности модельных
соединений. Аддитивный метод расчета термодинамических функций модельных
соединений, входящих в фрагментарный состав ОМУ или КС, был разработан
профессором А.М. Гюльмалиевым [1].
На основании рассчитанных термодинамических функции установлено, что
выбранная широкая фракция ПКС с к.к. 270ºС (донор водорода-пастообразователь) для
процесса каталитической гидрогенизации ТТУС, полученная из первичной
каменноугольной смолы, которая предварительно была подвергнута кавитационной
обработке, согласно результатам термодинамических расчетов, является эффективным
донором и переносчиком водорода, т.е. способна ингибировать процессы
полимеризации, стабилизируя радикалы, которые образуются в результате
гидрогенизационных процессов.
[1] Гюльмалиев А.М., Головин Г.С., Гладун Т.Г. М.: МГГУ, 2003. − 550 с.
[2] Липович В.Г., Калабин Г.А., Калечиц И.В. М.: Химия, 1988. – 336 с.
[3] Шахтахтинский Т.Н., Бахманов М.Ф. Баку: Элм, 1985. – 260 с.
ТЕРМОДИНАМИЧЕСКИЕ ОСНОВЫ И ПРОЦЕССЫ ХЛОРИРОВАНИЯ

Nb,Ta-СОДЕРЖАЩИХ ТЕХНОГЕННЫХ ПРОДУКТОВ
В РАСПЛАВЕ ХЛОРИСТЫХ СОЛЕЙ
1
Дробот Д.В.,2Чуб А.В. 2Цурика А.А., 1Кутылев С.А.
1
Московский государственный университет тонких химических технологий
имени М.В. Ломоносова, Москва, e-mail: sakutylev@mitht.ru
2
ОАО «Соликамский магниевый завод»
Вовлечение вторичных Nb,Ta-содержащих материалов в сферу промышленного

использования – задача, актуальность которой определяется ограниченностью
первичных сырьевых источников этих металлов в России и постоянно расширяющейся
номенклатурой функциональных материалов на их основе (от производства
низколегированных сталей до получения ферроэлектриков, люминофоров,
катализаторов нового поколения и т.д.). Хлорирование редкоэлементного сырья –
промышленный метод в технологии Ti, Nb, Ta, РЗЭ и др.
Работа посвящена изложению результатов создания базы данных по
термодинамике взаимодействия в системах, образованных хлоридами Nb, Ta, Ti Al, Fe
и хлоридом натрия во всех агрегатных состояниях (всего рассмотрено 763 реакции) и
использованию полученных результатов в совокупности с результатами уточнения
фазовых равновесий в системе NaCl – FeCl2 – FeCl3 для создания технологии
хлорирования Fe/Nb и других техногенных продуктов в расплаве NaFeCl4.
Термодинамические расчеты выполнены в рамках метода Темкина – Шварцмана.
Термодинамический подход правомерен поскольку температуры процессов велики и
рассматриваемые системы близки к равновесным.
База данных позволяет: а) выделять совокупность реакций по заданным
соединениям: б) по величинам потенциала Гиббса или энтальпий ; в) вводить ( в
зависимости от состава сырья, вовлекаемого в переработку) новые объекты. Эта часть
работы представляет интерес для специалистов работающих а области хлорной
металлургии редких элементов.
Результаты использованы для расчета теплового баланса процесса хлорирования
Fe/Nb и других материалов и создания аппаратуры для его осуществления. Процесс
реализован в полупромышленном масштабе.
[1] Чуб А.В., Добрынин А.И., Фомин А.В., Дробот Д.В., Цурика А.А. Ж. Цветная
металлургия. 2000. № 3. C.13-16.
ТЕРМОДИНАМИЧЕСКОЕ МОДЕЛИРОВАНИЕ В ЭЛЕКТРОННОМ

МАТЕРИАЛОВЕДЕНИИ
Кузнецов Ф.А.
Институт неорганической химии СО РАН им. А.В.Николаева, Новосибирск
e-mail: fk@niic.nsc.ru
Термодинамическое моделирование является эффективным средством решения

различных задач материаловедения. В докладе будут даны примеры применения этой
методологии в практике ИНХ СОРАН.
Технология полупроводникового кремния. Наиболее широко используемым в
настоящее время способом получения поликристаллического кремния является так
называемый Сименс технология. Это сложный многостадийный процесс с
использованием реакций в системе Si-Cl-H. Задачами оптимизации технологии
являются повышение выхода конечного продукта, обеспечение высокого уровня
чистоты, снижение стоимости производства. Термодинамические расчеты позволяют
найти оптимальные условия проведения многих этапов этого процесса: растворение
металлургического кремния, разделения смеси хлорсиланов, восстановление
трихлорсилана, утилизации тетрахлорида кремния, рециклирования водорода и
хлорсиланов. Разработанная методология успешно применена в практике
промышленного предприятия.
Оптимизация процессов MO CVD. Непрерывное увеличение количества
используемых в электронике материалов требует расширение набора применяемых
технологий. Чрезвычайно перспективным является применение процессов осаждения
из газовой фазы с использованием в качестве исходных веществ летучих элемент
органических соединений. Сложность этого типа процессов состоит в том, что в
зависимости от условий могут образовываться фазы или наборы фаз разного состава.
Экспериментальное нахождение оптимальных условий – длительная и дорогостоящая
процедура. Задачей термодинамического моделирования в этом случае является
определения набора условий, соответствующих образованию требуемых фаз. Будут
приведены примеры построения так называемых CVD диаграмм для ряда важных
применений MO CVD процессов.
Еще одним важным применением методологии термодинамического
моделирования является рассмотрение совместимости различных твердых фаз,
используемых для создания твердотельных структур. Часто при разработках новых
приборов используются комбинации материалов, обладающих требуемыми
физическими параметрами без учета возможностей взаимодействия соседствующих в
структурах веществ. Будут приведены примеры рассмотрения различных пар веществ,
применяемых в твердотельных структурах.
В ИНХ СО РАН развитие и применение методологии термодинамического
моделирования является частью комплексной программы, включающей большой набор
методов экспериментального исследования термодинамических и термохимических
параметров веществ и процессов, создание баз данных на основе собственных и
литературных данных, разработку математического обеспечения для поддержки банка
данных и проведение процедур термодинамического моделирования.
МОДИФИКАЦИЯ ОКСИДА ГРАФЕНА ИОНАМИ МЕТАЛЛОВ

Лауре И.В.
Институт общей и неорганической химии им. Н.С. Курнакова РАН, Москва
e-mail: laure@mail.ru
В последние годы научное сообщество активно продолжает изучать уникальный

материал графен. Он привлекателен особенными механическими, электрическими,
тепловыми и оптическими свойствами. Для того чтобы реализовать этот огромный
потенциал, необходимо осуществить промышленное производство и технологическую
сборку графена в определенном макро масштабе.
Одним из способов получения графена и материалов на его основе в ощутимых
количествах является многостадийный синтез из графита с использованием в качестве
прекурсора - оксид графена (ГО) с последующим его восстановлением. Примечательно,
что широкий спектр поверхностных функциональных кислородсодержащих групп в
плоскости и на краях оксида графена позволяет диспергировать его в воде и
органических растворителях, обеспечивая тем самым большие возможности
применения его для создания материалов.
Модификация указанного прекурсора ионами металлов, позволит, создавать
макро объекты с высокими прочностными свойствами. ГО – это нанообъект двумерной
формы, который представляет новый класс диспергируемых полиароматических
систем для проведения различных химических синтезов. Кроме уникальных свойств,
доступный продукт – что позволяет широко применить его в различных областях.
Мы провели серию экспериментов по подбору концентрации ионов металлов,
необходимых для координации с ГО разных концентраций. Серия опытов, позволила
нам набрать статистические данные по определению концентрации ионов металлов
различной валентности (I, II и III), которые необходимо взять для взаимодействия с ГО.
Мы определили минимальный порог концентрации каждого вида ионов металлов Ag+,
Cu2+, Fe2+, Fe3+ и Bi3+ необходимого для начала выпадения осадка при модификации с
ГО в различных его концентрациях (1, 2 и 3 мг/мл).
Анализ данных показывает, что происходит корреляция необходимого объема
или концентрации иона металла между величиной заряда. Также присутствует
зависимость между разными концентрациями ГО и минимальной концентрации иона
для начала выпадения осадка, так при СГО=1 мг/мл для иона Ag+ требуется 1,8·10-3
моль/мл иона металла, для Cu2+, необходимо 2,8·10-4 моль/мл иона металла, а при
координации с ионом трехвалентного железа 4,7·10-5 моль/мл иона металла.
Полученные соединения были, исследовали комплексом физико-химических
методом анализа. Было обнаружено, что при координации ионов металлов с ГО
происходит сшивка молекул оксида между собой и образуется каркасная структура. Мы
предполагаем, что взаимодействие ионов металлов с ГО происходит двумя способами:
через мостиковые группировки на краях молекул и через связывание отдельных слоев
друг с другом.
В заключение следует отметить, что проведенные исследования позволили
впервые создать модифицированные соединения оксида графена ионами металлов. Эти
исследования, несомненно, получат дальнейшее развитие, а полученные материалы
могут быть использованы для создания инновационных технологий в области новых
углеродных материалов на основе графена.
ТЕРМОДИНАМИКА РЕАКЦИЙ ЭТИЛЕНКАРБОНАТА С МЕТАНОЛОМ

Самуилов А.Я., Самуилов Я.Д.
Казанский национальный исследовательский технологический университет,
Казань, e-mail: ysamuilov@yandex.ru
Переэтерификация этиленкарбоната метанолом является одним из важнейших

методов получения диметилкарбоната. Диметилкарбонат является малотоксичным
соединением, легко разлагаемым в окружающей среде, и он находит применение как
“зеленый” растворитель. Он является промежуточным продуктом в бесфосгенных
способах получения поликарбонатов, изоцианатов, исходных соединений для
получения полиуретанов, и находит широкое применение в многочисленных
органических синтезах.
Выбор условий переэтерификации этиленкарбоната во многом зависит от
термодинамических закономерностей процесса. Попытки оценки термодинамических
характеристик взаимодействия этиленкарбоната с метанолом предпринимались.
Однако в данных работах авторы не учитывали стадийность обсуждаемого процесса, и
исходили из предположения, что спирты существуют только в виде мономеров. Однако
спирты представляют собой сильно ассоциированные соединения. В частности,
метанол в жидкой фазе в основном существует в виде линейных димеров и тримеров.
Кинетические и термодинамические параметры реакций с участием ассоциатов спиртов
и их мономерных форм сильно различаются. С целью решения вышеобозначенных
проблем были изучены термодинамические характеристики метанолиза
этиленкарбоната с учетом стадийности данного процесса и участия в нем линейных
ассоциатов спиртов.
Квантово-химическим методом B3LYP/6-311++G(df,p) определены
термодинамические параметры основных и побочной реакций в процессе образования
диметилкарбоната из этиленкарбоната и метанола. Показано, что в реакциях с участием
спиртов термодинамические параметры взаимодействий с отдельными типами
ассоциатов могут быть резко отличными. Характер температурных зависимостей
констант равновесия может сильно зависеть от типа ассоциата спирта, вступающего в
превращение. С увеличением степени ассоциации спиртов возрастают энтальпии и
энтропии взаимодействий. Определены температурные зависимости констант
равновесия превращений. Анализ термодинамических закономерностей
взаимодействия этиленкарбоната с метанолом указывает на то, что первая стадия этой
реакции характеризуется малыми величинами констант равновесия, вторая стадия
является практически необратимой. Сформулированы условия, которые необходимо
соблюдать при разработке технологии получения диметилкарбоната метанолизом
этиленкарбоната.
Работа выполнена в рамках реализации ФЦП «Научные и научно-педагогические
кадры инновационной России» на 2009-2013 годы, ГК № 16.740.11.0503.
454 ♦ RCCT-2013. Round table: Chemical thermodynamics teaching
ВЛИЯНИЕ МАТЕМАТИЧЕСКОЙ ПОДГОТОВЛЕННОСТИ АБИТУРИЕНТОВ

НА УСПЕШНОСТЬ ОСВОЕНИЯ ФИЗИЧЕСКОЙ ХИМИИ
ПРИ ОБУЧЕНИИ В УНИВЕРСИТЕТЕ
Белевцова Е.А., Рыжова О.Н.
Московский государственный университет имени М.В. Ломоносова,
Химический факультет, Москва, e-mail: liskin-mermaid@yandex.ru
В России в соответствии с Законом об образовании, отбор абитуриентов в вузы
осуществляется на основе баллов ЕГЭ по предметам, соответствующим специальности.
Лишь Московский и Санкт-Петербургский государственные университеты могут
проводить дополнительное вступительное испытание по профильному предмету. Таким
образом, испытания по математике при поступлении на химический факультет не
предусмотрено.
Между тем математическая подготовка выпускников школ неуклонно снижается.
С каждым годом первокурсники химического факультета МГУ испытывают все
большие затруднения при освоении математического анализа и других дисциплин
математического цикла, а также физики. Анализ успеваемости первокурсников
химического факультета МГУ на протяжении пяти лет подтверждает, что
недостаточная математическая подготовка абитуриентов влечет за собой снижение
качества усвоения химических знаний – прослеживается четкая корреляция между
падением успеваемости по математической дисциплине и различными химическими
дисциплинами.
К освоению физической химии, изучение которой начинается именно с
химической термодинамики, студенты химического факультета приступают в середине
III курса, после завершения основных математических курсов. Специфика физической
химии выражается в высокой насыщенности элементами высшей математики, поэтому
качественное обучение специалистов-химиков без соответствующей математической
подготовки может оказаться невыполнимой задачей.
Актуальной становится задача проверки уровня знаний абитуриентов-химиков в
условиях отсутствия вступительного экзамена по математике.
С целью определения степени насыщения математической составляющей был
выполнен анализ массива химических задач письменных конкурсных вступительных
испытаний с 1990 года по настоящее время. Мы разделяли задачи на чисто химические,
без элементов математики, и задачи, включающие математическую составляющую.
Последние классифицировались по типам необходимых математических операций.
Оказалось, что степень насыщения комплектов заданий математическим
содержанием на протяжении всего периода проведения письменного экзамена по
химии в МГУ возрастала. Если в начале 1990-х годов на 7 задач экзаменационного
билета приходилось в среднем 2 задачи с математическим содержанием, то в последние
годы таковыми являются до половины заданий (5 из 10). При этом прослеживается
тенденция к увеличению разнообразия математических операций.
Выявленные содержательные изменения в материалах вступительных экзаменов и
олимпиад носят весьма позитивный характер, они отражают своеобразную адаптацию
системы конкурсных вступительных испытаний к реформам системы образования, а
также математизацию химической науки.
Мы планируем постоянно отслеживать уровень подготовленности наших
абитуриентов, учитывать его при составлении комплектов конкурсных задач, и, по мере
необходимости, корректировать насыщенность материалов вступительных экзаменов
по химии математическим содержанием.
Authors Index
Abakumov G.A. 39, 82 Babanly N.B. 83

Abdusalyamova 152 Badalov A.B. 96, 152,
M.N. 153
Abildaeva A.Zh. 109 Badelin V.G. 173, 313
Abramova G.V. 78 Bagheri S.M. 183
Adamova L.V. 198 Bakovets V.V. 185
Adekenov S.M. 109 Balashova T.V. 39
Afineevskiy A.V. 398 Bancel Fabrice 400
Agafonova E.V. 199 Barabanov V.P. 155
Agafonova L.E. 79, 176 Barbin N.M. 413
Agieienko V.N. 200 Barbov A.V. 361
Aitekenov S.K. 408 Batyrova R.G. 289
Aksenova T.V. 175 Batyrshin N.N. 399
Alaverdiev I.J. 183 Bazaev A.R. 226, 244
Albov D.V. 147 Bekturganov N.S. 64
Alekseeva O.M. 338 Belevantsev V.I. 24
Aliev A.Sh. 206 Beljaeva L.A. 403
Aliev Z.S. 207 Belogurova O.A. 411
Alieva Z.M. 183 Belopolskaya T.V. 84
Alikhanyan A.S. 80, 102, Belousova Z.P. 220
111, 131 Belov A.V. 208
Aliyev E.N. 402 Belov G.P. 170
Aliyev Z.S. 272 Belov G.V. 25, 72
Alyoshin V.A. 169, 201 Belov N.A. 209
Amerkhanova Sh.K. 81, 202, Belova E.V. 210
203 Belyaev S. 400
Anashkin I.P. 34 Belyaeva L.A. 85
André Rémi 400 Bembel A.G. 339
Andreev O.V. 90, 204, Bencze L. 105
436 Benmounah A. 340
Anisimov M.A. 8 Berezina O.Y. 322
Anisimova V.I. 399 Bichan N.G. 211
Antonova O.A. 205 Binyukov V.I. 338
Anuchin K.M. 231 Biryukov A.I. 325
Anyfrieva O.I. 213, 273 Bissengaliyeva M.R. 60, 64
Aralkina N.V. 237 Blokhin A.V. 86, 156,
Arapova A.V. 82 180, 308,
Art’emkina Y.M. 208 330
Arutyunyan N.A. 401 Blokhina A.S. 198
Asadov М.М. 402 Bogatishcheva N.S. 139
Auzmendi-Murua I. 107 Bogdanov D.V. 274
Avchenko O.V. 30 Bokov N.A. 212
Avramenko N.V. 85, 403 Boldyrev M.I. 26
Babanly D.M. 206 Borisevich S.S. 45
Babanly M.B. 183, 207, Bozzelli J.W. 9, 106,
240, 272 107
Author index ♦ 457
Branovitskaya N.V. 146 Ciccioli A. 88

Brilliantov N.V. 343 Coquelet C. 262
Brodskaya E.N. 56, 57 Coxam J.-Y. 269
Brown J.S. 416 Deiters U.K. 199
Bruk L.G. 434 Demchuk Zh.A. 90
Brunetti B. 88 Dementiev A.I. 80
Bryukhanova K. 87 Dementiev P.D. 322
Bryzgalova A.N. 134, 213, Dezortsev S.V. 404, 406,
273 430, 433
Bubnov M.P 82 Dgyabiyeva Ali kyzy S. 220
Budkov Yu.A. 252, 343 Dibrivniy V.N. 91
Bulanov E.N. 27, 130 Dinmukhametova R.A. 31
Bulanova A.V. 115, 364 Dmitriev A.S. 98, 151,
Bulavin V.I. 214 405
Burmakina G.V. 321 Dmitrieva O.A. 230
Burmatnova T.S. 349 Dobrokhotova Zh.V. 92
Burmistrov V.А. 168 Dodonov V.A. 418
Bushuev M.V. 429 Dolgoshey V.B. 35
Buslov I.V. 329 Dolomatov M.Yu. 404, 406,
Butman M.F. 158 430, 433
Bychinsky V.A. 28, 30, 44, Domańska U. 407, 425
171 Domanski P.A. 416
Caminiti R. 177 Dorofeeva O.V. 93, 166
Cardona C.A. 10 Doronin Ya.I. 221
Castillo Alvaro 107 Dribinsky B.A. 246
Chaban V.V. 215, 243 Druzhinina A.I. 79, 119,
Chachkov D.V. 135, 155 176
Chausov I.S. 288 Dunaev A.M. 94, 158
Chekunova M.D. 326 Dunaev S.F. 401
Chelyuskina T.V. 216, 217 Dunaeva E.S. 210
Chepkasov I.V. 29, 38 Dunyashev V.S. 222
Cherepanov V.A. 181, 175 Dupal A.Ya. 223
Cherevko A.G. 341 Durov V.A. 224
Chernorukov N.G. 113 Dushina S.V. 233, 237
Chernov А.S. 268 Dyakonov G.S. 31
Chernova E.M. 89, 150, Dyakonov S.G. 31
162 Dzhapparov T.A. 226
Chernozhuk T. V. 218 Dzuban A.V. 408
Chernyavskaya N.V. 268 Edimecheva I.P. 180
Chernyshev Y.S. 254 Efremova E.I. 228
Chervonova U.V. 114 Egorov G.I. 227
Chibunova E.S. 219 Ekimovskaya A.A. 237
Chu H.L. 19 Elyshev A. V. 204
Chubarov V.M. 44 Emel’yanenko V.N. 95, 100,
Chudnenko K.V. 28, 30 178
Chupakhina T.I. 213, 273 Emelianov M.V. 428
Chusova T.P. 185, 187 Emelina A.L. 103, 116
Emelyanova K.A. 160 410, 415

Ermamadova S.G. 293 Gontrani L. 177
Ermokhin V.A. 115 Gorak Yu.I. 314
Eshov B.B. 96 Gorbatchuk V.V. 236, 344
Evstigneeva E.M. 97 Gorokhov L.N. 101, 141
Fabinskiy P.V. 229 Gotlib I.Yu. 56
Fedin V.P. 185 Gramma V.A. 147, 148,
Fedorov V.A. 229 149
Fedorova A.A. 356 Granitova O.V. 351
Fedoseev V.B. 342 Grazhdan K.V. 237
Fedoseeva E.N. 342 Gribchenkova N.A. 102
Fedotova M.V. 205, 230 Gridchin S.N. 238
Filina T.E. 351 Grishchenko R.O. 103, 119
Filonova E.A. 98, 151, Grishin N.N. 411
405 Gruba O.N. 108
Firer А.А. 223 Grunina N.A. 84
Firsov D.A. 231 Grushova E.I. 311
Flid V.R. 446 Gruzdev M.S. 114
Fomenkov P.E. 367 Gubanova G.N. 412
Fomina T.G. 146 Gulenova M.V. 418
Forero H.A. 10 Gurevich V.M. 104, 138,
Frenkel M. 11, 416 154
Frolkova A.K. 232, 302, Harutyunyan L.R. 260
309 Harutyunyan R.S. 260
Frolkova A.V. 309 Haustein M. 345, 355
Frolov A.I. 343 Held C. 17
Gafner Yu.Ya. 29 Hellmuth O. 346, 365
Gafurov B.А. 99 de Hemptinne J.C. 262
Galashova S.A. 410 Henriques D. 105
Galenko E.О. 297 Heo J. 416
Galyaltdinov S.F. 236, 344 Holubeva N. 247, 248
Galyametdinov Yu.G. 118, 305 Hosko J. 161
Gamov G.A. 233 Hudzik J.M. 9, 106
Garist I.V. 100 Huseynov F.N. 240
Gavrichev K.S. 87, 92, 104, Ibadova G.I. 207
138, 154 Ibavov N.V. 275
Gavrilova L.Ya. 181 Idrissi A. 243, 263
Gavrilova M.A. 233 Igumenov I.K. 179, 409
Gelfond N.V. 409 Ilatovskaya M.O. 317
Gerasymchuk S.I. 144 Ilinykh A.S. 413
Ghazoyan H.H. 234 Ilinykh N.I. 239
Gimadeev A.A. 155 Ilyasli Т.М. 207
Girichev G.V. 174 Imamaliyeva S.Z. 240
Gogol D.B. 60, 64 Inozemtcev J.O. 136
Golodkov O.N. 170 Iorish V.S. 25
Goloshchapov A.N. 338 Isaeva V.A. 257, 279
Golovanova O.A. 235, 255, Iskakova T.K. 40
Islomova M.S. 99 Kir’yanov K.V. 418

Ivanov A.S. 435 Kirienko D.A. 322
Ivanov D.A. 94, 158 Kiselev A.E. 419
Ivanova N.I. 403 Kiselev M.G. 343
Ivashkevich A.N. 241 Kiselev M.R. 228
Izadpanah A.A. 414 Kiseleva I.A. 140
Izmailov R.R. 415 Kistanova N.S. 421
Jaramillo J.J. 10 Kiyko A.V. 439
Kabanova E.G. 259 Klimov A.V. 231
Kabo A.G. 86, 330 Klimov V.L. 32, 33
Kabo G.J. 86, 180, Klinov A.V. 31, 34
308, 330 Knyazev A.A. 118
Kachalova G.S. 436 Knyazev A.V. 27, 60,
Kacher E.B. 427 113, 117,
Kalugin O.N. 200, 215, 130, 401
218, 242, Knyazeva S.S. 113
243, 263, Kochubey V.V. 144
296 Kohut S.V. 86, 156,
Kamkin N.N. 80, 111, 180
131 Kokurina N.Yu. 110, 124
Karabekova B.K. 244 Kolesnik Ya.V. 215
Karataeva I.M. 245 Kolesnikov A.L. 252
Karlina O.K. 32, 33 Kolker A.M. 114, 227
Karpova I.L. 35 Kolosov V.N. 420
Kasenov B. K. 109 Komilov К. 253
Kasenova Sh.B. 109 Komissarova L.N. 104
Kashina O.V. 429 Komshina M.E. 117
Kashtanov E.A. 110, 124 Kon’kova Т.С. 136
Kasyanenko N.A. 246 Koneva A.S. 254
Katsman E.A. 434 Kononova S.V. 412
Kayumova D.B. 80, 111 Konstantinov A.V. 115
Kazakov A. 416 Konyukhov V.Yu. 310, 437
Kazancev S.A. 31 Kopytin K.A. 347, 358
Kazhikenova A.Sh. 41 Korobov M.V. 85, 403
Kazmina T.M. 112 Korokin V.J. 27
Kerbaliyev R.A. 417 Korolev V.P. 205
Khakerov I.Z. 152 Korolkov V.V. 255
Khakimova D.K. 153 Korskanov V.V. 35
Khaltanova V.M. 438 Korunov A.A. 223
Khasanshin Т. 247, 248 Kos R.V. 314
Kheribet R. 340 Koschel D. 269
Kholodyuk E.A. 138 Kosova D.A. 116
Khondar O.G. 231 Kotel’nikova O.A. 351
Khoroshilov А.V. 154 Kovalenko N.A. 256, 281
Kibalnikova O.V. 249 Kovaleva J.A. 257
Kilina A.A. 250 Kovaleva Yu.A. 279
Kimyashov A.A. 251 Kowalski R. 258
Kozyulina A.V. 116 Lapshina E.S. 84

Krasheninnikova 117 Lapteva L.I. 47
O.V. Larina V.N. 124
Krasnov A.V. 174 Lazarev N.M. 39
Krasnykh E.L. 36, 186 Lebedev L.G. 281
Krementsova A.V. 338 Lebedeva M.V. 446
Kremnev D.V. 59 Lelet M.I. 125
Krivandin A.V. 338 Leonovich B.I. 423
Krivorogov M.V. 413 Letyanina I.A. 126
Krüger S. 355 Levitskaya T.N. 308, 330
Krupin A.S. 118 Lezov A.A. 254
Kryuchenkova N.G. 367 Lipeiko A.V. 215
Kryzhanov M.V. 431 Lirova B.I. 351
Kudin L.S. 94, 158, Litinskii G.B. 127
419 Litvinenko G.S. 40
Kudryashov S.Y. 347, 348, Lobacheva O.L. 261
358 Lobov I.A. 410
Kudryashova O.S. 421 Lomova T. N. 211
Kudryashova Z.A. 228, 274 Lopatin S.I. 128, 159,
Kudryavtseva I.V. 37 160, 318
Kulagina T.G. 170 Lozeiko T.V. 112
Kulakov A.A. 47 Luchai K.V. 236
Kuleznev V.N. 63 Lugo R. 262
Kumeev R.S. 219 Lukin M.V. 398, 424
Kuraeva Yu.G. 349, 359 Lukinova O.V. 243, 263
Kuranov G.L. 250 Lukoshko E. 425
Kuranova N.N. 237 Lukyanova V.A. 129
Kurbanova E.D 29, 38, 52 Lutikova E.A. 351
Kurbatova S.V. 220 Lutsyk V.I. 68, 264,
Kurdakova S.V. 119 265, 301,
Kush D.S. 124 422, 444
Kut’in A.M. 120, 432 Lyaschenko A.K. 245
Kutin A.A. 327 Lyashchenko A.K. 222, 266
Kutsenok I.B. 69, 70, 72 Lykasov A.A. 251
Kuvshinova S.A. 349 Lysenko V.A. 267, 329
Kuz’min A.E. 121 Lysyakova L.A. 246
Kuz’mina I.A. 122, 123 Lytkin A.I. 268
Kuznetsov N.T. 159 MacFarlane D.R. 12
Kuznetsov V.A. 285 Mączka M. 130
Kuznetsov V.N. 259 Magomedov M.N. 352
Kuznetsov V.S. 350 Mahmoudjanlo H. 414
Kuznetsova T.A. 367 Maiorova M.K. 444
Kuzovkova М.А. 305 Majer V. 269
Kоs Yu.V. 307 Makaev S.V. 270
Lachinyan M.L. 260 Makarov D.M. 227
Lamueva M.V. 422 Makarov I.A. 274
Lapi A. 88 Makarov P.Y. 70
Makrovets L.A. 42 Mirskaya V.А. 275

Maksimov A.I. 72 Mirzaev D.A. 426
Malakhov A.O. 271 Mirzoev A.A. 61, 426
Malkerova I.P. 80, 111, Mischenko G.A. 427
131 Mochalova A.E. 124
Malygina E.N. 422 Mögel H.-J. 345, 355
Malyshev V.P. 41 Mogloeva S.N. 422
Mamedova M.T. 353 Molostova E.Yu. 118
Mamontov M.N. 278, 290 Monayenkova A.S. 169, 201
Manin A.N. 132 Monina L.N. 276
Manin N.G. 299 Moricheva N.A. 142
Manyukova N.N. 32, 33 Moroshkina E.B. 277, 285
Marekha B.A. 243, 263 Morozova N.B. 179, 409
Marinichev A.N. 315 Motalov V. 105
Markarian S.A. 234 Motalov V.B. 94
Markin A.V. 126, 133, Motornova M.N. 278
163 Mousazadeh M. H. 43
Markus T. 105 Mozgunov N.E. 428
Marochkin I.I. 93 Mudretsova S.N. 147
Marry V. 58 Mukhetdinova A.V. 28, 44,
Maryasov A.G. 341 171
Maryunina K.Yu. 92 Mustaev A.R. 45
Mashadiyeva L.F. 272 Muzafarov A.M. 126, 164
Maskow T. 95 Mаkarova D.V. 305
Matigorov A. O. 204 Naiman M.O. 47
Matskevich M.Yu. 213, 273 Najmushin A.B. 427
Matskevich N.I. 134, 213, Nasriddinov S.K. 153
273 Nasrulin E.R. 68
Matveeva K.R. 421 Nasruloeva D.Kh. 99
Matyushin J.N. 136 Naumov V.V. 257, 279
Maximov A.I. 278 Nazanskiy S.L. 439
McLinden M.O. 416 Nazarevich D.А. 275
Medvedev D. A. 98 Nazarov M.S. 428
Mehling T. 298 Nechaevskiy S.Yu. 280
Mel, nikov A.B. 274 Nekhoroshev E.E. 281
Melchakova L.V. 140 Nenashev R.N. 137
Melnikov P.V. 288 Nesterov I.A. 145
Merkin A.A. 361 Nevsky A.V. 429
Mikhailov G.G. 42, 300 Nguyen Van Thuc 299
Mikhailov O.V. 135 Nigmatullina I.E. 430
Mikhailov V.A. 161 Nikiforova G. 87
Mill E.M. 338 Nikiforova G.E. 138
Milyaeva О.Y. 354 Nikiforova G.Ye. 154
Minikaeva G.F. 276 Nikitin E.D. 139
Miroshnichenko E.A. 136, 143 Nikolaeva A.L. 282
Miroshnichenko M.N. 420 Nikolaychuk P.A. 283
Mirsaidov I.U. 99 Nikolskiy V.M. 182
Nikonova O.V. 423, 443 Perlovich G.L. 132, 167

Nizhegorodova Yu.A. 209 Peshkina K.G. 286
Nogovitsin E.A. 252 Pestov S.M. 112, 157,
Nosikova L.A. 228 258, 357
Noskov B.A. 354 Petrik G.G. 48
Novikov A.N. 221, 284, Petrov B.I. 39
294 Petrova M.D. 297
Novikov V.B. 165 Pham Thi Lan 49
Obkhodskaya E.V. 440 Pikalova E.Yu. 98
Obushak N.D. 91 Pimenova S.M. 145
Ochkin A.V. 280 Pimerzin A.A. 50, 51,
Ogorodova L.P. 140 184, 362
Oja V. 13 Pisarenko Yu.A. 14
Ojovan M.I. 32, 33 Pivovarova N.A. 347, 358
Okishev K.Yu. 426, 441 Platonov V.I. 359
Onuchak L.A. 46, 347, Plehovich A.D. 432
349, 358, Plesovskyh A.S. 27
359 Poddubskij O. 247, 248
Orlov M.Y. 162 Podguzova T.S. 360
Orlov N.K. 103 Podyacheva K.I. 404, 433
Orlov V.M. 431 Pokintelitsa E. A. 287
Orlov V.N. 420 Polenov E.A. 288
Orlov Y.D. 150, 162 Polikhronidi N.G. 289
Orlov Yu.D. 89, 172 Polukhin V.A. 29, 38, 52
Osadchaya T.Yu. 356 Polyachenok L.D. 146
Osfouri S. 414 Polyachenok O.G. 146
Osin S.B. 141 Popov A.P. 139
Osina E.L. 101, 141 Popova E.N. 412
Osinnikova D.N. 285 Popova O.V. 321
Ostroushko A.A. 142 Portnova S.V. 36
Ovcharenko V.I. 92 Postnikov V.A. 287
Ovchinnikov V.V. 47 Povalisheva D.V. 80, 131
Panchenko V.G. 242 Povar I. 53
Panin A.I. 128, 160 Pozdeev A.N. 290
Panyushkin V.V. 329 Praliyev K.D. 40
Papina T.S. 129 Pratskova S.E. 291
Parfenova A.M. 403 Prikhodko I.V. 250
Parfenova M.D. 301 Prokhorova T.Yu. 420
Paricaud P. 262 Prokop R.T. 91
Le Parlouër Pierre 400 Prozorov D.A. 361, 424
Pashchenko L.L. 143 Pukinsky I.B. 250
Passarello J.P. 262 Pulatov P. 96
Paulechka Y.U. 86, 308, Punin Yu.O. 255
330 Punyak M. J. 91
Pavlova G.Yu. 32 Purygin P.P. 115
Pavlovski Yu.P. 144 Putin A.Yu. 434
Perenlei A. 217 Pyreu D.F. 238
Qiu S.J. 19 Safi B. 340

Raeva V.M. 292, 302 Safonova E.A. 254, 298
Rahimova R.N. 293 Safonova L.P. 299
Rajabov U.P. 293 Safronov A.P. 142
Rajewskiy J.A. 91 Safronova I.A. 364
Rakhimova B.B. 109 Safronova T.O. 157
Rakipov I.T. 54 Sagadeev E.V. 155
Ramazanova E.E. 402 Sagintaeva Zh.I. 109
Randzio S.L. 199 Saidi M. 340
Rassokhina L.Yu. 284, 294 Saifutdinov B.R. 362
Rasulov S.M. 295 Sakharova A.A. 301
Razozi M.B. 96 Salimov Z.E. 83
Rebelo L.P.N. 15 Salnikova E.I. 436
Repkin G.I. 306 Samar M. 340
Restrepo J.B. 10 Samoylova O.V. 300
Revina A.A. 446 Samsonov V.M. 339, 363
Riabchunova А.V. 296 Samuilov V. 247, 248
Rodnikova M.N. 316 Sankovich A.M. 156
Roganov G.N. 100 Sapchenko S.A. 185
Rojkov I.V. 161 Sarycheva N.S. 151
Romashkova K.A. 412 Savinov V.V. 301
Rubaylo A.I. 321 Sazonova A.Y. 302
Rukk N.S. 147, 148, Schiller P. 345, 355
149 Sedov I.A. 303, 304
Rumzev E.I. 274 Selivanova N.М. 305
Rusakova N.P. 150 Semenov I.M. 306
Rusanov А.I. 16 Seminozhenko D.G. 157
Rusejkina A.V. 297 Semyannikov P.P. 179, 409
Ruseykina A.V. 90 Senyavin V.M. 403
Rusinkevich A.A. 435 Serafimov L.A. 18
Russkikh O.V. 151 Sergeev D.N. 94, 158
Rustamov S.Т. 96, 152 Serheyev V.V. 307
Ruzanova G.E. 426 Sevastyanov V.G. 159
Ruzmatova G.K. 153 Sevastyanova L.G. 329
Ryabchunova A. V. 243 Seyidov N.M. 417
Ryabukhin A.G. 108 Sferrazza A. 177
Rykov A.V. 37 Shabaev I.V. 346, 365
Rykov S.V. 55 Shabanov A.L. 402
Rykov V.A. 55 Shaburov A.D. 426
Ryumin M. 87 Shafigulin R.V. 115, 364
Ryumin M.A. 92, 104, Shamsiev R.S. 147, 148,
154 149
Ryzhikh A.P. 24 Shamsutdinova R.D. 118
Ryzhova O.N. 93 Shapovalova A.A. 26, 56, 57
Sachkov V.I. 440 Sharipov D.Sh. 153
Sadovnikov А.I. 168 Sharipov I.H. 293
Sadowski G. 17 Sharlay E.V. 300
Sharnin V.A. 49, 66, 71, Smirnova I.V. 298

122, 123, Smirnova L.A. 124
233, 237, Smirnova N.A. 22, 250
257, 279, Smirnova N.N. 82, 126,
306 133, 163,
Sharonova Ye.A. 309 164
Shatalov K.I. 223 Smirnova O.I. 84
Shatalova O.V. 338 Smirnova V.E. 412
Shchamialiou A. 247, 248 Smirnyagina N.N. 438
Shchebetovskaya N.V. 287 Smolenkov Yu.Yu. 60, 64
Shchekin A.K. 346, 360, Snitsiriwat S. 9
365, 366 Sobechko I.B. 314
Shchurova M. A. 204 Sokolova E.P. 315
Shepelev M.V. 361 Sologubov S.S. 164
Shevelkov A.V. 272 Solokhin A.V. 439
Shevelyova M.P. 308, 330 Solomonov B.N. 165, 303,
Shibryaeva L.S. 338 304, 328
Shifrina Z.B. 163 Solonina I.A. 316
Shilov A.L. 318 Solov’ev S.N. 208, 223
Shirokova E.V. 316 Solovov R.D. 112
Shlyapov R.M. 203 Sosnowski S.A. 440
Shmukler L.E. 299 Sozykina A.S. 441
Shodorova S.Y. 68 Spinu O. 53
Shpineva M.A. 310, 437 Starukhin V.A. 61
Shugurov S.M. 128, 160, Starykh R.V. 265, 317
318 Steblevsky A.V. 102
Shulyak I.V. 311 Stepanov G.V. 289
Sibirtsev V.S. 59 Stepurko E.N. 86
Sidorov V.E. 161, 239 Stolov M.A. 304
Sikachov А. Yu. 145 Stolyarov A.V. 62
Simonenko E.P. 159 Stolyarova V.L. 159, 318
Simonenko N.P. 159 Storm S. 298
Simonin J.P. 58 Suchanova T.A. 274
Simonyan G.S. 312 Sukhanova T.E. 327
Sineva S.I. 317 Suleimanov E.V. 125
Sinyova S. 265, 400 Sun L.X. 19
Sirotkin D.A. 111, 131, Sungrapova I.D.-S. 444
316 Suntsov J.K. 319, 320
Sitnikov V.N. 162 Suntsova M.A. 93, 166
Sitnikova К.А. 122, 123 Surikov P.V. 63
Sizov V.V. 26, 57 Surov A.O. 167
Skorodumova N.A. 82 Sursyakova V.V. 321
Skryabina A.Yu. 147, 148, Suvorova I.A. 399
149 Svec P. 161
Slobodov A.A. 59, 427 Syrbu A.А. 168
Smaga S.R. 296 Syrbu Sv.А. 168
Smirnov V.I. 313 Sysoev S.V. 179, 409
Taimassova Sh.T. 60, 64 Ursaeva A.V. 426

Talyzin A.V. 85 Urusova А.S. 175
Tarahno E.V. 127 Uryash V.F. 110, 124
Tarakanova E.G. 331 Usacheva T.R. 49, 66, 67,
Tatevosyan S.S. 137, 322 71
Tatyanenko D.V. 366 Usol’tseva N.V. 350
Temkin O.N. 434 Uspenskaya I.A. 210, 256,
Teplova E.A. 364 278, 290,
Terekhova I.V. 219 408
Tiphlova L.A. 169, 201 V’unnik I.N. 214
Tkachev N.K. 286, 323 V’ynnik I.N. 242
Toikka А.M. 65, 324 Vakhitova E.R. 445
Tolkacheva L.N. 182 Valencia M.J. 10
Tolmachev A.M. 231, 367 Valueva S.V. 327
Tonkushina M.O. 142 Valyashko V.M. 20, 270
Tran Thi Dieu Thuan 66 Van-Chin-Syan Yu.Ya. 314
Trenina M.V. 59 Varfolomeev M.A. 54, 165,
Trofimov E.A. 300, 423, 328
442, 443, Varushchenko R.M. 79, 176
445 Vasilyev S.A. 339
Troitsky V.M. 316 Vasilyov V.A. 284
Trubin S.V. 179 Vassiliev V.P. 267, 329
Trusov B.G. 33 Vecchio S. 21, 88,
Tsereteli G.I. 84 177
Tsvetkov V.V. 51 Verevkin S.P. 95, 100,
Tsvetkov D.S. 98 165, 178,
Tsvetkova L.Ya. 170 184
Tsvetov N.S. 324 Victorov A.I. 22
Tsyngeev B.V. 444 Vigasina M.F. 140
Tsyuan Tszinchzhi 152 Vikulova E.S. 179
Tukumova N.V. 66 Vishnevskaya E.E. 51
Tulegenov A.S. 78 Vlasov A.Yu. 282, 315
Tupitsyn A.A. 28, 171 Vlasov M.V. 320
Turdukozhaeva A.M. 41 Voitkevich O.V. 86, 180
Turitsa V.V. 314 Volkova N.E. 181
Turovtsev V.V. 89, 150, Volkova М.А. 122, 123
162, 172 Vorob’ev A.B. 136
Tyulyaeva E. Yu. 211 Vorob’eva V.P. 68, 265
Tyunina E.Yu. 173, 326 Voronin A.P. 132
Tyunina V.V. 174 Voronin G.F. 69, 70,
Tyurin A. 87 408
Tyurin A.G. 291, 325 Voronina S.I. 71
Tyurin A.V. 92, 104, Voronina T.V. 59
137, 138 Voroshylova I.V. 243, 296
Tyuryukhanova A.P. 301 Voskov A.L. 72, 281,
Uali A.S. 81 408
Ulzhabayev K.M. 64 Vyazovkin I.V. 134, 273
Vydrin D.A. 42 Амерханова Ш.К. 449

Vylegzhanina M.E. 327 Андреев О.В. 334
Vylkov A.I. 405 Антонов А.С. 380
Wahab M. 345, 355 Асабина Е.А. 193
Warshavsky V.B. 360 Атаев Г.М. 369
Wolf Th. 213, 273 Ашимхан Н.С. 192, 195
Xiang C.L. 19 Бабиевская И.З. 448
Xu F. 19 Базулев А.Н. 380
Yakovlev A.A. 182 Байдаков В.Г. 370
Yanborisov V.M. 45 Байкенов М.И. 449
Yarishev N.G. 80 Байкенова Г.Г. 449
Yaryshev N.G. 111 Барановский Н.В. 73
Yashtulov N.A. 446 Бектуров Е.А. 196
Yermalayeu A.V. 184 Белевцова Е.А. 454
You S. 85 Бембель А.Г. 389
Yukhnevich G.V. 331 Бердибек Г.Б. 192
Yusibov Y.A. 83, 183 Бондарева Л.П. 371
Zaitsau Dz.H. 184 Борщев О.В. 387
Zaitsev A.I. 401, 447 Бруевич В.В. 387
Zakharova Yu.A. 163, 170 Буланова А.В. 383
Zamalyutin V.V. 147, 148, Буров Д.М. 333
149 Бычинский В. А. 191
Zamyatin V.M. 413 Валинурова Э.Р. 373, 391
Zaripov A.K. 253 Вандышев В.Н. 333
Zavrazhnov A.Ju. 332 Васильев С.А. 389
Zelenaya A.E. 422, 444 Васюкова Е.С. 194
Zelenina L.N. 179, 185, Веревкин С.П. 188
187 Верховых А.В. 382
Zhabina A.A. 186 Воронова М.И. 392
Zhang H.Z. 19 Гайнуллина Ю.Ю. 74
Zherdev V.P. 350 Галай Ю. В. 335
Zherikova K.V. 179, 187, Гапеев А.А. 371
409 Гарист И.В. 188
Zhernov I.V. 405 Гейдарова Ф.Ф. 368
Zhernovnikova A.M. 90 Герасимов А.В. 372
Zhou H.Y. 19 Герасимова Н.П. 335
Zhou Y.J. 19 Гермашева И.И. 394
Zhygir О.N. 35 Глухарева Н.А. 394
Ziganshin M.A. 236, 344 Горбачук В.В. 372, 377
Zinatulina A.R. 323, Григорьева А.В. 373
Zlomanov V.P. 137, 322, Гринев И.В. 378
332 Гросул А.А. 390
Zorin I.M. 274 Гусев С.В. 374
Zubkova M.Yu. 427 Гуськов В.Ю. 74, 375,
Zvereva I.A. 156 385, 393
Zyrianov A.M. 265 Гюльмалиев А.М. 449
Аббасов А.Д. 368 Даванков В.А. 376
Дергачева Н.П. 448 Паращук Д.Ю. 387

Джафарли М.М. 368 Пастухов А.В. 376
Дробот Д.В. 450 Перлова О.В. 388
Дробот Н.Ф. 448 Петьков В.И. 193
Елышев А.В. 334 Пимерзин А.А. 188
Емельяненко В.Н. 188 Плотникова Е.В. 384
Зиганшин М.А. 372, 377 Пономаренко С.А. 387
Зубков В.В. 378 Попова И.В. 390
Иванов Д.А. 387 Постников В.А. 387
Иванов С.П. 74 Прохоренко Н.Н. 75
Иовлев А.В. 387 Роганов Г.Н. 188
Кидяров Б.И. 379 Русанов А.И. 384
Ковба М.Л. 189 Рыжова О.Н. 454
Кожемяк М.А. 388 Сазонова В.Ф. 388
Колесникова Н.Р. 384 Самсонов В.М. 378, 380,
Колосов А.Ю. 380 389
Комаров П.В. 389 Самуилов А.Я. 453
Коробейников П.А. 190 Самуилов Я.Д. 453
Королева О.Н. 191 Сафронова Н.А. 194
Кочурова Н.Н. 381 Сдобняков Н.Ю. 380, 389
Кренев В.А. 448 Сейлханова Г.А. 192, 195,
Крестьянинов М.А. 392 196
Кудашева Ф.Х. 74, 373, Скоротецкий М.С. 387
375, 385, Смирнова Н.Н. 193
391 Соболева И.В. 384
Кудряшова О.С. 374 Соколов Д.Н. 380, 389
Кузнецов Г.В. 73 Солодовников А.О. 334
Кузнецов Ф.А. 451 Стрельцова Е.А. 390
Кутылев С.А. 450 Султанова А.Х. 391
Лауре И.В. 452 Суров О.В. 392
Леденков С.Ф. 333 Сухарева Д.А. 393
Лупоносов Ю.Н. 387 Сухарева Н.И. 335
Лучай К.В. 377 Тихова А.А. 394
Мамедова Ф.С. 368 Тихонов М.М. 386
Маркин А.В. 193 Тупицын А.А. 191
Менчук Е.М. 388 Турганалы Р.М. 196
Мирзоев А.А. 382 Туровцев В.В. 190
Митина Е.Г. 383 Усипбекова Е.Ж. 196, 195
Мовчан Т.Г. 384 Фомичев С.В. 448
Мозговой О.С. 385 Харитонцев В.Б. 334
Муханова А. 195 Цурика А.А. 450
Новожилов Н.В. 380 Челноков Д.А. 371
Носков Б.А. 386 Чернова Е.М. 190
Окишев К.Ю. 194 Чуб А.В. 450
Орлов Ю.Д. 190 Шафигулин Р.В. 383
Оспанова А.К. 192, 195 Шрубок А.О. 395
Павлова Л.А. 376 Щекин А.К. 384
Научное издание
Abstracts of the XIX International Conference on Chemical

Thermodynamics in Russia (June 24-28, 2013, Moscow)
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XIX International Conference on Chemical Thermodynamics in

Russia (RCCT-2013) (June 24-28, 2013, Moscow) : Abstracts. –

© MITHT Publisher, 2013

Members of the Organizing Committee

Local Organizing Committee:

Address of organizing committee:

PECULIAR THERMODYNAMICS OF SUPERCOOLED WATER

THERMOCHEMISTRY AND BOND DISSOCIATION ENERGIES OF NORMAL

APPLIED THERMODYNAMICS IN CHEMICAL AND BIOCHEMICAL ROUTES

THERMODYNAMICS AND CHEMICAL INFORMATICS: MARRIAGE MADE

TOWARDS THE HYDROGEN ECONOMY  PROGRESS

THERMODYNAMIC AND TRANSPORT PROPERTIES OF LIQUID PRODUCTS

PHYSICO-CHEMICAL BASIS FOR DEVELOPMENT

SALTY CHEMISTRY – INTERDISCIPLINARY CASE STUDIES

THERMODYNAMICS AND SUPRAMOLECULAR CHEMISTRY

THERMODYNAMICS OF BIOLOGICAL SYSTEMS

THERMODYNAMICAL-TOPOLOGICAL ANALYSIS AS THE BASIS OF RESEARCH

HYDROGEN STORAGE/PHASE CHANGE MATERIALS

Acknowledgements: This work was financially supported by the “973 Project”

SOME FEATURES OF SUB- AND SUPERCRITICAL PHASE BEHAVIOR

VAPORIZATION STUDY OF DIFFERENT CLASSES OF ORGANIC COMPOUNDS

MOLECULAR THERMODYNAMICS FOR SOFT SELF-ASSEMBLING SYSTEMS

The general issues

THE CONCEPTS ABOUT INITIAL COMPONENTS AND PHASES,

THERMOTOOL – SOFTWARE PACKAGE FOR CALCULATION

MODELING OF CU(II) IONS SOLVATION IN ACETONITRILE/WATER SYSTEM:

THERMODYNAMIC MODELING OF THE PHASE DIAGRAMS

ASSESSMENT OF THERMODYNAMIC PROPERTIES ON THE BASIS

THE FORMING OF MULTIFRACTAL AND COHERENT STRUCTURE AT VAPOR–GAS

SOLID SOLUTIONS IN THERMODYNAMIC MODELS

CLOSURE MODELLING OF ANALYTICAL THERMODYNAMICS

THERMODYNAMIC MODELLING AND EXPERIMENTAL INVESTIGATION

THERMODYNAMIC SIMULATION OF EXOTHERMIC REACTION PRODUCT

METHOD OF DETERMINATION OF INTERMOLECULAR INTERACTION

CONTRIBUTION OF THE IRREVERSIBLE PROCESSES

THE PREDICTION OF VAPORIZATION ENTHALPY FOR ACYCLIC

UNIFORM NONANALYTIC EQUATION OF STATE

EFFECTS ON THERMIC EVOLUTIONS OF CLUSTERS OF TRANSITION

INVESTIGATION OF THERMOCHEMICAL PROPERTIES OF THE

ENERGETIC SCHEMES OF FORWARD AND BACKWARD AND EXCHANGE

Energy schemes of forward and exchange Favorsky reactions, where

METHOD OF CALCULATION FOR TEMPERATURE DEPENDENCE OF VISCOSITY

DIAGRAMS OF PHASE EQUILIBRIUMS WITH CALCIUM AND BARIUM

FREE-VOLUME VISCOSITY MODEL FOR LIQUID METALS

THERMODYNAMIC MODEL AS THE APPROACH OF DEFINITION

STRUCTURE OF PREREACTION CENTRES OF DIENE POLIMERIZATION

Quantum-chemistry calculations were done on the cluster super computer of the

APPLICATION INVERSE GAS CHROMATOGRAPHY TO DETERMINE

SOME THERMODYNAMIC ASPECTS OF SUGARS

Ср 217.0 235.9 417.6 424.3 208.0

ON SINGULAR POINTS OF INTERMOLECULAR CURVES AND CONNECTIONS

FORMATION OF MOLECULAR COMPLEX BETWEEN TRIGLYCINE

PRACTICE AND PROBLEMS OF THERMODYNAMIC PROPERTIES CALCULATIONS

BOIL POINT OF HYDROCARBONS BY CORRELATION GAS

-14 The dotted line denotes the hypothetical isobar

THE BOND NATURE AND PROCESSES OF ATOMIC RECOORDINATION

THE USE OF THE BUFFER CAPACITY THEORY FOR THERMODINAMIC