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Adsorption, chemisorption, and catalysis

Article  in  Chemical Papers- Slovak Academy of Sciences · September 2014

DOI: 10.2478/s11696-014-0624-9

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 Chemical Papers 68 (12) 1625–1638 (2014)
DOI: 10.2478/s11696-014-0624-9

REVIEW

Adsorption, chemisorption, and catalysis

a,b
Milan Králik*

a VUCHT a.s., Areál Duslo a.s., 927 03 Šaľa, Slovakia

b Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava,

Radlinského 9, 812 37 Bratislava, Slovakia

Received 16 January 2014; Revised 14 June 2014; Accepted 25 June 2014

Dedicated to the memory of professor Elemír Kossaczký

A short history of the relationships among adsorption, chemisorption, and catalysis with solid
catalysts is reviewed. A special focus is on the development of quality and descriptions accuracy
using computers, both for the modeling of elementary physical phenomena and adsorption, as well
as for the solution of more complex problems like quantum chemical approach to chemisorption,
kinetics over solid catalysts, and reactor systems. Modern approaches to the characterization of solid
catalysts from the adsorption–desorption data based mainly on n-layer adsorption and non-linear
three parameter BET isotherm regarding the volume of micropores as one of the parameters are
demonstrated. Instrumentation techniques like infrared spectroscopy or NMR techniques for the
analysis of the strength of component chemisorption are mentioned. As for the kinetics, a vague
capability of the Langmuir–Hinshelwood–Hougen–Watson models to describe a reaction system
in more complicated cases, e.g. bimolecular surface reactions, is discussed. In this context, the
simplest model with a minimum number of parameters is advised. To estimate the most realistic
values, intrinsic reaction kinetic and mass transport phenomena are taken into account. Usefulness
of quantum mechanistic models for better understanding of the catalytic phenomena and more
efficient design of catalysts are outlined.

c 2014 Institute of Chemistry, Slovak Academy of Sciences

Keywords: adsorption, chemisorption, catalysis, infrared spectroscopy, quantum chemical models,

reaction kinetics, mass transport

Introduction A modern and still valid definition was introduced by

The phenomenon of catalysis is very old. Already
Aristotle (384–322 BC) wrote about active substances
(catalysts) and passive substances (reactants) under-
going transformation (Schwab, 1981). Observations in
the 17th and 18th century provided Berzelius (1835)
with a basis to define: “A catalyst is any substance (in-
cluding light) that directly alters the rate of a chem-
ical reaction without entering into the net chemical
reaction itself”. It is worthy to note that by this defini-
tion, a catalyst might increase or decrease the reaction
rate. However, in today’s definition, only substances
increasing the reaction rate are denoted as catalysts.
Ostwald (1896) who defined a catalyst as a substance
which accelerates a chemical reaction and it is not
consumed in the course of this reaction. Very impor-
tant were his thermodynamic considerations resulting
in the conclusion that a catalyst does not change the
chemical equilibrium of the reaction.
Experimental results and theoretical investigations
allow describing a catalytic process with a solid cata-
lyst as a sequence of actions:
– chemisorption of at least one of reaction compo-
nents;
– surface reaction of a chemisorbed component ei-
ther with other chemisorbed component or with a

*Corresponding author, e-mail: mkralik@vucht.sk, milan.kralik@stuba.sk

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component from the fluid phase surrounding the solid

catalyst;
– desorption of products.
Adsorption and chemisorption of reaction species
are unavoidable in a heterogeneously catalyzed pro-
cess and, in addition, all steps are accompanied by the
diffusion of reactants and products as well (Wisniak,
2010; Satterfield, 1980). The presented paper summa-
rizes data on adsorption, chemisorption, and catalysis
obtained in laboratories at the Slovak University of
Technology, as well as relevant important data from
other authors. Due to the enormous number of pa-
pers dealing with these topics, this paper cannot be
considered as a full review, but an attempt to suggest
suitable procedures for the study of heterogeneous cat-
alysts and of the adsorption/chemisorption effects on
their performance.

Adsorption

According to definition (Ruthven, 1984), adsorp-

tion is a process that occurs when a gas or liquid so-
lute (adsorptive) accumulates on the surface of a solid
or a liquid (adsorbent), forming a molecular, ionic, or
atomic film. Species (molecules, atoms, ions) of the
adsorptive adhered to the adsorbent are called adsor-
bate. The formed film of adsorbate is usually a multi-
layer for the gas phase adsorption and a monolayer for
the liquid phase adsorption. Physical adsorption is en-
abled by the van der Waals forces between molecules
and/or atoms on the adsorbent surface and adsorbate,
whereas adsorbate resembles a condensed liquid form
of the adsorptive. Adsorption from the gas phase very
often involves condensation of the adsorptive in pores
of the adsorbent.
For quantitative evaluation of the adsorbent ca-
pability, adsorption isotherms are applied. They are
expressed as a function obtained at a constant tem-
perature expressing an equilibrium amount of the ad-
sorptive adsorbed at a certain partial pressure or con-
centration (generally activity) of the adsorptive in
the gas or liquid (generally bulk) phase. Adsorption
isotherms start at zero activity up to a maximum;
for a gas phase it is a pressure related to the satu-
rated one at a temperature at which the adsorption
isotherm is determined. To obtain reliable experimen-
tal adsorption–desorption data, maximum outgassing
of the adsorbent and sufficient time for reaching an
equilibrium between the adsorptive and the adsorbate
are unavoidable conditions (Lecloux, 1981; Rouquerol
et al., 1994; Sing et al., 1985; Ruthven, 1984; Thomas
& Thomas, 1997).
Six types of isotherms reflecting the type of a
porous material are considered generally (Fig. 1,
IUPAC classification, Sing et al. (1985)). Texts in in-
dividual charts of Fig. 1 denote the main feature of the
adsorption process. Terms: micropores (diameter <
2 nm), mesopores (diameter = 2–50 nm), and macrop-
Fig. 1. Typical adsorption isotherms (IUPAC classification
(Sing et al., 1985)). Abscissas and ordinates express
relative pressure (x = p/ps ) and adsorbed amount
(vA /(cm3 g−1 )), respectively.
ores (diameter > 50 nm) are distinguished (Sing et al.,
1985; Hudec, 2012). When the adsorbent has a high
volume of micropores (type I) even at low activity of
the adsorptive, a large amount of it is accumulated
in the adsorbent. On the contrary, materials without
micropores accumulate material proportionally to the
activity of the adsorptive. Usually, the strength of the
adsorption of the second and next layers of the adsor-
bate differs from that of the first layer. If the adhesion
of the first layer is weak, then adsorbate has to cover
the surface first at a relatively large activity of the
adsorptive and then, the formation of the second and
next layers is performed only at a little increase of the
adsorptive activity (type III). Type IV represents ad-
sorbents with mesopores in which capillary condensa-
tion occurs (Lecloux, 1981). Type V is similar to type
IV but for the week adsorption of the adsorptive. Type
VI comprises multilayered adsorption, and/or adsor-
bents with different dimensions of mesopores. Adsorp-
tion processes accompanied with large condensation
of the adsorptive are typical with hysteresis presented
by desorption isotherms. Due to capillary condensa-
tion of the adsorptive, desorption proceeds at lower
activity than adsorption (Lecloux, 1981; Sing et al.,
1985; Hudec, 2012; Thomas & Thomas, 1997).
Description of adsorption isotherms
Attempts to describe adsorption isotherms have

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 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
led to various models. The Langmuir adsorption
model is based on the assumptions that:
– all sites on the adsorbent surface possess equal
affinity for the adsorbate;
– interactions among adsorbate molecules are neg-
ligible;
– the adsorption proceeds with formation of only
one layer of the adsorbate on the adsorbent surface
(the so called: monolayer adsorption) :
KLa x
va,La = VLa
1 + KLa x
where va,La /(cm3 g−1 ) is the adsorbed amount calcu-
lated according to the Langmuir adsorption isotherm,
VLa /(cm3 g−1 ) the monolayer (maximum) adsorption
capacity, KLa the equilibrium constant in the Lang-
muir adsorption isotherm, and x the relative pressure
(x = p/ps , where p and ps are adsorptive absolute
and saturated pressure at given temperature, respec-
tively).
For a low activity of the adsorptive (x → 0), the
Langmuir isotherm is reduced to the form of the Henry
isotherm:
va,He = VHe x (2)
where va,He /(cm3 g−1 ) is the adsorbed amount cal-
culated according to the Henry isotherm and VHe /
(cm3 g−1 ) the maximum adsorption capacity.
As it can be seen from the comparison of Eqs. (1)
and (2), coefficient VHe is constant only in a low range
of adsorptive activity starting from zero.
If exponential distribution of the adsorbent active
sites with respect to the adsorption heat is assumed, it
is possible to derive an empirical adsorption isotherm
(Freundlich, 1932):
va,Fr = VFr xkFr
where va,Fr /(cm3 g−1 ) is the adsorbed amount calcu-
lated according to the Freundlich adsorption isotherm,
VFr /(cm3 g−1 ) the maximum adsorption capacity, and
kFr a coefficient.
Maximum adsorption capacity VFr is usually posi-
tive and generally not an integer. Despite the fact that
Freundlich isotherm, Eq. (3), lacks the required linear
behavior in the Henry’s law region, data on heteroge-
neous adsorbents over a wide range of the adsorptive
concentrations can be correlated successfully (LeVan
et al., 1997).
The Temkin isotherm, firstly introduced as a foot-
note in the paper of Frumkin and Shlygin (1935),
considers a linear decrease in the binding energies
adsorbate–adsorbent, which leads to the equation:
RT
va,Tem = ln(ATem x)
bTem
where va,Tem /(cm3 g−1 ) is the adsorbed amount
calculated according to the Temkin isotherm, R
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(= 8.314 J K−1 mol−1 ) represents the universal gas
constant, T/K the absolute temperature, bTem a coef-
ficient, and ATem the Temkin binding coefficient.
Langmuir, Freundlich, and Temkin isotherms give
a very simplified idea of the adsorption mechanism.
More realistic is the Dubinin–Radushkevich (DR)
isotherm model that is based on the assumptions
(Lecloux, 1981) that:
– the Polanyi potential expresses the surface work-
ing function (Somorjai, 1994);
– the adsorption proceeds only in micropores (type
(1)
I adsorption model, Fig. 1).


va,DR = VDR exp −D [ln(x)]2 for x > 0 (5)
where va,DR /(cm3 g−1 ) is the adsorbed amount
calculated according to the Dubinin–Radushkevich
isotherm, VDR /(cm3 g−1 ) the maximum adsorption
capacity, and D a coefficient.
The most frequently used models for the descrip-
tions of type II and IV isotherms are BET isotherms,
whereas the assumptions are:
– adsorption sites form a regular array on the ad-
sorbent surface and the adsorption enthalpy (∆Hads )
for the first monolayer is constant;
– no interaction between the neighboring adsorbed
molecules (adsorbate);
– adsorption of the second and next layers is not
limited;
– formation of the second and next layers proceeds
with the same enthalpy as that of liquefaction, (∆Hliq )
Vm,N x CN
va,BET = (6)
(1 − x) 1 + (CN − 1)x
 
E1 − EL
(3) CN = exp (7)
RT
where va,BET /(cm3 g−1 ) is the adsorbed amount
calculated according to the BET isotherm, Vm,N /
(cm3 g−1 ) is the monolayer adsorption capacity,
E1 /(J mol−1 ) the activation energy for the adsorption
in the first layer, and EL /(J mol−1 ) is the activation
energy for the adsorption in the second and next lay-
ers.
Activation energies E1 and EL are considered to be
proportional to the enthalpy of condensation (∆Hads )
and liquefaction (∆Hliq ).
In case of micropores (type I isotherms), there
are generally three possibilities of employing the BET
model:
– Concept of the volume of micropores, M-BET,
being filled firstly and then multilayer BET adsorption
continues (Schneider, 1995; Hudec, 2012)
(4)
va,M-BET = VM-BET + va,BET (8)
where va,M-BET /(cm3 g−1 ) is the adsorbed amount
calculated according to the M-BET isotherm and
1628 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
Vm,BET /(cm3 g−1 ) the volume of micropores filled be-
fore the start of the BET type adsorption.
– Utilization of standard isotherms (Lecloux, 1981;
Hudec, 2012). The most commonly applied is the
equation of Harkins and Jurra (1944):
 0.5
13.99 x ∈ (0.05, 0.5)
tHJ = 0.1
log(x) + 0.034 t < 1 nm
where tHJ /nm is the average (statistical) thickness of
the adsorbate layer on the surface.
Lecloux (1981) introduced a more general isotherm
reflecting the difference between the adsorption
strength (enthalpy) of the first and the next layers
expressed by constant CN in Eq. (7). However, this
type of generalized isotherm is not used frequently in
practice.
– Linear combination of DR and BET isotherms:
va,DR−BET = va,DR + va,BET
Both Eqs. (8) and (10) have physical meaning but
the volumes of micropores differ. Horniakova et al.
(2001) and Kralik et al. (2008) showed that the volume
of micropores assessed by Eq. (8) is lower than that
obtained from Eq. (10). Due to the simpler concept of
the physical meaning, the Schneider modification (Eq.
(8)) is more advised (Schneider, 1995).
Surprisingly, for the description of microporous ad-
sorbents, the n-layer BET isotherm showed good in-
terpretation of experimental data (Horniakova et al.,
2001; Kralik et al., 2008).
Vm,nL CnL x 1 − (n + 1)xn + nx(n+1)
va,nL-BET =
(1 − x) 1 − x + CnL x(1 − xn )
(11)
where va,nL-BET /(cm3 g−1 ) is the adsorbed amount
calculated according to the n-layer BET isotherm, CnL
the constant for the n-layer adsorption, and n the max-
imum number of adsorbate layers (statistically, it can
have a non-integer positive value).
Besides the BET isotherm with micropores and the
n-layer BET isotherm, all others mentioned above are
usually applied in their linearized form. Estimation of
relevant parameters is commonly obtained by treat-
ing data with a standard SW built in apparatus for
adsorption–desorption data measurement. It is wor-
thy to stress that a non-linear treatment of data pro-
vides more reliable information. Fig. 2 shows a com-
parison of experimental data for a microporous mate-
rial (mordenite type zeolite with the Si/Al modulus
equal to 78) and calculated values obtained using dif-
ferent isotherms. As it can be seen, just the n-layer
BET isotherm was proved to be the best one for such
a description.
Another frequently appearing mistake is the inter-
pretation of results using the linearized form of the
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(9)
Fig. 2. Experimental adsorption isotherm (1) and various
model isotherms; parameters estimated using non-
linearized forms and non-linear regression: BET (2),
modified BET isotherm, considering micropores (3),
(10) combination of BET and Dubinin–Radushkevich iso-
therms (4), – n-layer BET isotherm (n = 1.4) (5). Fur-
ther details can be found in the paper by Horniakova
et al. (2001).
BET isotherm to treat experimental data for micro-
porous materials possessing a negative value of the
C-BET constant. As implied from Eq. (7), this con-
stant cannot be negative and such a situation indicates
a strong non-suitability of the multilayer BET model
(Hudec, 2012).
Employment of the n-layer isotherm for microp-
orous materials is also recommended by Rothenberg
(2008).
Effect of the condensation in meso- and macrop-
ores is used for the calculation of characteristic dimen-
sions of these pores using the modified Kelvin equation
(Lecloux, 1981; Hudec, 2012):
bK
rP = + tliq,M (12)
ln (1/x)
where rP /nm is the radius of a pore and bK is a con-
stant.
For nitrogen, as the adsorptive, the thickness of
the monolayer is tliq,M = tliq,N2 = 0.354 nm. Barrett
et al. (1951) extended this method by introducing a
different thickness of the monolayer adsorbate to Eq.
(12). This is called the BJH method and belongs to
the standard procedure of isotherm data treatment.
Lecloux (1981) applied the Broeckhoff and de
Boer’s approach (modified Kelvin equation) based on
adsorption thermodynamics. In spite of the signif-
icantly wider characterization of porous adsorbents
compared to the simple Eq. (12), this procedure is
not frequently applied as it requires very precise ex-
perimental data, and it is not commonly included in
the software of standard adsorption equipments.
 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
Databases of measured isotherms and power of
computers allow using methods of statistical me-
chanics. Adsorptive–adsorbent (G–S) and adsorbate–
adsorbent (L–S) interaction phenomena at a given
temperature and pressure are able to describe pore
size distribution and pore geometry. Such models
allow calculating density profiles and the adsorbed
amount can be derived. Obtained results are “cali-
brated” against real isotherm data of non-porous ma-
terials (Jagiello & Thommes, 2004).
There are many other modifications of adsorption
models described in detail by LeVan et al. (1997)
and Wisniak (2010). A good comparison of the ap-
plicability of individual isotherms including statistical
evaluation has been performed by Foo and Hameed
(2008). D˛abrowski (2001) in his broad review (640
references) discusses the history and suitability of in-
dividual isotherms, as well as their applicability for
the solution of practical adsorption problems and rela-
tionships with heterogeneous catalysis. From the cat-
alytic point of view it is necessary to distinguish be-
tween models used for the description of solid catalytic
materials and models suitable for the description of
a catalytic reaction. For the latter, exclusively the
Langmuir approach is applied. Accessibility of adsorp-
tion/catalytic sites can be increased by the increase of
macropores radius (rP > 25 nm), which is character-
ized more precisely by other methods than the adsorp-
tion/desorption isotherms. The most common is mer-
cury porosimetry, which allows distinguishing pores
with the radius of 1.6 nm at pressures up to 400 MPa
(Hudec, 2012). Of course, mechanical strength of the
material has to be sufficient to ensure no breakage
under such pressures. Microscopic techniques are also
useful in the characterization of macropores (Lecloux,
1981).
A good assessment of methods for the character-
ization of microporous solid materials can be found
in the book by Che and Vedrin (2012), chapter pre-
pared by Llewellyn et al. (2012). Besides the adsorp-
tion methods, evaluation of micropores and meso-
pores using combination of results obtained by Den-
sity Functional Theory and Gas Chromatographic
Mass Spectroscopy measurements (DFT/GCMS) with
subsequent isotherm reconstruction have proved to
be useful for research as well as technological pur-
poses. Dynamic features of adsorption are also dis-
cussed, whereas Pulsed Field Gradient Nuclear Mag-
netic Resonance (PFG NMR), Quasi-Elastic Neutron
Scattering, Zero Length Column (ZLC), and Optical
Impedance Spectroscopy (OIS, observations of probe
molecules by IR) are outlined.
Gas (vapor) phase adsorption
The gas (vapor) phase adsorption is usually a mul-
tilayer process. Depending on the adsorbent proper-
ties (mainly microporosity), the adsorbent–adsorbate
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1629
interaction and process conditions (temperature, pres-
sure, activity of the adsorptive), at least one of the
isotherm models listed above is suitable for the de-
scription.
Sorption of linear alkanes on molecular sieves was
measured by Bobok et al. (1970a), whereas a pre-
cise apparatus set up was found to be crucial for ob-
taining proper data. Due to the low rate of calcula-
tion devices in the past, analogue models were used
to simulate process dynamics (Ilavsky et al., 1970).
Besides reliable experimental techniques, an optimal
plan of experiments also contributes to gaining good
adsorption data (Bobok et al., 1982). Kossaczký and
Bobok (1974) described a numerical solution of dif-
fusion and adsorption of pentane inside a particle of
a molecular sieve Calsit 5A. Adiabatic equilibrium
desorption of carbon dioxide from molecular sieves
(fixed bed Calsit 5A) by a nitrogen stream can be
considered as a continuation of this work (Kossaczký
et al., 1979; Bobok et al. 1979). For the description
of the adsorption equilibrium, these authors used the
modified Henry’s relationship. Bobok et al. (1970b)
showed non-suitability of the Langmuir isotherm, as
well as that the Dubinin assumptions that the den-
sity of the adsorbed phase does not change with the
temperature is only a rough approximation for the
system comprising the pentane–molecular sieve Cal-
sit A. They suggested a modification by transform-
ing equilibrium data to another value of temperature,
different than that at which the isotherms were mea-
sured.
Bobok et al. (1975) applied the actual form of the
Freundlich isotherm for the description of equilibrium
data of the heptanes adsorption on molecular sieve
Calsit 5A.
Chovancová et al. (1986) studied the adsorption
dynamics of ethyl acetate, butyl alcohol, toluene,
and vapors of industrial solvents on activated car-
bon, whereas the breakthrough curves served as a ba-
sis for the design of industrial adsorbers. Kossaczký
et al. (1986) described nonisothermal adsorption of
carbon dioxide on the molecular sieve Calsit 5 by
a system of partial differential equations for mass
and heat balance. The partial differential equations
were transformed into ordinary differential equations
(ODE) applying reverse difference instead of deriva-
tion with respect to length. The fourth order Runge–
Kutta method was applied for the solution of the ob-
tained ODE. Estimation of heat and mass transport
parameters by experimental data fitting allowed de-
signing an adsorber system.
Dynamics of adsorption and values of the Knudsen
diffusion coefficients for heptane in a molecular sieve
NaY particle were estimated by Bobok et al. (1989). A
very simple linear model was applied for the descrip-
tion of the adsorption equilibrium, partial differential
equations expressing flow and adsorption phenomena
in a packed column and the transport in a particle
1630 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
were replaced by relationships emerging from momen-
tum analysis.
Besedová and Bobok (1995) and Besedová et al.
(2004) analyzed competitive adsorption of cumene
and acetone on activated carbon. Equilibrium of the
adsorption was expressed by isothermal and non-
isothermal Langmuir models considering one or two
types of adsorption centers; the latter proved to be
more accurate. Solution of ecological problems, as well
as demonstration of adsorption of non-polar adsorp-
tive on non-polar adsorbents were reported by Bobok
and Besedová (2001), who investigated the diffusion
of chlorinated hydrocarbons in particles of activated
carbon. The same research group (Bobok et al., 2004)
developed a corrected diffusion model involving pores
filling for the adsorption of ethanol vapors on acti-
vated carbon.
Demands on the calculation extent describing the
adsorption dynamics can be significantly decreased us-
ing efficient approximations; e.g. Rajniak et al. (1982)
and Rajniak (1985) analyzed one-component sorp-
tion in a single adsorbent particle considering linear-
driving-force approximation. The one-point colloca-
tion method proved to be very successful for the cal-
culation of adsorbate diffusion.
Desorption from a porous material can be more re-
alistically described by models based on the percola-
tion theory than by the simple Kelvin equation. In de-
rived models, adsorption–desorption hysteresis is as-
cribed to blocking of liquid adsorptive discharge from
larger pores by precedential emptying of smaller pores
surrounding the larger ones (Rajniak & Yang, 1993,
1996, Rajniak et al., 1999, Šoóš & Rajniak, 2001).
Generally it is considered that adsorption is not
connected with strong adsorbate–adsorbent interac-
tions. However, another general statement can be
added: that molecules (adsorptive) of a nature similar
to that of the adsorbent are adsorbed preferentially
in comparison with those of not similar nature. Thus
non-polar substances, e.g. hydrocarbons, are better
adsorbed on non-polar activated carbon, and polar
substances, e.g. amines, are better adsorbed on sil-
ica gel and zeolites. Probably the most relevant in-
dustrial example is Pressure Swing Adsorption (PSA).
Chemisorption of more polar CO2 is stronger on the
surface of an acidic form of zeolite (including entire
micropores) than on non-polar H2 . When pressure is
decreased, H2 is released firstly but CO2 only when
a further decrease in the overall pressure is achieved
(Ruthven, 1984; Chang et al., 2004).
Liquid phase adsorption
As mentioned above, the liquid phase adsorption
is a typical monolayer process (LeVan et al., 1997).
Therefore, suitable models for its description are the
Langmuir, Freundlich, and Henry models, but also
the Temkin and BET models are preferred. Báleš
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et al. (1983) studied adsorption equilibria of phe-
nol, p-cresol, and p-nitroaniline on activated carbon
in aqueous solutions using the Henry and Langmuir
isotherms. Langmuir modification for a binary mix-
ture gave a very good description of simultaneous ad-
sorption of p-cresol and p-nitroaniline.
Liquid phase adsorption is widely applied mainly
for “cleaning”, removing of non-desired species from a
mixture of components. A brief review of wastewater
treatment processes is offered by Grassi et al. (2012),
who described individual adsorbents (activated car-
bon, clays, minerals, low cost adsorbents) and their
capability to treat wastewaters with emerging pollu-
tants.
Adsorption (ion-exchange) equilibrium using ion
exchange materials is a specific problem (LeVan et
al., 1997). A nice example of the isolation of noble
metals from the spent ceramic automotive catalysts
is given by Shen et al. (2010). Besides the descrip-
tion of the equilibrium (Rh(III) chloride complexes
with the anionic exchange resin Diaion WA21J), these
authors also presented a simplified kinetic model for
the adsorption process. Dada et al. (2012) investi-
gated the sorption of Zn2+ on phosphoric acid modi-
fied rice husk and compared the application of Lang-
muir, Freundlich, Temkin, and Dubinin–Radushkevich
isotherms for the equilibrium description. In accor-
dance with the assumption of one layer adsorption
from the liquid phase, the Langmuir isotherm exhib-
ited the best description of the studied process; the
coefficient of determination (R2 ) reached the value of
0.99. Melo et al. (2013) studied adsorption equilibria of
Cu2+ , Zn2+ , and Cd2+ on EDTA-functionalized silica
spheres, which can be considered as a functionalized
adsorbent. Similarly to the previous authors, the best
results were obtained by fitting with the Langmuir
isotherm model, and, again, it fully corresponded with
the availability of adsorption centers for one layer.
Chemisorption
Similarities and differences between adsorp-
tion and chemisorption
Differences between adsorption and chemisorption
are listed in Table 1. It is worthy to stress that despite
similarities of a chemical compound and an adsorbate–
adsorbent complex, in the majority of chemisorption
processes, adsorbate–adsorbent bonds are significantly
weaker than those in typical chemical compounds. As
discussed bellow in the theory on catalysis, there is an
optimal strength of chemisorption (“the volcano curve
theory”) for a proper course of the catalytic process.
Catalysis
Catalysis is a phenomenon in which a substance
(catalyst) enhances the rate of a chemical reaction
 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014) 1631
Table 1. Differences between physisorption and chemisorption

Property Physical adsorption Chemisorption

Type of bonding forces Van der Wals Similar to a chemical bond

Adsorption heat Low, 10–40 kJ mol−1 High, 20–400 kJ mol−1

Chemical change of adsorptive None Formation of a surface compound

Reversibility Fully reversible, i.e. desorption of ad- The process is irreversible; “desorbed
sorbate occurs by decreasing the activ- compounds” are different from the ad-
ity of the adsorptive in the fluid sur- sorbed ones
rounding the surface

Activation energy Very low (close to zero) High, similar to a chemical reaction

Effect of temperature Negative In some extent of temperatures posi-

tive; so called activated adsorption

Specificity of adsorbate–adsorbent Very low High

interactions

Formation of multilayers Yes, in gas phase adsorption usually No

accompanied by liquefaction in micro-
and mesopores

whereas the substance itself is not consumed during

the reaction (Ostwald, 1896). Historically (Berkman
et al., 1940; Rothenberg, 2008), three groups of cat-
alytic systems are distinguished:
– homogeneous, i.e. reaction components and cat-
alytic moieties are in the same phase, for example hy-
drolysis of esters by mineral acids;
– heterogeneous, i.e. reaction components and cat-
alytic moieties are in different phases; the most com-
mon are reactants in gas or liquid and catalysts in
solid phase, e.g. synthesis of ammonia from nitrogen
and hydrogen over iron catalysts;
– biocatalysis or enzymatic catalysis.
To these, the next two groups should be added:
– heterogenized catalysis, i.e. a catalytically active
moiety is anchored to the surface or molecule, e.g. ion-
ized liquid of the second phase; a typical example is the
acid based catalysis performed by anionically modified
polymers (Rothenberg, 2008);
– electrocatalysis, i.e. employing some mechanisms
which contribute to the rate of half-cell reactions on
electrode surfaces (Koper, 2009).
In accordance with the adsorption and chemisorp-
tion phenomena, the following parts of this paper are
devoted mainly to heterogeneous catalysis.
Chemisorption and catalysis
Heterogeneous catalysis with solid catalysts is con-
nected with adsorption and mainly chemisorption di-
rectly or indirectly involved in all classical concepts of
catalysis (Schwab, 1981):
Fig. 3. Dependence of the reaction rate on the strength of
adsorption, the so called volcano plot introduced by
Sabatier. Dissociative adsorption as a rate determin-
ing step increases with the concentration of reactants,
the rate equation of positive order. Desorption as the
rate limiting step reveals the negative order of the rate
equation (van Santen, 2010).
– active centers, i.e. points on a catalyst surface at
which at least one of the reactants is chemisorbed;
– intermediate compounds formed as a result of the
interaction of reactants with active centers;
– complexes and clusters as a form of intermedi-
ates formed on catalytic centers, usually polynuclear,
more than one atom of a catalytic center is involved
in the interaction with the substrate; this concept is
also the basis for the quantum mechanical treatment
of chemisorption;
– multiplet hypothesis and geometric factor, i.e.
arrangement of active centers has to lead to proper
chemisorption of reactants, e.g. benzene parallel che-
misorbed on (111) faces of transition metals;
– volcano curve (Fig. 3), i.e. the strength of

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1632 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
Table 2. Activation of methane on different metals and surfaces (van Santen, 2010)
Metal and surface configuration Ea /(kJ mol−1 )
Ru (0001) 76
Ru (1120) 56
Rh (111) 67
Rh step 32
Rh kink 20
Pd (111) 66
Pd step 38
Pd kink 41
chemisorption has to be sufficient to modify electronic
structure of the substrate but not too strong to be
close to the compound formed by the catalytic center;
this is characterized by the dependence of the reaction
rate on the chemisorption heat;
– band theory, introduced by Schwab in 1940; ei-
ther an electron from the reactant enters the catalytic
center (usually a defect on a metal crystal) or electrons
can be donated by a reactant to the catalytic centers;
this theory was in 1951 extended also for semiconduc-
tors.
However, the acceptance of chemisorption as a
key factor in heterogeneous catalysis was not simple
(Robertson, 1983). The Faraday’s paper introducing
the adsorption theory to the Royal Society in 1834
was discussed for a long time and a final proof of its
validity was demonstrated by Langmuir in 1906. Af-
terwards, chemisorption as a key factor in heteroge-
neous catalysis was generally accepted.
Similarly to the classification of reactions to i)
acid–base, ii) redox, and iii) coordination, the cata-
lysts can be distinguished in the same way. A typical
example of solid acid catalysts are zeolites, which are
used either with a neutral component, support, as a
pure acid (e.g. for cracking in petrochemistry), or in
combination with other catalytic substances like tran-
sition metals as multifunctional catalysts in hydroc-
racking (Satterfield, 1980).
Catalysis by transition metals has its peculiar fea-
tures which have attracted attention of researchers
from the very beginning (Berkman et al., 1947). Tran-
sition metals are used as catalytic substances for oxi-
dation, reduction, and combined, e.g. reductive alky-
lation, processes. A very important feature of tran-
sition metals as catalysts is the occupation of elec-
tron orbitals, especially d-orbitals. Pauling (1949) in-
troduced the so called d-character parameter, which
is directly related to the chemisorption and catalytic
activity. Electrons from d-orbitals are easily movable
(transition metals are good conductors) and they can
interact with the adsorbate. Similarly, electrons from
the adsorbate can interact (enter) with the d-orbitals
of transition metals (Somorjai, 1994). As reported in
Table 2, strength and extent of chemisorption on the
metal surface depends on the type of the metal and
on the defects on the metal surface. Metal crystal-
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d-character/% (Bond, 1957)
50
50
50
50
50
46
46
46
Fig. 4. Reaction coordinates for non-catalyzed (the red curve)
and catalyzed (the purple curve) reactions. Red and
green curves describe situation without consideration of
reaction intermediates. Transition states are indicated
by the sign ‡, * indicates a catalytic site.
lites imperfections as kinks and steps are the most
reactive catalytic sites. However, from the deactiva-
tion point of view, these sites are mostly attacked by
reaction components. Smaller particles (with higher
surface concentration of catalytic sites) are less sta-
ble than the bigger ones. Therefore, for technological
purposes, a compromise between the catalytic activity
and stability has to be considered.
Kinetics and mass transport phenomena
A modern concept of the reaction kinetics descrip-
tion was introduced by Eyring (1935) and by Evans
and Polanyi (1935). This concept is based on the
assumption that reactants form an activated com-
plex which is subsequently transformed to products
(Fig. 4). The theory of activated complexes can be
extended to homogeneous as well as to heterogeneous
catalytic processes.
Let us consider a bimolecular reaction:
k+
A+B −−
←−−−−
−→
− R+S (13)
k−
If both reactants are chemisorbed on the catalysts
surface (species A* and B*), then a reaction between
 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
these chemisorbed species proceeds. For simplicity,
chemisorption of reactants (species A* and B*) is sup-
posed to proceed simultaneously and after the chem-
ical products (R* and S*) are released by desorption
from the catalytic sites simultaneously. Energies of the
chemisorbed species are lower than those of the non-
chemisorbed ones. Chemisorption of species A* and
B* proceeds via an activated chemisorbed complex
(BA*)‡ which is subsequently transformed to the acti-
vated chemisorbed complex of products (RS*)‡ . This
chemisorbed complex is split to chemisorbed species
R* and S* and finally, products are desorbed from
the surface.
Two types of kinetic models are considered for het-
erogeneous catalytic processes (Berkman et al., 1940;
Hougen & Watson, 1947; Thomas & Thomas, 1997;
Satterfield, 1980): i) empirical and ii) mechanistic.
The majority of empirical models is based on a
power law model. For a reaction of nR reactants, the
forward reaction can be written as:

nR
ξ˙V = kcat acat abi
i (14)
i=1
where ξ˙V /(mol m−3 s−1 ) is the reaction rate, kcat the
rate constant (units depend on the number of reac-
tants and stoichiometry), acat the activity of cata-
lyst, usually expressed as mass concentration units
(g m−3 ), ai the activity of reactant i, often expressed
in molar concentration units (mol m−3 ), and bi is the
C
C
stoichiometric coefficient for reactant i.
In practice, activities ai are also expressed as par-
tial pressures (pi ). The reaction rate can be also re-
lated to a unit mass of the catalyst or to the spe-
cific surface of the catalyst (Satterfield, 1980; Murzin
& Salmi, 2005). An example of the power law appli-
cation for the description of 4-aminodiphenyl amine
reduction alkylation with acetone and hydrogen was
presented by Králik et al. (1990).
If the content of the catalyst expressed as a mass
concentration is considered, the reaction rate of the
reversible reaction is described by the relationship:
ξ˙V = wcat (k+ cA cB − k− cR cS )
where wcat /(g m−3 ) is the mass concentration of cat-
alyst, k+ /(m6 g−1 s−1 mol−1 ) and k− /(m6 g−1 s−1
mol−1 ) are the rate constants for the direct and back
reactions, respectively, and ci /(mol m−3 ) is the molar
concentration of component i.
Evidently, the power law model, which can be de-
rived from the mass action and/or activation com-
plex theories, is not realistic for a surface reaction.
A pioneer work on the heterogeneous catalytic reac-
tions was presented by Hougen and Watson (1947),
who used the Langmuir monolayer adsorption model
(see Eq. (1)) and either a surface reaction of two
chemisorbed species or a reaction of the chemisorbed
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1633
moiety and a component from the fluid surround-
ing the heterogeneous catalyst. This type of models
is generally denoted as the Langmuir–Hinshelwood–
Hougen–Watson (LHHW) models. Essential assump-
tions for the LHHW models are as follows:
– all catalytic centers are of the same quality;
– chemisorption on catalytic sites does not change
the properties (energy) of the surrounding catalytic
sites;
– reaction consists of three elemental steps:
a. chemisorption;
b. surface reaction;
c. desorption of products;
– one of these steps is rate determining, others are
in equilibrium;
– reaction occurs either between chemisorbed
species or one component is chemisorbed and the other
one comes from the fluid;
– activity close to the surface is equal to that in
the fluid (in the interior of a porous catalyst).
If the reactants are chemisorbed on active sites of
different quality and the product and inert chemisorp-
tion are considered, Eq. (16) emerges:
ξ˙V,i = kcat,i wcat
C
N  
(K1,j aj )b1,j + (K2,j aj )b2,j
j=1
νij <0
d 1 d2
N
N
1+ (K1,j aj )b1,j 1+ (K2,j aj )b2,j
j=1 j=1
for i = 1, 2, . . . , NR ; j = 1, 2, . . . , NC (16)
where Kj,i are the adsorption constants, ν ij are the
stoichiometric coefficients for the reaction i and com-
ponent j, NR and NC correspond to the number of
reactions and components, respectively, and bk,j , d1 ,
and d2 are the coefficients in Eq. (16). The condition
ν ij < 0 in product terms indicates that only activities
of reactants entering the i-th reaction should appear
in the kinetic term.
Values of exponents for the activities of individual
(15) components are affected by the chemisorption process,
e.g. for non-dissociative regime the value of 1, for the
dissociative regime 0.5. Denominator exponents the-
oretically depend on the number of catalytic centers
taking part in the rate determining step of the reac-
tion; for a bimolecular surface reaction, the value of 2
is used.
Eq. (16) is rather complicated and moreover, the
estimation of individual parameters usually does not
provide a non-biased determination of the model type.
For example, Hougen and Watson (1947) reported
on the treatment of data obtained from isooctene
hydrogenation. They tested 16 models and realized
that four of them gave comparable quality of descrip-
tion.
1634 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)

Fig. 5. Individual steps in the heterogeneous catalytic G–L–S process.

When mass transport phenomena affect the rate

of the process, it is necessary to include these effects
into the data treatment. However, even with rather
sophisticated models (Biffis et al., 1996; Králik et al.,
1998), a unique and fully reliable description might
not be possible to find. In such situations, the best
way is to simplify Eq. (16) considering the strength of
the adsorption without or with dissociation in order to
get a minimum number of parameters. Thus, in case of
cyclohexene hydrogenation to cyclohexane over a resin
based palladium catalyst, Eq. (16) has been simplified
to (Biffis et al., 1996):
cbH
H2 cen
2

ξ˙V = kcat cPd  d (17)

1 + KH2 cbH
H2
2

A general picture of the G–L–S system (Fig. 5)

depicts the transport of reaction components based
on the film theory (Levenspiel, 1999):
– from G- to bulk of the L-phase (G–L transport);
– to the surface of a solid catalyst (L–S transport);
– inside a catalytic particle (diffusion).
Of course, for G–S and L–S systems the model is
simplified by excluding one phase transport step.
Levenspiel (2002) discusses rather complicated
models, which may not be reliable due to a number
of parameters and are difficult to be implemented in
practice. Anyway, a proper physical/chemical concept
of the processes running in the system is better than a
simplified “black box” approach. A complex descrip-
tion of the catalytic kinetics and effects of mass trans-
port phenomena can be found in the textbooks by
Murzin and Salmi (2005) or Vannice (2005). In con-
text with mass and heat transport phenomena and the
optimization of the location of catalytic substances,
the book by Morbidelli et al. (2005) is rather use-
ful.
Fig. 6. Illustration of physico-chemical techniques used for the
characterization of solid materials (Che and Vedrine
(2012), adapted from: cover of the series Studies in Sur-
face Science and Catalysis, Elsevier).
Characterization of solid catalysts and cat-
alytic systems
Besides the characterization of catalysts as “ad-
sorbents”, there are many classical and modern meth-
ods providing details of catalytic processes. Fig. 6 il-
lustrates the important features of various techniques
(Che & Vedrine, 2012).
The simplest experimental technique for chemi-
sorption identification is to carry out temperature
programmed desorption similarly to the acidity de-
termination (Satterfield, 1980; Thomas & Thomas,
1997). In Fig. 6, the surface is affected by aminic

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 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
species (neutral charge), which are bound to acidic
sites and after achieving an equilibrium they are re-
leased from the surface by heat. Magnetic field is
applied in NMR techniques, and photon beams are
used for visible and infrared spectroscopy (FTIR).
For example, Scholtzová et al. (2013) studied the
effect of the tetramethylammonium cation (TMA+ )
intercalated onto montmorrilonite (a useful adsor-
bent and, after activation with a mineral acid,
also an important solid acid catalyst) using mea-
sured FTIR spectra and calculated data based on
the Density Functional Theory (DFT). Both exper-
imental and calculated data showed that fixation of
the TMA+ cation in the interlayer space consist in
weak hydrogen bonds between the methyl groups
and the basal oxygen atoms of montmorillonite lay-
ers.
Characterization of chemisorbed species by High
Resolution Electron Energy Loss Spectroscopy
(HREELS) and Extended X-ray Absorption Fine
Structure (EXAFS) are also powerful techniques.
More comprehensive description of these methods can
be found in papers by Somorjai (1994) and those for
IR in McKelvy et al. (1998). The list of methods has
been given by Che and Vedrine (2012) and their very
detailed descriptions are provided in chapters of this
book.
A combination of IR and NMR techniques was pre-
sented by Hinedi et al. (1993). Balakrishnan et al.
(1990) studied chemisorption by FTIR of bimetallic
Pt–Au/SiO2 catalysts using H2 , O2 , and CO as adsor-
bates at room temperature. Somorjai (1994) published
a number of data concerning chemisorption on sur-
faces, e.g. vibration spectra and structure of methyli-
dene, acetylide, benzene, and organometalic struc-
tures. Evidently, chemisorbed species interact with
the adsorbent atoms close to chemical compounds,
but the binding energy between adsorbate and sur-
face atoms of adsorbent/catalyst is weaker. A brief
review of techniques used for the characterization of
solid catalysts and chemisorption is published in the
book by Rothenberg (2008). An interesting study by
Belskaya et al. (2012) reports on the analysis of ad-
sorbed probe molecules to determine the surface prop-
erties of supported Pt (Pd) catalysts. Infrared (IR)
intensities as determined by a combination of tem-
perature dependent IR spectroscopy and Temperature
Programmed Desorption (TPD) were used to iden-
tify the adsorption sites on Co and Co–Pd nanopar-
ticles by Risse et al. (2003). It was shown that CO
adsorption on metal atoms with low metal coordi-
nation leads to strong intensity enhancement of the
IR absorption as compared to regular surface sites.
Density Functional Theory (DFT) calculations show
that this intensity enhancement is due to the decou-
pling of the low coordinated metal atom bound to
CO from metal atoms embedded in the metal sur-
face.
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1635
Based on calorimetric measurements, Peter et al.
(2013) reported on the changes of the adsorption
strength on palladium particles with various sizes. For
O2 chemisorption, they found maximum adsorption
initiation energy on particles with the size of about
4 nm (particles of lower and higher dimensions were
less active) and for CO chemisorption, the highest ad-
sorption initiation energy was determined on the Pd
(111) surface.
Molecular modeling and catalysis
Availability of computers with high calculation
speed has provided possibilities of molecular model-
ing. These models can describe adsorption, chemisorp-
tion, as well as catalytic processes (Rothenberg, 2008;
Bell & Head-Gordon, 2011; Sautet, 2012). Two main
groups of methods are applied: i) classical mechanics
(CM) and ii) quantum mechanics (QM). QM meth-
ods are more precise but as they are based on the
Schrödinger’s equation (Schrödinger, 1926), they are
much more complicated and further simplifications are
applied (e.g. the Hartree–Fock approach with exact so-
lution of wave integrals, so called ab initio methods,
or with some pre-solved values of integrals).
For a higher number of entities, the Density Func-
tional Theory (DFT) can be employed. This method
uses the electronic density as the basic quantity in-
stead of a many-body electronic wave function. Its
main advantage is that the density is a function of
only three variables (instead of 3n variables) and thus
it is easier to deal with both in theory and in practice.
An interesting alternative combining the advantages
of both classical and quantum mechanics is to use hy-
brid QM/MM models.
Probably the most famous and useful application
of QM in practice is the analysis of individual steps
in ammonia synthesis (Grunze et al., 1978; Ertl, 1990,
2008). The maximum activation energy of only about
40 kJ mol−1 is required for the chemisorptive disso-
ciation of N2 and H2 , surface reaction and desorp-
tion of the formed NH3 while the formation of N +
3H requires the activation energy of 1129 kJ mol−1 .
The obtained results inspired many researchers to em-
ploy the QM approach for the description of cat-
alytic processes, elementary catalytic steps on the sur-
face, as well as characterization of catalytic surface by
chemisorption and QM calculations (Huang & Carter,
2008; Zaera, 2013; Berland & Hyldgaard, 2013; Far-
berow et al., 2013; Hu et al., 2013; Jiang et al., 2013;
Keil, 2013; Klappenberger, 2014).
He et al. (2014) and Lyu et al. (2014) analyzed
chemisorption of chlorinated nitrobenzenes (CNB) on
palladium nanoparticles. Their experiments and theo-
retical quantum chemical evaluation allowed explain-
ing the selectivity in the hydrogenation of CNB. Ex-
planation of the differences of these values was also
supported by the observations of Kratky et al. (2002).
1636 M. Králik/Chemical Papers 68 (12) 1625–1638 (2014)
Conclusions
A modern approach to heterogeneous catalytic
phenomena is fully based on the analysis and mod-
eling of electronic properties of reaction components
and their interactions with the solid catalyst. Various
characterization techniques are employed for the eval-
uation of the strength of chemisorbed species, whereas
the IR techniques are the most frequently applied.
Taking into the account adsorption (chemisorption)
as a key process, mechanistic models based on rate
determining steps are the most useful. A full descrip-
tion of a catalytic process involves the description of
mass and heat transfer phenomena. From the practical
point of view, effects of these factors on the deactiva-
tion of catalysts have to be considered; the most active
catalyst is usually not the best for technological pur-
poses. Thus, description of adsorption/chemisorption
properties of the catalyst and analysis of the suggested
reactor arrangement are unavoidable for the design of
a suitable catalyst. Despite the abundance of infor-
mation on the validity of calculations, catalytic ex-
periments remain the starting and final bases for the
development of models as well as for the design of cat-
alytic processes. Naturally, proper theoretical analysis
and combinatorial chemistry (for example: Huang and
Carter (2008)) can significantly reduce the number of
experiments and confirm the reliability of the obtained
data.
Acknowledgements. This publication is a result of the
project implementation: “Hydrogenation in the liquid phase”,
ITMS: 26220220144, supported by the Research & Develop-
ment Operational Programme funded by the ERDF. The author
thanks Maria Turakova for the help with manuscript finaliza-
tion.
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