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Advance Nuclear Chemistry
Advance Nuclear Chemistry

Rudra Narayan Sharma

CENTRUM PRESS
NEW DELHI-110002 (INDIA)
CENTRUM PRESS
H.O.: 4360/4, Ansari Road, Daryaganj,
New Delhi-110002 (India)
Tel: 23278000, 23261597, 23255577, 23286875
Email: centrumpress@gmail.com
Visit us at: www.centrumpress.com

Advance Nuclear Chemistry

© Reserved

First Edition, 2017

ISBN 978-93-5084-887-6

PRINTED IN INDIA
Printed at Replika Press Pvt. Ltd., Sonipat, Haryana
Contents

Preface
1. Molecular Bonding in Nuclear Atoms
2. Modern Atomic Theory in Chemistry
3. Chemical Elements of Atom
4. Quantized Nature of Electrons in Atom
5. Nature of Electrons in Atom
6. Electron Configuration in Atomic Orbitals
7. Ionizing Radiation: Sources and Effects
8. Wave-Particle Duality
Bibliography
Preface

Nuclear chemistry is the study of the chemical and physical properties of elements as
influenced by changes in the structure of the atomic nucleus. Modern nuclear chemistry,
sometimes referred to as radiochemistry, has become very interdisciplinary in its
applications, ranging from the study of the formation of the elements in the universe to the
design of radioactive drugs for diagnostic medicine. In fact, the chemical techniques
pioneered by nuclear chemists have become so important that biologists, geologists, and
physicists use nuclear chemistry as ordinary tools of their disciplines. While the common
perception is that nuclear chemistry involves only the study of radioactive nuclei, advances in
modern mass spectrometry instrumentation has made chemical studies using stable,
nonradioactive isotopes increasingly important. There are essentially three sources of
radioactive elements. Primordial nuclides are radioactive elements whose half-lives are
comparable to the age of our solar system and were present at the formation of Earth. These
nuclides are generally referred to as naturally occurring radioactivity and are derived from
the radioactive decay of thorium and uranium. Cosmogenic nuclides are atoms that are
constantly being synthesized from the bombardment of planetary surfaces by cosmic particles
(primarily protons ejected from the Sun), and are also considered natural in their origin. The
third source of radioactive nuclides is termed anthropogenic and results from human activity
in the production of nuclear power, nuclear weapons, or through the use of particle
accelerators.
Some methods first developed within nuclear chemistry and physics have become so
widely used within chemistry and other physical sciences that they may be best thought of as
separate from normal nuclear chemistry. For example, the isotope effect is used so
extensively to investigate chemical mechanisms and the use of cosmogenic isotopes and long-
lived unstable isotopes in geology that it is best to consider much of isotopic chemistry as
separate from nuclear chemistry. Another important area of nuclear chemistry is the study of
how fission products interact with surfaces; this is thought to control the rate of release and
migration of fission products both from waste containers under normal conditions and from
power reactors under accident conditions. It is interesting to note that, like chromate and
molybdate, the 99TcO4 anion can react with steel surfaces to form a corrosion resistant layer.
NMR spectroscopy uses the net spin of nuclei in a substance upon energy absorption to
identify molecules. This has now become a standard spectroscopic tool within synthetic
chemistry. One major use of NMR is to determine the bond connectivity within an organic
molecule. NMR imaging also uses the net spin of nuclei (commonly protons) for imaging.
This is widely used for diagnostic purposes in medicine, and can provide detailed images of
the inside of a person without inflicting any radiation upon them. In a medical setting, NMR is
often known simply as “magnetic resonance” imaging, as the word ‘nuclear’ has negative
connotations for many people.
The present book covers all of the chemical aspects of nuclear science starting from the
physical basics and including such diverse areas as the chemistry of transactinides and exotic
atoms as well as radioactive waste management and radiopharmaceutical chemistry relevant
to nuclear medicine. The will be a valuable resource guide for nuclear scientists, biologists,
chemists, physicists, physicians practicing nuclear medicine, graduate students and teachers
involved in the chemical and radiopharmaceutical aspects of nuclear science.

— Rudra Narayan Sharma

 Chapter 1: Molecular Bonding in Nuclear Atoms

Chemical Bond
You probably learned some time ago that chemical bonds are what hold atoms together to
form the more complicated aggregates that we know as molecules and extended solids.
Chemists talk about bonds all the time, and draw pictures of them as lines joining atom
symbols. Teachers often identify them as the little sticks that connect the spheres that represent
atoms in a plastic molecular model. So it’s not surprising that we sometimes tend to think of
chemical bonds as “things”. But no one has ever seen a chemical bond, and there is no reason
to believe that they really even exist as physical objects.
“Sometimes It Seems to me that a bond between two atoms has become so real,
so tangible, so friendly, that I can almost see it. Then I awake with a little
shock, for a chemical bond is not a real thing. It does not exist. No one has
ever seen one. No one ever can. It is a figment of our own imagination.”
C.A. Coulson (1910-1974) was an English theoretical chemist who played a central role
in the development of quantum theories of chemical bonding.
It is more useful to regard a chemical bond as an effect that causes certain atoms to join
together to form enduring structures that have unique physical and chemical properties. So
although the “chemical bond” is no more than a convenient fiction, chemical bonding, which
leads to the near-infinity of substances (31 million in mid-2007), lies at the very core of
chemistry.
The forces that hold bonded atoms together are basically just the same kinds of
electrostatic attractions that bind the electrons of an atom to its positively-charged nucleus.
This is the most important fact about chemical bonding that you should know, but it is not of
itself a workable theory of bonding because it does not describe the conditions under which
bonding occurs, nor does it make useful predictions about the properties of the bonded atoms.
Our views of what constitutes chemical bonding are still evolving, according to a 2007
article in Chemical and Engineering News (85 37-40). This “buckyball-and-mitt”
synthesized in 2007 by Andrzej Sygula is a case in point. The buckyball C60 resides in the
C60H28 “buckybowl”. There are no traditional “chemical bonds” here!

Molecule
A more restrictive definition distinguishes between a “true” molecule that exists as an
independent particle, and an extended solid that can only be represented by its simplest
formula. Methane, CH4, is an example of the former, while sodium chloride, which does not
contain any discrete NaCl units, is the most widely-known extended solid. But because we
want to look at chemical bonding in the most general way, we will avoid making this
distinction here except in a few special cases. In order to emphasize this “aggregate of atoms”
definition, we will often use terms such as “chemical species” and “structures” in place of
“molecules” in this lesson.
 The definition written above is an operational one; that is, it depends on our ability to
observe and measure the molecule’s properties. Clearly, this means that the molecule must
retain its identity for a period of time long enough to carry out the measurements. For most of
the molecules that chemistry deals with, this presents no difficulty. But it does happen that
some structures that we can write formulas for, such as He2, have such brief lives that no
significant properties have been observed. So to some extent, what we consider to be a
molecule depends on the technology we use to observe them, and this will necessarily change
with time.
Structure
And what are those properties that characterize a particular kind of molecule and
distinguish it from others? Just as real estate is judged by “location, location, location”, the
identity of a chemical species is defined by its structure. In its most fundamental sense, the
structure of a molecule is specified by the identity of its constituent atoms and the sequence in
which they are joined together, that is, by the bonding connectivity. This, in turn, defines the
bonding geometry— the spatial relationship between the bonded atoms.
The importance of bonding connectivity is nicely illustrated by the structures of the two
compounds ethanol and dimethyl ether, both of which have the simplest formula C2H6O. The
structural formulas reveal the very different connectivities of these two molecules whose
physical and chemistry properties are quite different:

Structures Without Molecules: Stability and Reactivity

The precise definition of bonding energy is described in another lesson and is not
important here. For the moment you only need to know that in any stable structure, the
potential energy of its atoms is lower than that of the individual isolated atoms. Thus the
formation of methane from its gaseous atoms (a reaction that cannot be observed under
ordinary conditions but for which the energetics are known from indirect evidence)
4 H(g) + C(g) → CH4
is accompanied by the release of heat, and is thus an exothermic process. The quantity of heat
released is related to the stability of the molecule. The smaller the amount of energy released,
the more easily can the molecule absorb thermal energy from the environment, driving the
above reaction in reverse and leading to the molecule’s decomposition.
A highly stable molecule such as methane must be subjected to temperatures of more than
1000°C for significant decomposition to occur. But the noble-gas molecule KrF2 is so weakly
bound that it decomposes even at 0°C, and the structure He2 has never been observed. If a
particular arrangement of atoms is too unstable to reveal its properties at any achievable
temperature, then it does not qualify to be called a molecule.
There are many molecules that are energetically stable enough to meet the above
criterion, but are so reactive that their lifetimes are too brief to make their observation
possible. The molecule CH3, methyl, is a good example: it can be formed by electrical
discharge in gaseous CH4, but it is so reactive that it combines with almost any molecule it
strikes (even another CH3)within a few collisions.
It was not until the development of spectroscopic methods (in which a molecule is
characterized by the wavelengths of light that it absorbs or emits) that methyl was recognized
as a stable albeit shamelessly promiscuous molecule that is an important intermediate in many
chemical processes ranging from flames to atmospheric chemistry.

Chemical Structures

Chemical species are traditionally represented by structural formulas such as the one
for ascorbic acid (vitamin C) which we show here. The lines, of course, represent the
“chemical bonds” of the molecule. More importantly, the structural formula of a molecule
defines its connectivity, as was illustrated in the comparison of ethanol and dimethyl ether
shown above.
One limitation of such formulas is that they are drawn on a two-dimensional paper or
screen, whereas most molecules have a three-dimensional shape. The wedge-shaped lines in
the structural formula are one way of indicating which bonds extend above or below the
viewing plane. You will probably be spared having to learn this convention until you get into
second-year Chemistry.
But what would a molecule “really” look like if you could view it through a magical
microscope of some kind? A possible answer would be this computer-generated view of
nicotine. At first you might think it looks more like a piece of abstract sculpture than a
molecule, but it does reveal the shape of the negative charge-cloud that envelops the
collection of atom cores and nuclei hidden within. This can be very important for
understanding how the molecule interacts with the similar charge-clouds that clothe solvent
and bioreceptor molecules.
The purpose of rendering a molecular structure in a particular way is not to achieve
“realism” (whatever that might be), but rather to convey useful information of some kind.
Modern computer rendering software takes its basic data from various kinds of standard
structural databases which are compiled either from experimental X-ray scattering data, or
are calculated from theory.
As was mentioned above, it is often desirable to show the “molecular surface”— the veil
of negative charge that originates in the valence electrons of the atoms but which tends to be
spread over the entire molecule to a distance that can significantly affect van der Waals
interactions with neighboring molecules. It is often helpful to superimpose images
representing the atoms within the molecule, scaled to their average covalent radii, and to
draw the “bonding lines” expressing their connectivity.
Knowing the properties of molecular surfaces is vitally important to understanding any
process that depends on one molecule remaining in physical contact with another. Catalysis is
one example, but one of the main interests at the present time is biological signalling, in
which a relatively small molecule binds to or “docks” with a receptor site on a much larger
one, often a protein. Sophisticated molecular modelling software such as was used to produce
these images is now a major tool in many areas of research biology.
Visualizing very large molecules such as carbohydrates and proteins that may contain
tens of thousands of atoms presents obvious problems. The usual technique is to simplify the
major parts of the molecule, representing major kinds of extended structural units by shapes
such as ribbons or tubes which are twisted or bent to approximate their conformations. These
are then gathered to reveal the geometrical relations of the various units within the overall
structure. Individual atoms, if shown at all, are restricted to those of special interest.
Some of these images can stand as artistic creations in their own right. This seems to be
especially true of those that render special aspects of molecular surfaces; the two on the left
below could well be mistaken for paintings by Jean Mirο and Salvador Dalí, respectively.
Study of the surface properties of large molecules is crucial for understanding how
proteins, carbohydrates, and DNA interact with smaller molcules, especially those involved
in transport of ions and small molecule across cell membranes, immune-system behavior, and
signal transduction processes such as the “turning on” of genes.

Observable Properties of Bonded Atom Pairs

When we talk about the properties of a particular chemical bond, we are really
discussing the relationship between two adjacent atoms that are part of the molecule.
Diatomic molecules are of course the easiest to study, and the information we derive from
them helps us interpret various kinds of experiments we carry out on more complicated
molecules.
It is important to bear in mind that the exact properties of a specific kind of bond will be
determined in part by the nature of the other bonds in the molecule; thus the energy and length
of the C– H bond will be somewhat dependent on what other atoms are connected to the
carbon atom. Similarly, the C-H bond length can vary by as much a 4 percent between
different molecules. For this reason, the values listed in tables of bond energy and bond
length are usually averages taken over a variety of compounds that contain a specific atom
pair.
In some cases, such as C—O and C—C, the variations can be much greater, approaching
20 percent. In these cases, the values fall into groups which we interpret as representative of
single- and multiple bonds: double, and triple.
Potential Energy Curves
The energy of a system of two atoms depends on the distance between them. At large
distances the energy is zero, meaning “no interaction”. At distances of several atomic
diameters attractive forces dominate, whereas at very close approaches the force is
repulsive, causing the energy to rise. The attractive and repulsive effects are balanced at the
minimum point in the curve. Plots that illustrate this relationship are known as Morse curves,
and they are quite useful in defining certain properties of a chemical bond.
The internuclear distance at which the potential energy minimum occurs defines the bond
length. This is more correctly known as the equilibrium bond length, because thermal motion
causes the two atoms to vibrate about this distance. In general, the stronger the bond, the
smaller will be the bond length.
Attractive forces operate between all atoms, but unless the potential energy minimum is
at least of the order of RT, the two atoms will not be able to withstand the disruptive
influence of thermal energy long enough to result in an identifiable molecule. Thus we can say
that a chemical bond exists between the two atoms in H2. The weak attraction between argon
atoms does not allow Ar2 to exist as a molecule, but it does give rise to the van Der Waals
force that holds argon atoms together in its liquid and solid forms.
Potential energy and kinetic energy Quantum theory tells us that an electron in an atom
possesses kinetic energy K as well as potential energy P, so the total energy E is always the
sum of the two: E = P + K. The relation between them is surprisingly simple: K = –0.5 P.
This means that when a chemical bond forms (an exothermic process with ΔE <0), the
decrease in potential energy is accompanied by an increase in the kinetic energy (embodied in
the momentum of the bonding electrons), but the magnitude of the latter change is only half as
much, so the change in potential energy always dominates. The bond energy – ΔE has half the
magnitude of the fall in potential energy.

Bond Energies
The bond energy is the amount of work that must be done to pull two atoms completely
apart; in other words, it is the same as the depth of the “well” in the potential energy curve
shown above. This is almost, but not quite the same as the bond dissociation energy actually
required to break the chemical bond; the difference is the very small zero-point energy. This
relationship will be clarified below in the section on bond vibrational frequencies.
How Bond Energies are Measured
Bond energies are usually determined indirectly from thermodynamic data, but there are
two main experimental ways of measuring them directly: The direct thermochemical
methodinvolves separating the two atoms by an electrical discharge or some other means, and
then measuring the heat given off when they recombine. Thus the energy of the C—C single
bond can be estimated from the heat of the recombination reaction between methyl radicals,
yielding ethane:
CH3 + CH3 → H3C–CH3
Although this method is simple in principle, it is not easy to carry out experimentally.
The highly reactive components must be prepared in high purity and in a stream of moving
gas.
The spectroscopic methodis based on the principle that absorption of light whose
wavelength corresponds to the bond energy will often lead to the breaking of the bond and
dissociation of the molecule. For some bonds, this light falls into the green and blue regions
of the spectrum, but for most bonds ultraviolet light is required. The experiment is carried out
by observing the absorption of light by the substance being studied as the wavelength is
decreased. When the wavelength is sufficiently small to break the bond, a characteristic
change in the absorption pattern is observed. Spectroscopy is quite easily carried out and can
yield highly precise results, but this method is only applicable to a relatively small number of
simple molecules.
The major problem is that the light must first be absorbed by the molecule, and relatively
few molecules happen to absorb light of a wavelength that corresponds to a bond energy.
Experiments carried out on diatomic molecules such as O2 and CS yield unambiguous values
of bond energy, but for more complex molecules there are complications.
For example, the heat given off in the CH3 combination reaction written above will also
include a small component that represents the differences in the energies of the C-H bonds in
methyl and in ethane. These can be corrected for by experimental data on reactions such as:
CH3 + H → CH4
CH2 + H → CH3
By assembling a large amount of experimental information of this kind, a consistent set of
average bond energies can be obtained. The energies of double bonds are greater than those
of single bonds, and those of triple bonds are higher still.
Use of Bond Energies in Estimating Heats of Reaction
One can often get a very good idea of how much heat will be absorbed or given off in a
reaction by simply finding the difference in the total bond energies contained in the reactants
and products. The strength of an individual bond such as O–H depends to some extent on its
environment in a molecule (that is, in this example, on what other atom is connected to the
oxygen atom), but tables of “average” energies of the various common bond types are widely
available and can provide useful estimates of the quantity of heat absorbed or released in
many chemical reaction.
As an example, consider the reaction of chlorine with methane to produce
dichloromethane and hydrogen chloride:
CH4(g) + 2 Cl2(g) → CH2Cl2(g) + 2 HCl(g)
In this reaction, two C–H bonds and two Cl–Cl bonds are broken, and two new C–H and
H–Cl bonds are formed. The net change associated with the reaction is 2(C–H) + 2(Cl–Cl) –
2(C–Cl) – 2(H–Cl) = (830 + 486 -660-864) kJ which comes to –208 kJ per mole of methane;
this agrees quite well with the observed heat of reaction, which is – 202 kJ/mol.
Bond Lengths and Angles
Bond lengths are affected by the sizes of the atoms; thus those involving hydrogen can be
quite short. The shortest bond of all, H– H, is only 74 pm. Multiply-bonded atoms are closer
together than singly-bonded ones; this is a major criterion for experimentally determining the
multiplicity of a bond.
Bond lengths depend mainly on the sizes of the atoms, and secondarily on the bond
strengths, the stronger bonds tending to be shorter. Bonds involving hydrogen can be quite
short; The shortest bond of all, H–H, is only 74 pm. Multiply-bonded atoms are closer
together than singly-bonded ones; this is a major criterion for experimentally determining the
multiplicity of a bond. This trend is clearly evident in the above plot which depicts the
sequence of carbon-carbon single, double, and triple bonds.
The most common method of measuring bond lengths in solids is by analysis of the
diffraction or scattering of X-rays when they pass through the regularly-spaced atoms in the
crystal. For gaseous molecules, neutron- or electron-diffraction can also be used.
The complete structure of a molecule requires a specification of the coordinates of each
of its atoms in three-dimensional space. This data can then be used by computer programs to
construct visualizations of the molecule as discussed above. One such visualization of the
water molecule, with bond distances and the HOH bond angle superimposed on a space-
filling model, is shown here. (It is taken from an excellent reference source on water). The
colors show the results of calculations that depict the way in which electron charge is
distributed around the three nuclei.

Bond Stretching and Infrared Absorption

When an atom is displaced from its equilibrium position in a molecule, it is subject to a
restoring force which increases with the displacement. A spring follows the same law
(Hooke’s law); a chemical bond is therefore formally similar to a spring that has weights
(atoms) attached to its two ends. A mechanical system of this kind possesses a natural
vibrational frequency which depends on the masses of the weights and the stiffness of the
spring. These vibrations are initiated by the thermal energy of the surroundings; chemically-
bonded atoms are never at rest at temperatures above absolute zero.
On the atomic scale in which all motions are quantized, a vibrating system can possess a
series of vibrational frequencies, or states. These are depicted by the horizontal lines in the
potential energy curve shown here. Notice that the very bottom of the curve does not
correspond to an allowed state because at this point the positions of the atoms are precisely
specified, which would violate the uncertainty principle.
The lowest-allowed, or ground vibrational state is the one denoted by 0, and it is
normally the only state that is significantly populated in most molecules at room temperature.
In order to jump to a higher state, the molecule must absorb a photon whose energy is equal to
the distance between the two states.
For ordinary chemical bonds, the energy differences between these natural vibrational
frequencies correspond to those of infrared light. Each wavelength of infrared light that
excites the vibrational motion of a particular bond will be absorbed by the molecule. In
general, the stronger the bond and the lighter the atoms it connects, the higher will be its
natural stretching frequency and the shorter the wavelength of light absorbed by it. Studies on
a wide variety of molecules have made it possible to determine the wavelengths absorbed by
each kind of bond.
Actual infrared spectra are complicated by the presence of more complex motions
(stretches involving more than two atoms, wagging, etc.), and absorption to higher quantum
states (overtones), so infrared spectra can become quite complex. This is not necessarily a
disadvantage, however, because such spectra can serve as a “fingerprint” that is unique to a
particular molecule and can be helpful in identifying it. Largely for this reason, infrared
spectrometers are standard equipment in most chemistry laboratories.
Infrared Absorption and Global Warming
The aspect of bond stretching and bending frequencies that impacts our lives most
directly is the way that some of the gases of the atmosphere absorb infrared light and thus
affect the heat balance of the Earth. Owing to their symmetrical shapes, the principal
atmospheric components N2 and O2 do not absorb infrared light, but the minor components
water vapour and carbon dioxide are strong absorbers, especially in the long-wavelength
region of the infrared. Absorption of infrared light by a gas causes its temperature to rise, so
any source of infrared light will tend to warm the atmosphere; this phenomenon is known as
the greenhouse effect.
The incoming radiation from the Sun (which contains relatively little long-wave infrared
light) passes freely through the atmosphere and is absorbed by the Earth’s surface, warming it
up and causing it to re-emit some of this energy as long-wavelength infrared. Most of the
latter is absorbed by the H2O and CO2, the major greenhouse gasis in the unpolluted
atmosphere, effectively trapping the radiation as heat. Thus the atmosphere is heated by the
Earth, rather than by direct sunlight. Without the “greenhouse gases” in the atmosphere, the
Earth’s heat would be radiated away into space, and our planet would be too cold for life.
Radiation balance of the Earth In order to maintain a constant average temperature, the
quantity of radiation (sunlight) absorbed by the surface must be exactly balanced by the
quantity of long-wavelength infrared emitted by the surface and atmosphere and radiated back
into space. Atmospheric gases that absorb this infrared light (depicted in red on the right part
of this diagram) partially block this emission and become warmer, raising the Earth’s
temperature.
Since the beginning of the Industrial Revolution in the 19th century, huge quantities of
additional greenhouse gases have been accumulating in the atmosphere. Carbon dioxide from
fossil fuel combustion has been the principal source, but intensive agriculture also contributes
significant quantities of methane (CH4) and nitrous oxide (N2O) which are also efficient far-
infrared absorbers. The measurable increase in these gases is believed by many to be
responsible for the increase in the average temperature of the Earth that has been noted over
the past 50 years— a trend that could initiate widespread flooding and other disasters if it
continues.

Molecular Orbital Theory

Modern chemistry has depended upon the use of models of increasing comlexity. Atoms
can be represented as spheres connected by cyclinders or sticks. In order to understand the
mechanism of many reactions, Lewis Theory, developed by Robinson and Ingold, can provide
a succesful answer.
Lewis Theory uses curly arrows to denote electron migration during a chemical reaction
and has led to a greater understanding of the factors controlling chemical reactions. Pauling
with others, developed Resonance Theory, which provided the rationale to an all-embracing
orbital theory.
The use of “canonical forms” and “resonance hybrids”, alonng with extensive use of
curvy arrows has provided the fundamental background to modern organic theory, but for e.g.
Diels-Alder and pericyclic reactions, the curly arrow format is not very clear and in some
instances the reactions are described as no-machanism reactions. Woodward and Hoffmann
showed that by examining the interaction of the frontier molecular orbitals (i.e. the Highest
Occupied, HOMO and Lowest Unoccupied, LUMO) both the regio- and stereospecificity
could be accountred for.
Woodward and Hoffmann work was assimilated into general organic reaction theory.

Atomic and Molecular Orbitals

By sharing electron, molecules can form bonds, and it is possible to regard the sharing of
two electrons by two atoms as constituting a chemical bond. Atoms can share one, two or
three electrons (forming single, double and triple bonds).
A hydrogen atom consists of a nucleus (a proton) and an electron. It is not possible to
accurately determine the position of the electron, but it is possible to calculate the probability
of finding the electron at any point around the nucleus. With a hydrogen atom the probability
distribution is spherical around the nucleus and it is possible to draw a spherical boundary
surface, inside which there is a 95% possibility of finding the electron.
The electron has a fixed energy and a fixed spatial distribution called an orbital. In the
helium atom there are two electrons associated with the helium nucleus. The electrons have
the same spatial distribution and energy (i.e. they occupy the same orbital), but they differ in
their spin (Pauli exlusion principle). In general: electrons in atomic nuclei occupy orbitals of
fixed energy and spatial distribution, and each orbital only contains a maximum of two
electrons with anti-parallel spins.
In physics, periodic phenomena are associated with a “wave equation”, and in atomic
theory the relevant equation is called the “Schrödinger Equation”. The wave equation
predicts discrete solutions in one dimension for a particle confined to a box with infinite
walls. y1-y4 represent solutions of increasing energy. In three dimensions, the equation
determines the energy and defines the spatial distribution of each electron. Solutions of the
wave equations in three-dimensions allows calculation of the “shape” of each orbital. The
first five solutions of the wave equation for an electron associated with a proton
In the hydrogen atom, the 1s atomic orbital has the lowest energy, while the remainder
(2s, 2px, 2py and 2pz) are of equal energy (ie.degenerate), but for all other atoms, the 2s
atomic orbital is of lower energy than the 2px, 2py and 2pz orbitals, which are degenerate.
In atoms, electrons occupy atomic orbitals, but in molecules they occupy similar
molecular orbitals which surround the molecule. The simplest molecule is hydrogen, which
can be considered to be made up of two separate protons and electrons. There are two
molecular orbitals for hydrogen, the lower energy orbital has its greater electron density
between the two nuclei. This is the bonding molecular orbital-and is of lower energy than the
two 1s atomic orbitals of hydrogen atoms making this orbital more stable than two separated
atomic hydrogen orbitals.
The upper molecular orbital has a node in the electronic wave function and the electron
density is low between the two positively charged nuclei. The energy of the upper orbital is
greater than that of the 1s atomic orbital, and such an orbital is called an antibonding
molecular orbital. Normally, the two electrons in hydrogen occupy the bonding molecular
orbital, with anti-parallel spins. If molecular hydrogen is irradiated by ultraviolet (UV) light,
the molecule may absorb the energy, and promote one electron into its antibonding orbital
(σ*), and the atoms will separate. The energy levels in a hydrogen molecule can be
represented in a diagram-showing how the two 1s atomic orbitals combine to form two
molecular orbitals, one bonding (σ) and one antibonding (σ*).
Orbitals for Selected Molecules
This section illustrates pictorially molecular orbitals for several organic and inorganic
molecules. If possible-the energy level diagram is included and clicking upon the relevant
level will generate the accompanying molecular orbital in the right-hand frame. Please
choose from:
• Saturated molecules
• Molecules with double bonds
• Molecules with triple bonds
• Molecules with electron lone pairs
• Conjugated and aromatic molecules
• Other interesting molecules.
Saturated Molecules
These are molecules in which all valence electrons are involved in the formation of
single bonds. There are no non-bonded lone pairs. These molecules are generally less
reactive than either electron-rich or electron-deficient species, with all occupied orbitals
having relatively low energies.
Methane: The valence molecular orbitals of methane are delocalized over the entire
nuclear skeleton-that is, it is not easy to assign any one orbital to a particular C-H bond. It is
possible to see how complex the orbital structure becomes with the increase in energy.
Methane has four valence molecular orbitals (bonding), consisting of one orbital with one
nodal plane (lowest occupied) and three degenerate (equal energy) orbitals that do have a
nodal plane.
Ethane: The ethane molecule has fourteen valence electrons occupying seven bonding
molecular orbitals. As can be seen from the energy diagram-four of the molecular orbitals
occur as degenerate pairs. Like in methane-the molecular orbitals of ethane show increasing
nodal structure with increasing orbital energy.
Molecules with Double Bonds
In molecules where the number of bonding electron pairs exceeds the number of unions
between atoms, the extra electrons occupy higher energy molecular orbitals than the orbitals
found in molecules where the number of bonding electron pairs equals the number of unions
between atoms. These are double bonds, and the orbitals have a nodal plane containing the
atoms sharing these p-type orbitals.
Ethene: The simplest alkene is ethene. Its chemistry is dominated by two “frontier
orbitals”, that is the Highest Occupied Molecular Orbital (HOMO) and the Lowest
Unoccupied Molecular Orbital (LUMO). For the ethene orbital energy diagram these are
shown as pCC for the HOMO, and p*CC for the LUMO.
An important property of the ethene molecule, and alkenes in general is the existence of a
high barrier to rotation about the C=C which tends to hold the molecule flat.
Molecules with Electron Ione Pairs
 Hydrogen Fluoride: A simple diatomic molecule is Hydrogen fluoride. There are eight
valence electrons which occupy four molecular orbitals. The two highest energy MO’s are
degenerate, are p-type and have no electron density associated with the hydrogen atom, ie.
they are Non-Bonding Orbitals (NBO) and in Lewis Theory are represented as two “Lone
Pairs”. Another important difference between Hydrogen Fluoride and previous molecules is
that the electron density is not equally distributed about the molecule. There is a much greater
electron density around the fluorine atom. This is because fluorine is an extremely
electronegative element, and in each bonding molecular orbital, fluorine will take a greater
share of the electron density.
Water: In the water molecule the highest occupied orbital, (1b1) is nonbinding and highly
localized on the oxygen atom, similar to the nonbinding orbitals of hydrogen fluoride. The
next lowest orbital (2a1) can be thought of as a nonbinding orbital, as it has a lobe pointing
away from the two hydrogens. From the lower energy bonding orbitals, it is possible to see
that oxygen also takes more than its “fair share” of the total electron density.
Ammonia: Ammonia has two pairs of degenerate orbitals, one bonding and one
antibonding, and like hydrogen fluoride and water has a nonbinding orbital (2a1). This highest
occupied orbital has a lobe pointing away from the three hydrogens, and corresponds to a
lone pair orbital localized upon the nitrogen, whereas the three lowest energy MO’s lead to
the description of the three N-H bonds of the Lewis structure. The lone pair is relatively high
in energy, and is responsible for the well known Lewis base properties of ammonia.
Conjugated and Aromatic Molecules
π bonds in close proximity will often interact. Some of the delocalized molecular
orbitals that result will be stabilized, while others will be destabilized. The individual
combinations may be polarized, providing an increase in wave function amplitude on some
centers at the expense of a decrease in amplitude on others. This gives rise to the possibility
of more varied reactivity patterns than are observed for simple alkenes.
Aromatic molecules exhibit a wide range of reactivity patterns toward both electron rich
and electron deficient species. These mainly depend on the structures and energies of the
frontier π-type molecular orbitals, the HOMO and LUMO. Except for non-bonded lone pairs,
the σ framework plays little role in the overall reactivity.
Trans-1,3-Butadiene: The energies of the p-molecular orbitals of conjugated molecules
like butadiene - occur in pairs, with their energies equal to (α ± xβ), where a and b are
constants. For each bonding orbital of and energy a-xb there is a corresponding antibonding
orbital of energy α + xβ. The p-molecular orbitals are extended over the whole molecule.
Cyclopentadiene: This molecule is a relatively acidic hydrocarbon, and the anion is
formed by the treatment of cyclopentadiene with a strong base. From the cyclic polyene
diagram it can be seen that cyclopentadiene has three p bonding orbitals which are
delocalised over the five carbon atoms. The uppermost % bonding orbitals are a degenerate
pair, and are the highest occupied molecular orbitals (HOMO’s).
Benzene: Benzene is the archetypal aromatic compound. It has a symmetrical p system
and so is not over reactive on any one site. From the cyclic polyene diagram it can be seen
that benzene has six p-molecular orbitals, (which contain the six ^-electrons), three bonding
and three anti-bonding.
 The upper bonding degenerate pair of orbitals are the HOMO’s of benzene. The p orbital
manifold, but also of interest is that the pattern of the π orbitals is repeated within the σ
system. The σ functions - like the π orbitals are delocalized throughout the carbon skeleton.
Bonding in Benzene: From the above diagram it can be seen that the lowest lying
orbital, %1, the orbital coefficients are such that the bonding character between each pair of
adjacent carbon atoms is equal. In π2 bonding only occurs between atoms C2 and C3 and
between C5 and C6 since the coefficients on C1 and C4 are zero. In %3, C1, which is bonded
to C2 and C6 and C4 is bonded to C3 and C5, there are anti-bonding interactions between C2
and C3 and between C5 and C6.
Therefore if we consider the pair of orbitals π2 and π3 the contribution to the C-C π
bonding is equal for each bond. Since there are three occupied bonding orbitals and six CC
linkages - the π bond order is ½.

Solid-state Chemistry
Solid-state chemistry is the study of the synthesis, structure, and physical properties of
solid materials. It therefore has a strong overlap with solid-state physics, mineralogy,
crystallography, ceramics, metallurgy, thermodynamics, materials science and electronics
with a focus on the synthesis of novel materials and their characterization.
History
Because of its direct relevance to products of commerce, solid state inorganic chemistry
has been strongly driven by technology well in advance of atomic-level descriptions or in the
academic studies. Applications discovered in the 20th century include zeolite and platinum-
based catalysts for petroleum processing in the 1950’s, high-purity silicon as a core
component of microelectronic devices in the 1960’s, and “high temperature”
superconductivity in the 1980’s. The invention of X-ray crystallography in the early 1900s by
William Lawrence Bragg enabled further innovation.
Synthetic Methods
Given the diversity of solid state compounds, an equally diverse array of methods are
used for their preparation. For organic materials, such as charge transfer salts, the methods
operate near room temperature and are often similar to the techniques of organic synthesis.
Redox reactions are sometimes conducted by electrocrystallisation, as illustrated by the
preparation of the Bechgaard salts from tetrathiafulvalene.
Oven Techniques
For thermally robust materials, high temperature methods are often employed. For
example, bulk solids are prepared using tube furnaces, which allow reactions to be conducted
up to ca. 1100 °C. Special equipment e.g. ovens consisting of a tantalum tube through which
an electric current is passed can be used for even higher temperatures up to 2000 °C. Such
high temperatures are at times required to induce diffusion of the reactants, but this depends
strongly on the system studied. Some solid state reactions already proceed at temperatures as
low as 100 °C.
Melt Methods
One method often employed is to melt the reactants together and then later anneal the
solidified melt. If volatile reactants are involved the reactants are often put in an ampoule that
is evacuated -often while keeping the reactant mixture cold e.g. by keeping the bottom of the
ampoule in liquid nitrogen- and then sealed. The sealed ampoule is then put in an oven and
given a certain heat treatment.
Solution Methods
It is possible to use solvents to prepare solids by precipitation or by evaporation. At
times the solvent is used hydrothermally, i.e. under pressure at temperatures higher than the
normal boiling point. A variation on this theme is the use of flux methods, where a salt of
relatively low melting point is added to the mixture to act as a high temperature solvent in
which the desired reaction can take place.
Gas Reactions
Many solids react readily with reactive gas species like chlorine, iodine, oxygen etc.
Others form adducts with other gases, e.g. CO or ethylene. Such reactions are often carried
out in a tube that is open ended on both sides and through which the gas is passed. A variation
of this is to let the reaction take place inside a measuring device such as a TGA. In that case
stoechimetric information can be obtained during the reaction, which helps identify the
products.
A special case of a gas reaction is a chemical transport reaction. These are often carried
out in a sealed ampoule to with a small amount of a transport agent, e.g. iodine is added. The
ampoule is then placed in a zone oven. This is essentially two tube ovens attached to each
other which allows a temperature grandient to be imposed. Such a method can be used to
obtain the product in the form of single crystals suitable for structure determination by X-ray
diffraction. Chemical vapour deposition is a high temperature method that is widely
employed for the preparation of coatings and semiconductors from molecular precursors.
Air and Moisture Sensitive Materials
Many solids are hygroscopic and/or oxygen sensitive. Many halides e.g. are very ‘thirsty’
and can only be studied in their anhydrous form if they are handled in a glove box filled with
dry (and/or oxygen-free) gas, usually nitrogen.

Characterization
New Phases, Phase Diagrams, Structures
The synthetic methodology and the characterization of the product often go hand in hand
in the sense that not one but a series of reaction mixtures are prepared and subjected to heat
treatment. The stoichiometry is typically varied in a systematic way to find which
stoichiometries will lead to new solid compounds or to solid solutions between known ones.
A prime method to characterize the reaction products is powder diffraction, because many
solid state reactions will produce polycristalline ingots or powders. Powder diffraction will
facilitate the identification of known phases in the mixture. If a pattern is found that is not
known in the diffraction data libraries an attempt can be made to index the pattern, i.e. to
identify the symmetry and the size of the unit cell. (If the product is not crystalline the
characterization is typically much more difficult.)
Once the unit cell of a new phase is known, the next step is to establish the stoichiometry
of the phase. This can be done in a number of ways. Sometimes the composition of the
original mixture will give a clue, if one finds only one product -a single powder pattern- or if
one was trying to make a phase of a certain composition by analogy to known materials but
this is rare.
Often considerable effort in refining the synthetic methodology is required to obtain a
pure sample of the new material. If it is possible to separate the product from the rest of the
reaction mixture elemental analysis can be used. Another ways involves SEM and the
generation of characteristic X-rays in the electron beam. The easiest way is to solve the
structure is by using single crystal X-ray diffraction.
The latter often requires revisiting and refining the preparative procedures and that is
linked to the question which phases are stable at what composition and what stoichiometry. In
other words what does the phase diagram looks like. An important tool in establishing this is
thermal analysis techniques like DSC or DTA and increasingly also, thanks to the advent of
synchrotrons temperature-dependent power diffraction.
Increased knowledge of the phase relations often leads to further refinement in synthetic
procedures in an iterative way. New phases are thus characterized by their melting points and
their stoichiometric domains. The latter is important for the many solids that are non-
stoichiometric compounds. The cell parameters obtained from XRD are particularly helpful
to characterize the homogeneity ranges of the latter.
Further Characterization
In many -but certainly not all- cases new solid compounds are further characterized by a
variety of techniques that straddle the fine line that (hardly) separates solid-state chemistry
from solid-state physics.
Optical Properties
For nonmetallic materials it is often possible to obtain UV/VIS spectra. In the case of
semiconductors that will give an idea of the band gap.
Electrical Properties
Four-point (or five-point) probe methods are often applied either to ingots, crystals or
pressed pellets to measure resistivity and the size of the Hall-effect. This gives information
on whether the compound is an insulator, semiconductor, semimetal or metal and upon the
type of doping and the mobility in the delocalized bands (if present). Thus important
information is obtained on the chemical bonding in the material.
Magnetic Properties
Magnetic susceptibility can be measured as function of temperature to establish whether
the material is a para-, ferro- or antiferro-magnet. Again the information obtained pertains to
the bonding in the material. This is particularly important for transition metal compounds. In
the case of magnetic order neutron diffraction can be used to determine the magnetic structure.
 Electron Pairs in Solid State Chemistry
Chemists like the concept of electron pairs since the early days of Lewis. Bonding and
nonbonding electron pairs are the basis to argue about shapes of molecules and characteristic
coordinations in solids.
Stabilization of a complex cluster unit by a single multi-centre electron pair-this is, in
condensed form, the essential type of chemical bonding in the recently discovered cluster
compounds ATh12N6X29 (A = Li,...,Rb; X = Cl, Br). While all of them contain a hitherto
unknown cluster type that is built up from twelve metal atoms.
The first one relies on (i) six nitrogen-centered thorium tetrahedra [Th4N] which are
condensed via edges in a cyclic manner, while the second one focuses on (ii) an empty
octahedron of thorium atoms [Th6] that is capped by six additional thorium atoms but leaving
two opposite faces open. The resulting tetrahedral voids are filled by nitrogen atoms. In any
case, this star-shaped cluster is coordinated by a total of 41 halogen atoms in a rather
complex way, furthermore interconnecting the individual cluster units in a variety of different
and complex modes.
The solid state structures of chlorides and bromides exhibit remarkable differences with
respect to both lattice symmetry as well as halide substructure, however, the cluster units
[Th12N6 X41]13-themselves are almost identical. One reason for this finding is already
indicated by a rather primitive electron count for the “ionic limit” according to A+ (Th4+)12
(N3-)6 (X-)29, yielding a surplus of (1+48-18-29=)2 electrons that are available for metal-
metal bonding.
Molecular orbital calculations both confirm and further clarify this description. In
addition to strongly ionic Th-N and Th-(Cl, Br) bonds, there is a significant contribution of
covalent bonding between thorium atoms detectable, and it is associated with an energetically
well-separated highest occupied molecular orbital (HOMO) of a1g symmetry. It is evident that
only 6d atomic orbitals from the central thorium atoms mix strongly into this molecular
orbital, incorporating the two “surplus” electrons and thus stabilizing the entire cluster unit by
the formation of a six-centre two-electron bond. Besides this multi-centre orbital, the
electronic structure of these clusters parallels the pattern found in other nitride halide
compounds with similar tetrahedral arrangements. The cyclic condensation of the tetrahedra
inevitably leads to the formation of this additional orbital (and vice versa), being essential
for the stability of these compounds.
Also, an application of topological counting rules illustrates this finding. Such empirical
rules are surprisingly successful for the description of molecular cluster compounds (and thus
widely used in the chemical literature).
They provide simple formulae to estimate so-called “magic” numbers for optimum
stability of various geometrical fragments. For example, if the central octahedron of the
cluster unit is not explicitly accounted for, e.g. by only counting the edges or formally
decomposing the cluster into tetrahedra, the total electron count is two electrons lower
compared to the description of a capped octahedron. In other words, the recognition of the
central octahedron as the host for multi-centre metal-metal bonding is a prerequisite for an
adequate designation of the chemical bonding in this cluster type.
 Stabilization of a complex halide structure via a Jahn-Teller reduction of an excess
electron pair’s antibonding character—that is, on the other hand, the idea of chemical bonding
inside the newly characterized phase In4Br7.
In4Br7 is a member of the large family of complex indium halides, materials that are
characterized by an astonishing structural variety which may be traced back to the indium
atom’s multi-valency (mono, di-, and trivalent indium) and the possibility to mix these
valencies in varying combinations in the solid state. The more reduced (bromide) phases
deserve special attention since they are all containing In+ cations that show fairly uncommon,
strongly distorted coordination polyhedra (7-12-fold coordination with strongly widened In+-
Br- bond lengths). A naive solid-state chemical interpretation would call for “directed
electron lone-pairs” being responsible for this finding, however, band structure investigations
reveal the cause in a strongly antibonding combination between almost doubly filled, non-
directional indium 5s functions and neighboring bromine 4p hybrids. Any coordination
polyhedron giving sufficient space for In+, aside from repelling bromine-bromine
interactions, is almost equally appropriate.
Because of that antibonding excess electron pair in the indium 5s atomic orbital, the
overall bonding is weak in reduced indium bromides (and halides in general). The resulting
soft crystal potential for In+ is nicely reflected in significantly enlarged displacement factors
in all known crystal structure investigations. Moreover, energy hypersurface calculations for
the In+/Br- combination indicate that the latter one is a very good candidate for a second-
order Jahn-Teller instability.
The last prediction has now been experimentally verified for the case of trigonal In4Br7;
its crystal-chemical formulation may be described as (In3+)3(In+)5(Br-)14 = In8Br14. On the
macroscopic level, In4Br7 exhibits an extraordinarily high sensitivity (and chemical
reactivity), not only when brought into contact with air or humidity but also when subjected to
visible light and mechanical stress, followed by rapid decay.
There are, of course, the overall weak In+-Br- interactions to be accounted for this high
sensitivity; however, band structure calculations reveal that one out of three positions for
monovalent indium, characterized by a 6+6=12-fold coordination by bromine anions, is the
source of an unusual electronic instability, thereby being able to localize In4Br7’s high
reactivity to a good extent from crystallography.
The key to understanding lies in the lowest crystal orbital (LUCO, with almost pure 5px,y
character) that is centered on this particular monovalent indium cation. Because of the
LUCO’s small energetic distance from the occupied band levels, it may mix with the highest
bands (antibonding indium 5s regime) upon atomic displacement, by that reducing the total
energy.
Such an effect, equivalent to a second-order Jahn-Teller distortion, manifests at low
temperature (90 K) from the measured electron density, showing that indium no longer resides
on the crystallographic high-symmetry position but has moved away from it by roughly 40 pm.
Note that classifying this effect by assuming a nonbonding “directed electron lone-pair” is
completely erroneous. On the contrary, the atomic dislocation results from a bonding
contribution that slightly weakens the overall antibonding In+-Br- interactions close to the
Fermi energy.
 Chemical Kinetics
Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical
processes. Chemical kinetics includes investigations of how different experimental conditions
can influence the speed of a chemical reaction and yield information about the reaction’s
mechanism and transition states, as well as the construction of mathematical models that can
describe the characteristics of a chemical reaction.
In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics
by formulating the law of mass action, which states that the speed of a chemical reaction is
proportional to the quantity of the reacting substances.

Rate of Reaction
Chemical kinetics deals with the experimental determination of reaction rates from which
rate laws and rate constants are derived. Relatively simple rate laws exist for zero order
reactions (for which reaction rates are independent of concentration), first order reactions,
and second order reactions, and can be derived for others. In consecutive reactions the rate-
determining step often determines the kinetics. In consecutive first order reactions, a steady
state approximation can simplify the rate law.
The activation energy for a reaction is experimentally determined through the Arrhenius
equation and the Eyring equation. The main factors that influence the reaction rate include: the
physical state of the reactants, the concentrations of the reactants, the temperature at which the
reaction occurs, and whether or not any catalysts are present in the reaction.

Factors Affecting Reaction Rate

Nature of the Reactants
Depending upon what substances are reacting, the time varies. Acid reactions, the
formation of salts, and ion exchange are fast reactions. When covalent bond formation takes
place between the molecules and when large molecules are formed, the reactions tend to be
very slow.
Physical State
The physical state (solid, liquid, or gas) of a reactant is also an important factor of the
rate of change. When reactants are in the same phase, as in aqueous solution, thermal motion
brings them into contact. However, when they are in different phases, the reaction is limited
to the interface between the reactants. Reaction can only occur at their area of contact, in the
case of a liquid and a gas, at the surface of the liquid. Vigorous shaking and stirring may be
needed to bring the reaction to completion.
This means that the more finely divided a solid or liquid reactant, the greater its surface
area per unit volume, and the more contact it makes with the other reactant, thus the faster the
reaction. To make an analogy, for example, when one starts a fire, one uses wood chips and
small branches—one doesn’t start with large logs right away. In organic chemistry On water
reactions are the exception to the rule that homogeneous reactions take place faster than
heterogeneous reactions.
Concentration
Concentration plays a very important role in reactions according to the collision theory
of chemical reactions, because molecules must collide in order to react together. As the
concentration of the reactants increases, the frequency of the molecules colliding increases,
striking each other more frequently by being in closer contact at any given point in time. Think
of two reactants being in a closed container. All the molecules contained within are colliding
constantly. By increasing the amount of one or more of the reactants it causes these collisions
to happen more often, increasing the reaction rate.
Temperature
Temperature usually has a major effect on the rate of a chemical reaction. Molecules at a
higher temperature have more thermal energy. Although collision frequency is greater at
higher temperatures, this alone contributes only a very small proportion to the increase in rate
of reaction. Much more important is the fact that the proportion of reactant molecules with
sufficient energy to react (energy greater than activation energy: E > Ea) is significantly
higher and is explained in detail by the Maxwell–Boltzmann distribution of molecular
energies. The ‘rule of thumb’ that the rate of chemical reactions doubles for every 10° C
temperature rise is a common misconception. This may have been generalized from the
special case of biological systems, where the Q10 (temperature coefficient) is often between
1.5 and 2.5. A reaction’s kinetics can also be studied with a temperature jump approach. This
involves using a sharp rise in temperature and observing the relaxation rate of an equilibrium
process.
A catalyst is a substance that accelerates the rate of a chemical reaction but remains
chemically unchanged afterwards. The catalyst increases rate reaction by providing a
different reaction mechanism to occur with a lower activation energy.
In autocatalysis a reaction product is itself a catalyst for that reaction leading to positive
feedback. Proteins that act as catalysts in biochemical reactions are called enzymes.
Michaelis-Menten kinetics describe the rate of enzyme mediated reactions.
A catalyst does not affect the position of the equilibria, as the catalyst speeds up the
backward and forward reactions equally.
In certain organic molecules specific substituents can have an influence on reaction rate
in neighbouring group participation.
Agitating or mixing a solution will also accelerate the rate of a chemical reaction, as this
gives the particles greater kinetic energy, increasing the number of collisions between
reactants and therefore the possibility of successful collisions.
Pressure
Increasing the pressure in a gaseous reaction will increase the number of collisions
between reactants, increasing the rate of reaction. This is because the activity of a gas is
directly proportional to the partial pressure of the gas. This is similar to the effect of
increasing the concentration of a solution.
Equilibrium
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solicited us. The man remained under the umbrella, and took no
notice. They were “Susmanis,” or gypsies. These people have no
particular religion—certainly they are not Mussulmans; they live by
singing, dancing, and prostitution. The woman, who had
considerable attractions, followed us for nearly a mile, and begged
hard for a present. Sana is always infested by bands of these
“Susmanis,” who prey on the pilgrims.
We are now on the direct pilgrims’ road to Kerbela, where are
buried the imams, or saints, of the Sheahs, Hussein and Hassan,
one of the greatest shrines of Persian pilgrims. More groups of
“Susmanis” accost us, and demand alms, openly proclaiming their
trade.
We reach Sana, and pitch the tent in a large garden with plenty of
running water, where we are able to get a good bath next day. The
climate is here very pleasant; although it is early in spring, the sun is
very powerful, and the night no longer chilly. The greater part of the
afternoon is taken up with a long wrangle with the head-men of the
village as to the price of poles for the telegraph-line. Pierson’s ideas
and theirs differ widely as to the value of these, but a threatened
reference to the Imād-u-dowlet (“Pillar of the State”), the Governor of
Kermanshah, soon reduces the price, for these sharks would much
prefer dealing with the Feringhi than their fellow-countrymen, as the
latter would probably take the poles for nothing.
Another day’s journey brings us to Besitūn, which is distinguished
by an inscription carved on the face of a perpendicular cliff, with
colossal figures, of which a correct and learned description has been
given by Sir Henry Rawlinson. At the foot of this cliff are a few
fragments of what is supposed to have been “Shushan the palace.”
It is said that here, when Sir Henry Rawlinson was engaged in
copying the inscriptions, on a scaffolding on the face of the cliff, at a
great height from the ground, that he fell over backwards, and was
caught by his trusty Arab muleteer, Hadji Khaleel; and that, in
gratitude, Sir Henry, who at that time held a diplomatic position in
Persia, made the Hadji British Agent in Kermanshah. This is the
legend among the natives. I give it as I heard it.
 I had the pleasure of the honest old Hadji’s acquaintance in that
place, and was shown much kindness by him. Whether or no this
legend had any ground I cannot say; but Hadji Khaleel was a
charming old man, honest as the day, though with somewhat rough
manners.
His son, Agha Hassan, who was, at the time I speak of, his right
hand, is now the British Agent, and has become, by successful
commerce, the wealthiest man in the province. Agha Hassan rode
out to meet us, his father, Hadji Khaleel being ill, and Pierson told me
that he recognised and spoke in rapturous terms of my “Senna,” to
whom by this time I had become much attached, and who once had
belonged to him.
An istikhbal of a colonel, his attendants, and two led-horses, were
sent out to do Pierson honour by the Governor; kalians were smoked
on the high road, and we came in sight of Kermanshah after crossing
the Kara-Su River by a fairly well-made bridge.
The place looks well, and appears surrounded by a grassy plain, a
very unusual sight in Persia. The town had an air of prosperity, and
the people were well fed and well clothed. It occupied several small
hills, and hence appeared considerably larger than it was.
Like all Persian towns, the streets were narrow, and, save in the
bazaars, in which were the shops, one saw nothing but dead walls;
each house having an arched entrance closed by a heavy, unpainted
wooden door, with many big nails in it.
The causeway was generally some three feet wide, and raised a
yard from the ground, and frequently ran on both sides of a path a
yard wide and often two feet deep in mud or water, looking like a
ditch, but it was really the road (save the mark!) for horses, mules,
and camels. Many of the houses were built of burnt bricks, and the
place seemed busier than Hamadan. I noticed many Arabs about
wearing the gay Baghdad dress, with fez and small turban. The town
was straggling, with many open spaces.
Quarters were assigned to us in the house of a man who was
ejected to enable us to occupy them; they were not in themselves a
bad place, but were in the worst and most disreputable part of the
town; while the house I was obliged to rent was actually next door
but one to that occupied by the public executioner, one Jaffer, and
where dwelt the public women, the monopoly of whom was the
largest source of this man’s revenue. All this is now changed, and
Europeans can in most parts of Persia live where they like, the
householders being only too glad to get a solvent tenant. Save in the
capital, houses rarely are rented by Persians, it being usual to
borrow a spare house, or, if a man has more than one, to put a
relation in, rent-free.
The farce of the danger of living in the Persian towns is still kept
up in Ispahan (the Ispahanis are the quietest men in Persia), where
the English inhabit an unclean Armenian village, paying high rents,
when houses in the town could be had much better and cheaper; the
real reason probably being that the Armenians may enjoy the
immunity they have from all control, caused by the presence of the
European. But it has not answered, for in Ispahan the European is
looked on as merely a clean and sober Armenian. Still, as an
experiment of what the Armenian would be when practically
unrestrained, it is valuable.
The Hamadan Armenian is hard-working and respectable, if
occasionally a drunkard, looked on by his Persian fellow-subject as a
friend and a good citizen. While the Ispahani looks on the Julfa
Armenian as a race apart, and merely the panderer to his vice and
the maker of intoxicating liquors; and the hang-dog Armenian, with
his sham Turkish or European dress and the bottle of arrack in his
pocket, scowls staggering along in secure insolence, confident in the
moral protection given him by the presence of the Englishman,
whom he robs; respecting neither his priest, whom he has been
taught to despise; nor the missionary, whom he dislikes at heart
(though he has educated his children gratuitously), and whom his
priest openly reviles.
A curious instance of the religious stability of the Julfa Armenian is
shown in the fact, that a Protestant on any dispute with the
missionary becomes Catholic or Old Armenian. The Old Armenian,
after a row with the priest, becomes either Protestant or Catholic.
The Catholics, as a rule, do not relapse or become perverts. In fact,
a common threat with the Armenian to his spiritual pastor and
master, missionary, priest or padre, is to say, “Do it, and I’ll turn,” and
some have many times; in fact, a very small temporal matter often is
the cause of conversions as sudden as insincere.
We were glad enough to get in, and had hardly got our boots off
ere a number of trays of sweetmeats were brought for Pierson, on
the part of Hadji Khaleel, with compliments, and a similar present
was sent from the Imād-u-dowlet, who sent his farrash-bashi (literally
chief carpet-spreader, but really his minister) to represent him. This
man was well bred, well meaning and obliging, and afterwards,
through a singular circumstance, one of my best friends among the
Persians.
I continued to stay with Pierson, not moving into my own quarters
till he left Kermanshah.
 CHAPTER X.
KERMANSHAH.

Kermanshah—Imād-u-dowlet—We visit him—Signs of his wealth—Man nailed to a

post—Injuring the wire—Serrum-u-dowlet—Visits—We dine with the son of
the Governor—His decorations and nightingales—Dancing girls—Various
dances—The belly dance—Heavy dinner—Turf—Wild geese—The swamp—
A ducking through obstinacy—Imādieh—Wealth of the Imād-u-dowlet—The
Shah loots him—Squeezing—Rock sculptures—Astrologers—Astrolabes—
Fortune-telling—Rammals—Detection of thieves—Honesty of servants—
Thefts through pique—My lost pipe-head—Tragedy of two women.

Kermanshah is decidedly the cheapest place in all cheap Persia.

Bread was selling at seven pounds for twopence; mutton, seven
pounds for fourteenpence, or twopence a pound; and other things in
proportion. It costs here threepence a day to keep a horse (1867).
The day after our arrival Pierson went to visit the Imād-u-dowlet,
uncle (?) of the king, and Governor of the province. He is a man of
very large fortune, and is liked as a Governor, being stern, but
generally just, his wealth putting him above any wish to oppress the
little people. We rode to the maidān, or public square, then in under
an archway and up a steep incline, which conducted us to the
interior of the citadel, in which the Imād lived.
As we entered we noticed a man nailed by the ear to a wooden
telegraph post.
The Imād-u-dowlet received Pierson very kindly, and laughed and
joked a great deal. His eldest son, the “Serrum-u-dowlet,” a man of
five-and-thirty, was present; he spoke a little French and was very
friendly and complimentary.
The wealth of the Governor was shown in his coffee-cup holders,
of gold enamelled, and decorated with rows of diamonds; his water-
pipes (kalians) all of gold; and his own special one, the bottle of
which was of gold so thickly encrusted with emeralds that it
appeared like green glass; all the stones were pale, and
consequently of comparatively little value separately.
The Governor in appearance was a man of five-and-forty, with a
heavy black beard and thick moustache; but he was really sixty-five:
this youthful look was due to hair-dye.
He told us that the man who was nailed to the telegraph-post was
a villager who had been detected red-handed in breaking the
telegraph-wire, and that he was to remain thirty-six hours, when he
would be imprisoned. “It is a capital warning to other offenders,” said
the Imād. At this time the line was frequently damaged, several miles
at a time often being pulled down by malicious travellers and
villagers, particularly on the frontier near Kermanshah. Pierson,
however, begged that the man might be removed at sunset, on the
ground that he would cease to act as a warning at night. This was
reluctantly agreed to.
The latest gossip of Teheran was retailed, and a few vague
remarks were made as to the politics of Europe. I was asked to feel
the Imād’s pulse, and did not fail to try both wrists, as I found if I did
not do so I was supposed not to know my business. This was hardly
charlatanry, but merely a deference to the prejudices of the place.
After the usual tea and pipes had been gone through we retired.
The man was still nailed to the post, surrounded by a gaping
crowd of villagers. He amused himself by cursing Pierson as “reis-i-
seem” (“master of the wire”) as we passed him. The Imād, however,
unpinned him at sunset, as he had promised.
The next morning the “Serrum-u-dowlet” called to return Pierson’s
visit to his father, and asked us to dine with him that evening,
entreating us to come in time for tea in the afternoon. The whole
forenoon was occupied in receiving visits from the personages of
Kermanshah.
At five we repaired to the house of the “Serrum-u-dowlet.” We
found him sitting with his brother in a large talár, or archway, one
side of which was open to the air. The whole room was decorated in
the strangest taste; there were the usual mirrors and florid mural
paintings; these in this case were life-size full-length portraits of
posture dancers and dancing girls, and were in ancient costumes,
having been painted fifty years ago. The takhjahs in the walls were
filled with chromo-lithographs in very dubious taste; several odd
chandeliers hung at various heights as ornaments, some twenty pair
of old carriage-lamps were stuck into staples in the walls, and as
many small cages stood about, each containing a bulbul, or
nightingale. What with the noise these birds made, and the splashing
of a fountain which played furiously in a basin of yellow Yezd marble
in the centre, it was difficult to catch what was said. Pipes were
brought, and a long desultory conversation ensued, in the course of
which our host’s guns, dogs, and miscellaneous property were
exhibited and duly admired.
The noise was deafening, and directly we had walked round the
garden a band of musicians, some twenty strong, made night
hideous with their strains and singing. Wine was now produced, and
freely partaken of by both brothers, and trays of sweetmeats were
handed round and afterwards placed on the ground around us.
Spirits, in the form of arrack, the strong coarse spirit of the country,
were pressed on us, but we declined. Our host and his brother,
however, drank it like water.
On a whispered order being given to the servants four Susmani
girls and a buffoon now appeared. These commenced a kind of
posture dance, the buffoon singing and making remarks, which
produced a good deal of laughter from the host and his brother, but
were unintelligible to me, and simply disgusting, as Pierson told me,
who could understand.
The girls were pretty in a way, brunettes with large eyes; their
faces were much painted, and they were fine girls; their ages were
from twelve to seventeen. Their dance had no variety, they spun
round, the hands high in air, while the fingers were snapped with a
loud report. A very free exhibition of considerably developed charms
took place. Every now and then the dancer would make what we call
a cheese; then, standing with the feet motionless, the body was
contorted and wriggled, each muscle being made to quiver, and the
head being bent back till it almost touched the ground; the fingers
being snapped in time to the music; or tiny cymbals, some inch in
diameter, were clashed between the forefinger and thumb of each
hand. The musicians, who played continuously, kept up a sort of loud
chant the whole time. The girls now showed some skill as
equilibrists, balancing full glasses, lighted candles, etc., and an
exhibition of posturing was gone through. They stood on their heads
and walked on their hands; they then danced a scarf-dance.

FEMALE DANCERS AND EQUILIBRISTS.

(From a Native Drawing.)

We had not noticed that the buffoon had retired, but he now re-
entered, disguised in a remarkable manner. He seemed a figure
some four feet high, with a face huge and like a full moon. This was,
in fact, carefully painted on his bare abdomen, the whole
surmounted by a gigantic turban. He had constructed a pair of false
arms, and, with a boy’s coat and large girdle, he presented the effect
of a dwarf with a huge round fat face; his head, chest, and arms
were hidden in the enormous white turban. The face represented
was one of intense and dismal stupidity, and his whole appearance
was most ludicrous; in fact, it was only on afterwards seeing the man
disrobe, that we made out how it was done.
He danced in and out among the girls, who stood in a row
snapping their fingers and posturing: but what was our astonishment
when we saw the dismally stupid face expand into a grin, which
became at length a laughing mask; it resumed its dismal stupidity—it
grinned—it laughed. The musicians played and shouted their chant
more and more loudly, and the face of the figure assumed the most
ludicrous contortions. We all were unable to restrain our laughter,
and the triumphant buffoon retired well rewarded by the Serrum-u-
dowlet. The four dancers now became rather too personal in their
attentions, and begged for coin. We gave them a few kerans, but
were glad when they retired on dinner being announced. We both
pronounced them monotonous and uninteresting.
After a heavy Persian dinner—much such a one as we had at
Merand—we, with some trouble, got away at eleven p.m. Our hosts
seemed inclined to make a very wet night of it; in fact, their frequent
acceptance of cupfuls of raw spirits from the hands of the dancers
had made them see things generally in a rosy light. They wept when
we left!
We rode home through the silent streets of Kermanshah, the only
light being our farnooses, or cylindrical lamps, made of copper and
calico, something in the fashion of a Chinese lantern; and the full
moon.
We met no one in the streets, which were deserted save by the
dogs, and the whole town seemed sunk in sleep. The Persian is an
early bird, going to bed at nine, and rising at four or half-past four. It
is very difficult to break oneself of this habit of early rising on
returning to Europe. One is looked on as very eccentric on getting up
at half-past four, and is hunted from room to room by the
housemaids. Certainly the early morning is the best part of the day
all over the world, but we Europeans in our wisdom have altered it.
“Nous avons changé tout cela”—and we prefer living by gaslight,
electricity, etc.
 The next morning the Serrum-u-dowlet came over to take our
photographs, and was very friendly; he took them really well, and is
a clever fellow.
We went for a ride, and had the unwonted luxury of a two hours’
canter over good turf. I never had this anywhere else in Persia but
once. While near the river we saw plenty of duck, and Pierson told
me that they are always to be had in the Kermanshah river.
In Kermanshah I found that the grassy plain round the town had
many attractions. Some two miles’ canter on it brought me to a
swamp where there were always snipe, except in the hot weather, an
occasional duck, and even at times wild geese. A ludicrous incident
happened to me one day in regard to the latter. As I was cantering
up to the swamp with my groom, I saw on the other side of a herd of
cattle a flock of geese grazing. To dismount and take my gun from
him was the work of an instant, and I quickly inserted a cartridge
charged with No. 4, and a wire ditto, for my left barrel. I walked
stealthily among the cattle towards the flock of geese, but the game
took no notice of me, and allowed me to get within thirty yards; then
it came across me, how if these were tame geese, what a fire of
chaff I should get from Pierson. I did not think of shouting, as of
course I should have done, which would have settled the question,
but I retreated stealthily to where my groom was standing with the
horses. I saw that he was full of excitement, and felt that I had made
a fool of myself. “Shikar?” (“Are they wild ones?”) said I. “Belli, belli,
sahib!” (“Yes, yes, sir!”)
Back I went, but alas! only to be too well convinced that they were
wild ones, for the whole flock sailed away ere I could get within a
hundred and fifty yards. I have often shot geese—that is, a goose at
a time—but I never had such another chance. The birds really
behaved just as tame ones would; I can only suppose that my being
among the grazing cows I was looked upon as harmless. I did not
relate that afternoon’s adventure to Pierson for some time after.
The swamp, which was about a mile long, and at the widest parts
only five hundred yards, was in the centre impossible to cross, save
in summer, when there was no sport there. One side had not nearly
so much cover as the other, but there were no holes; the other side
was full of them, and it was only after a long time that I got
thoroughly acquainted with the geography. In after days I had a
guest who was very hot on sport of all kinds; and as the swamp was
all I could show him at the time, it was arranged that we were to
have a day there.
I, having a holy horror of wet feet, used to go in with a pair of duck
trousers and Persian shoes regardless of water, and march on
frequently up to my waist, changing on coming out. I suggested this
mode to my sporting friend, but he looked on it as very infra dig. and
unsportsmanlike, and set out in a most correct get-up of shooting-
coat with many pockets, and the usual lace-up shooting-boots.
Nothing would induce him to take a change in case of a wetting, and
off we went. As his gun had no sling—almost a necessity in Persia,
where the weapon is so frequently carried on horseback—his groom
carried it in its case.
We got to the swamp, and, knowing the place, I said, “You take the
left side—there are no holes; and I who know the holes will take the
right, which is full of them.”
But my friend was not to be led; he remarked that the right was
certainly the best side, and as guest he ought to have it. To this I of
course agreed, but I pointed out that the holes were deep and
dangerous, and that I knew them, and he did not. But, no, he
insisted. I could, of course, only give in.
The place was alive with snipe. I went to the left, or more open
side, and was over my ankles in a moment. My enthusiastic friend
was in to his knees. We blazed away, and were getting on well, when
my friend lost his ramrod. Persia being a very dry place, all wood
shrinks, and it had probably slipped out. There was nothing for it but
to take the cleaning-rod from the case and use that; the difficulty was
how to carry it, as we were firing frequently, and he didn’t want to
unscrew it. My friend had no belt, and so thrust it down his back,
between his shirt and waistcoat. We began again, and were soon in
the thick of them. We had now got to the widest part of the swamp; I
was separated from my guest by deep water-holes, and was looking
at him when with a shout he suddenly disappeared, and it was
evident he was in a water-hole. I rushed out and ran round the head
of the swamp to his assistance; the servants were out of call. When I
got there he was nearly done for; he had fallen head foremost into a
hole, and could not get out, as the reeds gave way when he pulled
them, and there was only a bottom round the edge of soft mud. The
loading-rod had somehow got down his back, and he could not get
hold of it, while it crippled him; and he had a very white face indeed
when I helped him out by holding my gun out to him. He had lost his
gun, but my groom dived and brought it out.
I wished him to canter home at once, but he did not like to be seen
in the pickle he was in—mud, green mud, from head to foot; and he
insisted on waiting till his man brought a change. This took an hour,
and the day, though bright, was cold and windy. So there he stood in
his wet clothes, his teeth chattering, trying to keep himself warm by
jumping; but his struggles in the water-hole had so weakened him
that he could hardly stand. Of course he had a severe go of
intermittent fever, which laid him up for a fortnight. In after excursions
he was content to leave me the right or dangerous side, which I from
habit was able to safely travel in.
Pierson and I visited a magnificent palace which was in course of
construction by the Imād-u-dowlet. Some idea of its size may be
given when I say that there was stabling for two hundred horses. In
Persia, when a man passes fifty, he begins to be seized with a mania
for building, but he takes care not to finish the works he undertakes,
being thoroughly persuaded of the certainty of his own death in case
of the completion of the edifice.
Some ten years after I had left Kermanshah, Imādieh—so the
place was called—was presented (I dare say much against the
grain) to the king. At that time the Imād-u-dowlet had become the
actual freeholder of the whole of the Kermanshah valley, and his
wealth was immense in money and flocks and herds. But the
inevitable evil day arrived. The Shah recalled him to Teheran, and
the squeezing process commenced; large sums of money were
wrung from him, and the royal treasury correspondingly enriched. It
is always so in Persia; a man is allowed to quietly enrich himself, but
when he has achieved immense wealth he becomes a mark for
oppression in his turn. To use the common expression of the country,
“He is ripe; he must be squeezed.”

THE TOMBS OF THE KINGS. (NAKSH-I-RŪSTAM.)

Just by Imādieh, at the base of a high cliff, is an excavated arched

chamber, at the back of which, carved from the living rock, is an
equestrian statue armed with a lance; it is of colossal size, and some
fourteen feet high (?). Both figure and horse are much damaged by
time and the hand of man, and it is difficult to make much out of the
detail. There are two other figures, one at either extremity of the
back of the arch.
Over the entrance of the arched chamber, which forms a
delightfully cool place to have tea in, are carved in the face of the cliff
itself two figures of Fame (?) (or winged female figures); to the best
of my remembrance they have trumpets. These are more in the
Roman style, or may be even modern (pseudo-classic), for the early
Kings of Persia employed foreign artificers to decorate their palaces;
instance being seen in Ispahan, particularly in the large oil-paintings,
which are certainly not by Oriental artists. Of the great antiquity of
the figures within the arch there can be no doubt, and they are more
than alto-relievo, for they are only affixed to the rock by a small strip,
and are much under-cut. They have been frequently scientifically
described, and appear to be the work of the Sassanian kings.
There are several similar though less pretentious figures: one at
Naksh-i-Rūstam,[14] near Persepolis; another, called by the people
“Ferhad and Shireen,” near Shiraz; but these latter are simply rough
carvings in relief.
A stone platform has been built in front of the archway, and below
this flows a great volume of spring-water that comes from a natural
tunnel beneath the statues. A large hauz or tank is kept constantly
full by this, and when we were there it was ornamented by a flock of
some sixty tame geese, the only ones I had seen, save those in
Teheran, and the recent sight of them had something to do with my
hesitation when in search of sport on the occasion which I have
noted.
The shade and coolness, the noise of flowing water, and the huge
tank with the geese on it (and a swimming goose in a large piece of
water is a decidedly handsome bird, when you have no swans),
rendered this place a favourite one to drink tea and smoke pipes in.
The Naib-ul-ayālut, the second son of the Imād-u-dowlet, was a
man who devoted much attention to astrology and the pursuit of the
philosopher’s stone. He entertained us one day with tea at the
statue, and gave us an impromptu exhibition of fireworks; and as
they were discharged from the edge of the tank, it acted like a mirror,
and the effect was good in the extreme.
Astrology is at a premium in Persia; the monajem, or astrologers,
are consulted on almost every subject. Each village has its diviner,
and each big town supports several, the head of whom boasts the
sounding title of “monajem-bashi” (chief astrologer).
 Their great occupation is to predict fortunate hours, days, etc.
They will fix on a day for a great man to start on a journey or arrive at
a place, and the man will be careful to follow the astrologer’s
direction, for they have a great belief in bad and good luck. The rules
by which the astrologers make their calculations are very
complicated; strange to say, there are many of them who really
believe in their own profession. Each has his astrolabe of brass or
silver; some of the brass ones are very large and handsome: I have
known as much as one thousand kerans paid for a good one. They
are manufactured in the country. The king’s astrologer is a very great
man indeed, and no important act is undertaken without consulting
him. Often the astrologer goes further than his own special business
of “ruling the planets,” and by means of rolling six dice, which revolve
on a rod run through the centre of them, he pretends to read the
future—in fact, he is a fortune-teller. Many, too, are rammals, or
discoverers of stolen property. This is often ingeniously done, after a
good deal of hocus pocus, by working on the fears of the thieves.
The old, old plans are adopted: sticks are given to the suspected,
and they are told they will grow if they are guilty; the conscience-
stricken breaks a piece off. Or they are told to dip their hands into a
pot placed in a dark room; this is full of dye stuff; the guilty man does
not dip his hand, and is so detected. Or, more frequently, all the
suspects are sworn to innocence in the name of some local saint,
and are informed that the vengeance of the saint will fall on the guilty
man if the property is not returned; in the morning it often
mysteriously reappears. These men, then, are of use, and by their
means property may often be recovered that would otherwise never
be traced.
I myself have employed them successfully on several occasions.
As a rule, thefts by domestics of anything valuable are very rare,
though pilfering goes on a good deal, for the Persian servant looks
on his master’s tea, sugar, and grain as lawful plunder; when things
are taken, it is usually done by a servant merely in the hope of
getting a rival into trouble, and an edict that the servants will have to
pay a little more than the value of the lost property is enough to bring
it back; it is impossible to detect under these circumstances the
abstractor. But if a thief is really among the household, the servants
as a rule find him out and clamour for his discharge.
Such an event happened when my best pipe-head suddenly
disappeared. I sent for the rammal, and after various mysterious
ceremonies unsuccessfully gone through, the man retired promising
me my property before noon the next day. Next morning one of my
men calmly informed me that he had seen the prophet Mahommed
in a dream, who addressed him thus—
“‘Hadji, my son, are you well?’
“‘Alas! no, holy prophet; I am in deep grief, my heart is burnt up
with misery.’
“‘Why is this, son Hadji?’
“‘My master has lost a pipe-head, O prophet, and I—I, the
innocent Hadji—may be suspected; the hearts of all the servants are
tightened (idiom) by this sad fear.’
“‘Be not afraid, son Hadji; if you look at the top left-hand corner of
your master’s tank, you will find it.’
“I swooned away with delight, sahib, and am only waiting your
permission to make a search.”
I smiled, and of course there they found my pipe-head. As I knew
theft was not intended, I said nothing, but I did not reward the vision-
seeing finder.
One day in Kermanshah I was surprised to meet a procession in
the streets. First came all the lutis or buffoons, the public musicians
singing and dancing, then a crowd of drunken roughs, then a few
soldiers with fixed bayonets, then the “farrash-bashi,” or “principal
tent-pitcher”—in reality the Imād-u-dowlet’s head-man—on
horseback; then the executioner, clad in red, and his aides; then two
wretched women, their heads shaved and rubbed with curds, their
faces bare and blackened, dressed in men’s clothes, and both
seated on one donkey, led by a negro, with their faces to the tail
(their feet had been beaten to a pulp); then a crowd of some two
thousand men, women, and children. On inquiry I learnt that these
women were attendants at a public bath, and had betrayed the wife
of a tradesman into the hands of an admirer, who had secreted
himself in the bath with their connivance. The woman complained,
the man fled, and justice (Persian justice) was being done on the two
unfortunate women. The Imād-u-dowlet had severely bastinadoed
them and then gave them over to the executioner to be paraded
through the town and then banished—after they had been handed
over to the tender mercies of all the ruffians of the city. The first part
of the sentence had been carried out, and they had been led thus
through the bazaars from dawn till afternoon; the executioner taking,
as is customary, a small tax from each trader according to his
degree. Such is the Persian custom from old times. I learnt
afterwards that the mob defiled these women, and one died of her
injuries; the other poor wretch either took poison or was given it by
her offended relatives the next morning.
Such is Persian justice.
 CHAPTER XI.
I GO TO ISPAHAN.

Deficiency of furniture—Novel screws—Pseudo-masonry—Fate of the Imād-u-

dowlet’s son—House-building—Kerind—New horse—Mule-buying—Start for
Ispahan—Kanaats—Curious accident—Fish in kanaats—Loss of a dog—
Pigeons—Pigeon-towers—Alarm of robbers—Put up in a mosque—Armenian
village—Armenian villagers—Travellers’ law—Tax-man at Dehbeed—Ispahan
—The bridge—Julfa.

In these early days of the Telegraph Department we all had

considerable difficulty in getting furniture; the little good furniture
Pierson and I had, viz., two tables, came from Baghdad, and was
originally made in India. I was delighted to get from my friend the
farrash-bashi a magnificent arm-chair made of mahogany and
stuffed in velvet. Even the word for a chair, “sandalli,” was not used
in Kermanshah, but “kūrsi,” a platform, was the expression; and the
rough chairs we got made, of plane or poplar, painted bright green or
red in water-colour and unvarnished, and pinned together by wooden
pegs in lieu of mortises, were uneasy in the extreme, always coming
to grief; and the travelling camp-stools, with no back, were nearly as
bad. In Ispahan the natives are clever as carpenters, and now make
chairs, tables, and even chests of drawers very fairly. I once had
some made by a very clever young Armenian carpenter, and the
chests of drawers were very good indeed, but I found that the locks
and hinges were nailed on instead of screws being used. I sent them
back, and then, rather than buy screws, which are somewhat
expensive in Persia, the carpenter cut slots with a file in the head of
each round-headed nail, sending them to me and triumphantly
demanding his money, supposing that now at least I was satisfied.
But on putting a screwdriver to them, I detected the ingenious
deception, and remembering the Persian proverb, “If you can deal
with an Armenian, you can deal with the devil,” I had to put pressure
on the man to get screws really put on.
The farrash-bashi’s arm-chair arrived with five pounds in cash, ten
loaves of sugar—loaf-sugar was one and sixpence a pound at that
time and only used by the rich—several pounds of tea, and twenty
mule-loads of barley—not a bad fee. I was surprised at the largeness
of it, and found that the farrash-bashi was a “mason,” which
accounted for it.
One of the king’s servants conceived the brilliant idea of
introducing pseudo-masonry into Persia for the sake of his own
aggrandisement. He inaugurated so-called lodges of masons
(Feramūsh-khana, “the house of forgetfulness,” is the name used in
the country for a masonic lodge) all over Persia, specially impressing
on the neophytes the doctrine that implicit obedience was in all
things temporal to be yielded to the superior, and exacted large
contributions. With a people so excitable as the Persians, anything
mysterious has a great charm. The astute mirza took care only to
initiate rich neophytes, or at all events men of position, and a
gigantic political engine was the result (of course all this was quite
contrary to the spirit of masonry, which especially avoids politics).
The king got wind of the matter, and the clever Armenian (for he was
a son of poor Armenians of Julfa) was banished the kingdom, or fled
to save his throat. But time went on, the past was condoned, and the
poor Armenian boy now occupies a high diplomatic position at a
great European Court, and holds the title of prince.
It appears that the farrash-bashi’s handsome fee was not so much
caused by gratitude for professional treatment, but was merely a way
of “rendering unto Cæsar the things which are Cæsar’s,” for he had
seen a masonic jewel of mine similar to one worn by the maker of
mock masons, and hence the chair and the rest of it.
A curious episode now occurred. The Imād-u-dowlet had a son,
his youngest and favourite. This fellow was guilty of every crime that
is possible. While we were in Kermanshah he had attempted his
father’s life, and actually wounded him with slugs from a pistol
discharged at a few yards’ distance. The Imād at length confined him
in chains to his chamber. At the intercession of his brothers, the
chains after forty-eight hours were removed, and in a week or so he
was received into apparent favour, and set at liberty. But from what
we learnt afterwards, this was merely a manœuvre to quiet the
minds of the townspeople—his destruction had been resolved on.
One morning a man of the Imād’s rushed into our courtyard and
implored me to start at once for Imādieh, where, it was stated, the
prince had wounded himself with his gun. I left at once on a very
good horse of Pierson’s, and galloped violently to the place.
Here I found the Imād’s doctor, Mirza Zeynal Abdeen. He was as
white as a sheet, and hurried me to the edge of the large tank; there
lay the corpse of the Imād’s son; a few servants stood round, and
seemed frightened out of their wits. Mirza Zeynal Abdeen was
beside himself, and besought me to do something.
I told him the man had been dead some time. This seemed to
astonish him. On closer inspection I found that death had been
caused by a gun-shot wound, fired with the muzzle touching, or
almost touching, the junction of the chin and neck; so close had the
weapon been placed that the flesh was burnt by the flame. The
entire charge was lodged in the brain. Nobody could give any
information, but the man’s discharged gun lay by him. I have no
doubt that the matter was really an execution, for one of the wrists
was bruised by finger-marks, and doubtless the unfortunate man had
been held down and slain with his own weapon.
An account was given that he had thrown the gun up and caught it
several times, but, missing it, that the butt struck the pavement and
the gun exploded; but the muzzle must have been nearly touching
when discharged. There being nothing more to do, I promised to
break the news to the Imād-u-dowlet, though doubtless he was well
aware of the result.
I got on the horse Pierson had lent me on account of its swiftness,
to return, but he could hardly move, so I took my servant’s. As we
crawled towards the town, my servant leading the foundered animal,
we had to take him into a village; he lay down and died, and I rode
home on the servant’s horse. On the way, every now and then, I met