SCH 1110 CHEMISTRY I [42

Hours]
Prerequisites: None
Purpose
To enable the learner to have an in-depth understanding of the underlying principles
and concepts of physical and inorganic chemistry.

Learning outcomes
At the end of the course the students should be able to
i. Understand structure of the atom and periodicity
ii. Draw the electronic configuration of different elements and ions
iii. To write, balance and carryout calculations of chemical reactions
iv. Describe an equilibrium reaction, predict how different factors affect it and
calculate the equilibrium constants.
v. Calculate energy changes that take place during bond formation and bond
breaking.

Course Description
The Atom: Fundamental particles of the atom, isotopes. Atomic models: Thompson,
Rutherford's planetary model, Bohr atomic model, Sommerfield-Bohr model, Borh-
Sommerfield‘s Electromagnetic Waves; electromagnetic spectrum, Planks quantum
theory of waves. Atomic model of atomic spectra, line spectra, dual nature of electrons,
introduction to quantum theory, quantum numbers, Aufbau’s principle, Hund’s rule,
Pauli’s exclusion principle, atomic orbitals and electron configurations of elements.
Wave mechanical concept of atomic structure; de Broglie’s concept of dual nature of
matter, Heisenburg’s uncertainty principle, electron charge cloud concept and atomic
orbitals. Periodic Trends; electronegativity, electron affinity, ionization energy and
sizes. Chemical reactions; atomic mass, avogadro’s number, mole, molecular mass,
percentage composition, determination of empirical and molecular formula, chemical
reactions and equations, stoichiometry, balancing reactions, reactants and products,
limiting reagents and product yields. Bonding: Covalent, ionic, metallic, Van der Waals
hydrogen bonding. Physical chemistry: Equilibrium: Introduction to chemical and
physical equilibrium, factors that affect the equilibrium, equilibrium constants Kc and Kp
and their relationship, Hess’s law, Le-Chateliers principle, Chemical energetics and
bonding.
Teaching Methods
Lecturers, Tutorials, Case Studies, Presentations and Guest Lecturers.
Instructional Materials/Equipment
White Board, Markers, Flip Chart, Handouts, LCD Projector and Computer.
Course Assessment
Assignments 5%
Practicals 10%
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Continuous Assessment Tests 15%
Final Examination 70%
Total 100%
Core Text Book
Arum Bahl, G.D Tuli and S. Chand. (2014) Essentials of physical chemistry.
Multicolour edition.
Other References
a) Sethi, M. S.. (2011). Chemical bonding. Discovery Publishing House
b) Cotton, F.A (2003). Chemical applications of group theory 3rd ed. Wiley

Course Journals
a) Journal of Structural Chemistry
b) Journal of Structure and Bonding
STRUCTURE OF ATOM –CLASSICAL MECHANICS

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CATHODE RAYS – THE DISCOVERY OF ELECTRON
The knowledge about the electron was derived as a result of the study of the
electric discharge in the discharge tube (J.J. Thomson, 1896). The discharge
tube consists of a glass tube with metal electrodes fused in the walls (Fig. 1.1).
Through a glass side-arm air can be drawn with a pump. The electrodes are
connected to a source of high voltage (10,000 Volts) and the air partially
evacuated.
The electric discharge passes between the electrodes and the residual gas in the
tube begins to glow.
If virtually all the gas is evacuated from within the tube, the glow is replaced
☺ by faintly luminous ‘rays’ which produce fluorescence on the glass at the
end far from the cathode. The rays which proceed from the cathode and

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 move away from it at right angles in straight lines are called Cathode
Rays.

MEASUREMENT OF e/m FOR ELECTRONS

The ratio of charge to mass (e/m) for an electron was measured by J.J. Thomson
(1897) using the apparatus shown in Fig. 1.2.
Electrons produce a bright luminous spot at X on the fluorescent screen. Magnetic
field is
applied first and causes the electrons to be deflected in a circular path while the spot
is shifted to Y.
The radius of the circular path can be obtained from the dimensions of the apparatus,
the current and number of turns in the coil of the electromagnet and the angle of
deflection of the spot. An electrostatic field of known strength is then applied so as to
bring back the spot to its original position. Then from the strength of the electrostatic
field and magnetic field, it is possible to calculate the velocity of the electrons.

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DETERMINATION OF THE CHARGE ON AN ELECTRON
The absolute value of the charge on an electron was measured by R.A. Milikan
(1908) by what is known as the Milikan’s Oil-drop Experiment. The apparatus used
by him is shown in Fig. 1.3. He sprayed oil droplets from an atomizer into the
apparatus. An oil droplet falls through a hole in the upper plate. The air between the
plates is then exposed to X-rays which eject electrons from air molecules. Some of
these electrons are captured by the oil droplet and it acquires a negative charge.
When the plates are earthed, the droplet falls under the influence of gravity. He
adjusted the strength of the electric field between the two charged plates so that a
particular oil drop remained suspended, neither rising nor falling. At this point, the
upward force due to the negative charge on the drop, just equalled the weight of the
drop. As the X-rays struck the air molecules, electrons are produced. The drop
captures one or more electrons and gets a negative
charge, Q. Thus,
Q = ne
where n = number of electrons and e = charge of the electron. From measurement
with different drops, Milikan established that electron has the charge – 1.60 × 10– 19
coulombs.

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Nearly all of the ordinary chemical properties of matter can be examined in terms of
atoms
consisting of electrons, protons and neutrons. Therefore for our discussion we will
assume that atom
contains only these three principal subatomic particles.
Other Subatomic Particles
Besides electrons, protons and neutrons, many other subatomic particles such as
mesons,
positrons, neutrinos and antiprotons have been discovered. A great deal of recent
research is producing
a long list of still other subatomic particles with names quarks, pions and gluons.
With each discovery,
the picture of atomic structure becomes increasingly complex. Fortunately, the three-
particle (electron,
proton, neutron) picture of the atom still meets the needs of the chemists.
ALPHA PARTICLES
Alpha particles are shot out from radioactive elements with very high speed. For
example, they
come from radium atoms at a speed of 1.5 × 107 m/sec. Rutherford identified them to
be di-positive

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ISOTOPES
WHAT ARE ISOTOPES?
Contrary to Dalton’s Atomic theory, all atoms of a given element are not necessarily
identical. In fact, most elements have been shown to be composed of two or more
types of atoms mixed in a fixed proportion.
(1) The different atoms of such an element contain equal number of protons and,
therefore, have the same
atomic number.
(2) The atoms which vary from one another have different number of neutrons in the
nucleus. Thus they have
different atomic masses.
The atoms of an element which have the same number of protons and different
number of neutrons are called Isotopes.
Alternatively, isotopes may be defined as:
The atoms of an element which have the same atomic number but different
atomic masses or mass numbers.
The name ‘isotope’ was assigned to them by Soddy because they have the same
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atomic number and hence occupied the same place in the periodic table (Greek, isos =
same; topos = place).
Isotopes have similar chemical properties as they have the same electronic
configuration. However, they differ in respect of physical properties which depend on
atomic mass.
SYMBOLIC REPRESENTATION OF ISOTOPES
In denoting particular isotopes of an element, the following notation has been
internationally
adopted. The symbol of the element is written with atomic mass at the head and
atomic number at
the bottom. Alternatively, the name of the element is followed by the atomic mass
with a hyphen (-)
in between. Thus the isotopes of carbon (atomic number 6) having atomic masses 12
and 14 may be
written as

12
C or Carbon-12 reads ‘carbon twelve’, meaning isotope of carbon with a mass of
approximately
12 amu.

EXAMPLES OF ISOTOPES
Since isotopes of an element have the same atomic number, each of these contains
equal number of protons. They have different atomic masses which is accounted for
by the different number of neutrons present in the nucleus. Thus the isotopes of an
element are characterised by different number of neutrons in the nucleus.

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WAVE MECHANICAL CONCEPT OF ATOM
Bohr, undoubtedly, gave the first quantitative successful model of the atom. But now
it has been superseded completely
by the modern Wave Mechanical Theory. The new theory rejects the view that
electrons move in closed orbits, as was visualised by Bohr. The Wave mechanical
theory gave a major breakthrough by suggesting that the electron motion is of a
complex nature best described by its wave properties and probabilities.
While the classical ‘mechanical theory’ of matter considered matter to be made of
discrete particles (atoms, electrons, protons etc.), another theory called the ‘Wave
theory’ was necessary to interpret the nature of radiations like X-rays and light.
According to the wave theory, radiations as X-rays and light, consisted of continuous
collection of waves travelling in space.
The wave nature of light, however, failed completely to explain the photoelectric
effect i.e. the emission of electron from metal surfaces by the action of light. In their
attempt to find a plausible explanation of radiations from heated bodies as also the
photoelectric effect, Planck and Einstein (1905) proposed that energy radiations,
including those of heat and light, are emitted discontinuously as little ‘bursts’, quanta,

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or photons. This view is directly opposed to the wave theory of light and it gives
particle-like properties to waves. According to it, light exhibits both a
wave and a particle nature, under suitable conditions. This theory which applies
to all radiations, is
often referred to as the ‘Wave Mechanical Theory’.
With Planck’s contention of light having wave and particle nature, the distinction
between particles and waves became very hazy. In 1924 Louis de Broglie advanced a
complimentary hypothesis for material particles. According to it, the dual character–
the wave and particle–may not be confined to radiations alone but should be extended
to matter as well. In other words, matter also possessed particle as well as wave
character. This gave birth to the ‘Wave mechanical theory of matter’. This theory
postulates that electrons, protons and even atoms, when in motion, possessed wave
properties and could also be associated with other characteristics of waves such as
wavelength, wave-amplitude
and frequency. The new quantum mechanics, which takes into account the
particulate and wave
nature of matter, is termed the Wave mechanics.

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DISTRIBUTION OF ELECTRONS IN ORBITALS
In passing along the periodic table of the elements from one element to the other, we find that
one electron is added every time to the next atom. Where should the incoming electron go? The
answer is provided by the possible values of the quantum numbers that can be assigned to the
electron in accordance with Pauli’s exclusion principle–prohibiting an orbital to accommodate two
electrons with the same set of quantum numbers.
On the basis of magnetic measurements, which also help to determine the electronic configuration
of elements, Hund put forward another empirical rule, popularly known after his name as Hund’s
Rule of Maximum Multiplicity. It states that : Electrons are distributed among the orbitals of a
subshell in such a way as to give the maximum number of unpaired electrons and have the
same direction of spin.

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PHYSICAL EQUILIBRIUM
Physical equilibria do not involve changes to the chemical properties of substances involved. For instance,
the equilibrium of liquid water with water vapour in a partially filled bottle. It is a physical equilibrium since
the water molecules have only changed from liquid to vapour.

Definitions
Phase
A phase is defined as any homogeneous and physically distinct part of a system which is separated from
other parts of the system by interfaces.
A part of a system is homogeneous if it has identical physical properties and chemical composition
throughout the part.
o A phase may be gas, liquid or solid.
o A gas or a gaseous mixture is a single phase.
o Totally miscible liquids constitute a single phase.
o In an immiscible liquid system, each layer is counted as a separate phase.
• Every solid constitutes a single phase except when a solid solution is formed.
• A solid solution is considered as a single phase. o Each polymorphic form
constitutes a separate phase.

The number of phases does not depend on the actual quantities of the phases present. It also does not
depend on the state of subdivision of the phase.
Examples
Counting the number of phases
1. Liquid water, pieces of ice and water vapour are present together. The number of phases is 3 as
each form is a separate phase. Ice in the system is a single phase even if it is present as a number
of pieces.
2. Calcium carbonate undergoes thermal decomposition.
The chemical reaction is: CaCO3(s) CaO(s) + CO2 (g)
Number of phases = 3
This system consists of 2 solid phases, CaCO3 and CaO and one gaseous phase, that of CO2.
3. Ammonium chloride undergoes thermal decomposition.

The chemical reaction is:

NH4Cl(s) NH3 (g) + HCl (g)
Number of phases = 2
This system has two phases, one solid, NH4Cl and one gaseous, a mixture of NH3 and HCl.
4. A solution of NaCl in water Number of phases = 1

5. A system consisting of monoclinic sulphur, rhombic sulphur and liquid sulphur Number of
phases = 3

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This system has 2 solid phases and one liquid. Monoclinic and rhombic sulphur, polymorphic forms,
constitute separate phases.

Components
The number of components of a system at equilibrium is the smallest number of independently varying
chemical constituents which the composition of each and every phase in the system can be expressed. It
should be noted that the term “constituents” is different from “components”, which has a special definition.
When no reaction is taking place in a system, the number of components is the same as the number of
constituents. For example, pure water is a one component system because all the different phases can be
expressed in terms of the single constituent water.
Examples
Counting the number of components
1. The sulphur system is a one component system. All the phases, monoclinic, rhombic, liquid and
vapour – can be expressed in terms of the single constituent – sulphur.

2. A mixture of ethanol and water is an example of a two component system. We need both ethanol and
water to express its composition.

3. An example of a system in which a reaction occurs and an equilibrium is established is the thermal
decomposition of solid CaCO3.
In this system, there are three distinct Phases: solid CaCO 3, solid CaO and gaseous CO2. Though there are
3 species present, the number of components is only two, because of the equilibrium:
CaCO3 (s) CaO(s) + CO2(g)
Any two of the three constituents may be chosen as the components. If CaO and CO 2 are chosen, then the
composition of the phase CaCO3 is expressed as one mole of component CO2 plus one mole of component
CaO. If, on the other hand, CaCO3 and CO2 were chosen, then the composition of the phase CaO would be
described as one mole of CaCO3 minus one mole of CO2.

4. A system in which ammonium chloride undergoes thermal composition.

NH4Cl (s) NH3(g) + HCl (g)
There are two phases, one solid-NH4Cl and the other gas – a mixture of NH3 and HCl. There are three
constituents. Since NH3 and HCl can be prepared in the correct stoichiometric proportions by the reaction:
NH4Cl → NH3+HCl
The composition of both the solid and gaseous phase can be expressed in terms of NH 4Cl. Hence the
number of components is one.
If additional HCl (or NH3) were added to the system, then the decomposition of NH4Cl would not give the
correct composition of the gas phase. A second component, HCl (or NH 3) would be needed to describe the
gas phase.

Degrees of freedom (or variance)

The degrees of freedom or variance of a system is defined as the minimum number of variables such as
temperature, pressure, concentration, which must be arbitrarily fixed in order to define the system
completely.
Examples
Systems of different variance
a) A gaseous mixture of CO2 and N2. Three variables: pressure, temperature and composition are
required to define this system. This is, hence, a trivariant system.
b) A system having only liquid water has two degrees of freedom or is bivariant. Both temperature and
pressure need to be mentioned in order to define the system.
c) If to the system containing liquid water, pieces of ice are added and this system with 2 phases is
allowed to come to equilibrium, then it is an univariant system. Only one variable, either temperature or
pressure need to be specified in order to define the system. If the pressure on the system is maintained at
o
1 atm, then the temperature of the system gets automatically fixed at 0 C, the normal melting point of ice.

d) If in the system mentioned above, a small quantity of water is allowed to evaporate and then the
system is allowed to come to equilibrium, then the number of phases in equilibrium will be three. This
system has no degrees of freedom or it is invariant.
o
Three phases, ice, water, vapour can coexist in equilibrium at 0.0075 C and 4.6mm of Hg pressure only. A
change in temperature or pressure will result in one or two phases disappearing. Hence the degree of
freedom of a system may also be defined as the number of variables, such as temperature, pressure and
concentration that can be varied independently without altering the number of phases. The phase rule
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The phase rule is the relationship between the number of phases, P, the number of components, C and the
number of degrees of freedom, F of a system at equilibrium at a given P and T. The rule is P+F = C+2,
where 2 stands for the intensive variables pressure, P and temperature, T. This is a general rule applicable
to all types of reactive and nonreactive systems. In a nonreactive system, the various components are
distributed in different phases without any complications, such as reacting chemically with each other. First
let us derive this rule for the nonreactive system and then show that the same rule applies to the reactive
system as well.

What is a phase diagram?

A phase diagram is one in which the relationships between the states or phases of a substance can be
summarized. The diagram shows the various phases present at different temperatures and pressures. They
are also called equilibrium diagrams.
We can see important properties like melting point, boiling point, transition points and triple points of a
substance on the phase diagram. Every point on the phase diagram represents a state of the system as it
described T and p values. The lines on the phase diagram divide it into regions.
These regions may be solid, liquid or gas. If the point that describes a system falls in a region, then the
system exists as a single phase. On the other hand, if the point falls on a line, then the system exists as two
phases in equilibrium. The liquid-gas curve has a definite upper limit at the critical temperature and
pressure as liquid and gas become indistinguishable above this temperature and pressure. The phase
diagram for water
The simplest case of a one component system is one in which there is only one solid phase. In a system
having more than one solid phase, there are a number of possible equilibria and the phase diagram gets
o
quite complicated. In the case of “water” system, above –20 C and below 2000 atm pressure, there is only
one solid phase, namely, ordinary ice.

Figure 4: The phase diagram for water

Phase boundaries show the values of p and T at which two phases coexist in equilibrium.

Critical Point
• In a closed rigid vessel, boiling does not occur.
• As the temperature is raised the density of vapor increases and the density of the liquid decreases.
• When the density of the vapor and liquid phases are equal the surface between the two phases
disappears.
• The temperature at which this occurs is called the critical temperature, Tc.
• The vapor pressure at the critical temperature is called the critical pressure, pc.

Triple Point
• There is a set of conditions under which three different phases of a substance (typically solid, liquid
and vapor) all simultaneously coexist in equilibrium.
• This point is called the triple point.
• For any pure substance the triple point occurs only at single definite pressure and temperature. The
triple point of water lies at 273.16 K and 611 Pa.
• The triple point marks the lowest pressure at which a liquid phase can exist.
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Equilibrium between liquid and vapour (vaporization curve)
The system at the triple point is gradually heated at constant volume, the temperature and pressure do not
change till the entire solid melts to give liquid water. There are only 2 phases in the system – liquid water
and vapour. If the heating is continued at constant volume, the temperature and vapour pressure of the
system vary along the curve OA figure 4. The curve OA is known as the vaporization curve and along the
curve OA liquid water and vapour are in equilibrium with each other.

Equilibrium between solid and vapour (sublimation curve)

At the point B (Fig.4) ice is in equilibrium with its vapour. The pressure at B is the vapour pressure of ice at
the temperature at B. If this temperature at B is gradually raised keeping the volume constant, vapour
pressure of ice also increases. If the vapour pressure of ice is plotted against temperature, the curve BO,
the sublimation curve is obtained. Along the curve BO, ice and water vapour are in equilibrium with each
other.

Equilibrium between solid and liquid (fusion curve)

If solid water (ice) at some high pressure is heated slowly, it starts melting after a certain temperature is
reached. Temperature of the system then remains constant till the entire solid phase is converted to liquid.
The temperature at which the solid melts to give liquid depends on the pressure on the solid phase. The
line OC (Fig.4) depicts the various conditions of temperature and pressure at which ice and water are in
equilibrium with each other.
CHARACTERISTICS OF CHEMICAL EQUILIBRIUM
(1) Constancy of concentrations
When a chemical equilibrium is established in a closed vessel at constant temperature, concentrations of
the various species in the reaction mixture become constant. The reaction mixture at equilibrium is called
Equilibrium mixture. The concentrations at equilibrium are called Equilibrium concentrations. The
equilibrium concentrations are represented by square brackets with subscript eq or eqm, [ ]. Thus [A]
denotes the equilibrium concentration of substance A in moles per litre.
(2) Equilibrium can be initiated from either side
The state of equilibrium of a reversible reaction can be approached whether we start with reactants or
products, for example, the equilibrium

is established if we start the reaction with H2 and I2, or 2 HI.

Fig.5. Shows whether we start with 1 mole of I2 and 1 mole of H2, or with 2 moles of HI in a vessel of the
same volume, the same mixture of H2, I2 and HI is obtained.

(3) Equilibrium cannot be attained in an open vessel

The equilibrium can be established only if the reaction vessel is closed and no part of the reactants or
products is allowed to escape out. In an open vessel, the gaseous reactants and/or products may escape
into the atmosphere leaving behind no possibility of attaining equilibrium. However, the equilibrium can be
attained when all the reactants and products are in the same phase i.e., ethanol and ethanoic acid.
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 (4) A catalyst cannot change the equilibrium point
When a catalyst is added to a system in equilibrium, it speeds up the rate of both the forward and the
reverse reaction to an equal extent. Therefore a catalyst cannot change the equilibrium point except that it
is achieved earlier. This enhances the rate of the reaction. The rapid increase of the rate of an equilibrium
reaction on the addition of a catalyst is illustrated in Fig. 6.

(5)Value of Equilibrium Constant does not depend upon the initial concentration of reactants
It has been found that equilibrium constant must be the same when the concentrations of reacting species
are varied over a wide range.
(6) At Equilibrium ΔG = 0
At equilibrium the Gibbs free energy (G) is minimum and any change taking place at equilibrium proceeds
without change in free energy i.e. ΔG = 0.

EQUILIBRIUM CONSTANT: EQUILIBRIUM LAW

Let us consider a general reaction

and let [A], [B], [C] and [D] represent the molar concentrations of A, B, C and D at the equilibrium point.
According to the Law of Mass action.

Where k1 and k2 are rate constants for the forward and reverse reactions. At equilibrium, rate of forward
reaction = rate of reverse reaction.

At any specific temperature k1/k2 is constant since both k1 and k2 are constants. The ratio k1/k2 is called
Equilibrium constant and is represented by the symbol Kc, or simply k. The subscript „c’ indicates that the
value is in terms of concentrations of reactants and products. The equation above may be written as

This equation is known as the Equilibrium constant expression or Equilibrium law. Consider the reaction

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Here, the forward reaction is dependent on the collisions of each of two A molecules. Therefore, for writing
the equilibrium expression, each molecule is regarded as a separate entity i.e.,

Then the equilibrium constant expression is

As a general rule, if there are two or more molecules of the same substance in the chemical equation, its
concentration is raised to the power equal to the numerical coefficient of the substance in the equation.

Equilibrium Constant Expression for a Reaction in General Terms The general

reaction may be written as

Where a, b, c and d are numerical quotients of the substance, A, B, C and D respectively. The equilibrium
constant expression is

where Kc is the Equilibrium constant. The general definition of the equilibrium constant may thus be stated
as: the product of the equilibrium concentrations of the products divided by the product of the equilibrium
concentrations of the reactants, with each concentration term raised to a power equal to the coefficient of the
substance in the balanced equation.

How to Write the Equilibrium Constant Expression?

(1) Write the balanced chemical equation for the equilibrium reaction. By convention, the substances
on the left of the equation are called the reactants and those on the right, the products.
(2) Write the product of concentrations of the „products‟ and raise the concentrations of each
substance to the power of its numerical quotient in the balanced equation.
(3)Write the product of concentrations of „reactants‟ and raise the concentration of each substance to the
power of its numerical quotient in the balanced equation.
(4) Write the equilibrium expression by placing the product concentrations in the numerator and reactant
concentrations in the denominator. That is,

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EQUILIBRIUM CONSTANT EXPRESSION IN TERMS OF PARTIAL PRESSURES
When all the reactants and products are gases, we can also formulate the equilibrium constant expression
in terms of partial pressure. The relationship between the partial pressure (p) of any one gas in the
equilibrium mixture and the molar concentration follows from the general ideal gas equation

The quantity n/V is the number of moles of the gas per unit volume and is simply the molar concentration.
Thus, p = (Molar concentration) × RT
i.e., the partial pressure of a gas in the equilibrium mixture is directly proportional to its molar concentration
at a given temperature. Therefore, we can write the equilibrium constant expression in terms of partial
pressure instead of molar concentrations. For a general reaction

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the equilibrium law or the equilibrium constant may be written as

Here Kp is the equilibrium constant, the subscript p referring to partial pressure. Partial pressures are
expressed in atmospheres.

HOW Kc AND Kp ARE RELATED?

Let us consider a general reaction

Where, all reactants and products are gases. We can write the equilibrium constant expression in terms of
partial pressures as

Assuming that all these gases constituting the equilibrium mixture obey the ideal gas equation, the partial
pressure (p) of a gas is

Where, n/V is the molar concentration. Thus the partial pressures of individual gases, A, B, C and D are:

Substituting these values in equation (1), we have

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where Δn = (l + m) – (j + k), the difference in the sums of the coefficients for the gaseous products and
reactants.
From the expression above it is clear that when Δn = 0, Kp = Kc.

LE CHATELIER’S PRINCIPLE

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Henry Le Chatelier proposed a general principle which applies to all systems in equilibrium. This important
principle called the Le Chatelier’s principle may be stated as: when a stress is applied on a system in
equilibrium, the system tends to adjust itself so as to reduce the stress.
There are three ways in which the stress can be caused on a chemical equilibrium:
1. Changing the concentration of a reactant or product.
2. Changing the pressure (or volume) of the system.
3. Changing the temperature.

Thus when applied to a chemical reaction in equilibrium, Le Chatelier‟s principle can be stated as: if a
change in concentration, pressure or temperature is caused to a chemical reaction in equilibrium, the
equilibrium will shift to the right or the left so as to minimise the change. Now we proceed to illustrate the
above statement by taking examples of each type of stress.

EFFECT OF A CHANGE IN CONCENTRATION

We can restate Le Chatelier‟s principle for the special case of concentration changes: when concentration of
any of the reactants or products is changed, the equilibrium shifts in a direction so as to reduce the change in
concentration that was made.

Addition of an inert gas

Let us add an inert gas to an equilibrium mixture while the volume of the reaction vessel remains the same.
The addition of the inert gas increases the total pressure but the partial pressures of the reactants and
products are not changed. Thus the addition of an inert gas has no effect on the position of the equilibrium.

Effect of change of concentration on Ammonia Synthesis reaction

Let us illustrate the effect of change of concentration on a system at equilibrium by taking example of the
ammonia synthesis reaction:

When N2 (or H2) is added to the equilibrium already in existence (equilibrium I), the equilibrium will shift to
the right so as to reduce the concentration of N2 (Le Chatelier‟s principle). The concentration of NH3 at the
equilibrium II is more than at equilibrium I. The results in a particular case after the addition of one mole/litre
are given below.

Obviously, the addition of N2 (a reactant) increases the concentration of NH3, while the concentration of H2
decreases. Thus to have a better yield of NH3, one of the reactants should be added in excess.
A change in the concentration of a reactant or product can be effected by the addition or removal

of that species. Let us consider a general reaction

When a reactant, say, A is added at equilibrium, its concentration is increased. The forward reaction alone
occurs momentarily. According to Le Chatelier‟s principle, a new equilibrium will be established so as to
reduce the concentration of A. Thus the addition of A causes the equilibrium to shift to right. This increases
the concentration (yield) of the product C.

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Following the same line of argument, a decrease in the concentration of A by its removal from the
equilibrium mixture, will be undone by shift to the equilibrium position to the left. This reduces the
concentration (yield) of the product C.

EFFECT OF A CHANGE IN PRESSURE

To predict the effect of a change of pressure, Le Chatelier‟s principle may be stated as: when pressure is
increased on a gaseous equilibrium reaction, the equilibrium will shift in a direction which tends to decrease the
pressure.
The pressure of a gaseous reaction at equilibrium is determined by the total number of molecules it
contains. If the forward reaction proceeds by the reduction of molecules, it will be accompanied by a
decrease of pressure of the system and vice versa. Let us consider a reaction,

The combination of A and B produces a decrease of number of molecules while the decomposition of C into
A and B results in the increase of molecules. Therefore, by the increase of pressure on the equilibrium it will
shift to right and give more C. A decrease in pressure will cause the opposite effect. The equilibrium will
shift to the left when C will decompose to form more of A and B.

The reactions in which the number of product molecules is equal to the number of reactant molecules,

are unaffected by pressure changes. In such a case the system is unable to undo the increase or decrease
of pressure.
In light of the above discussion, we can state a general rule to predict the effect of pressure changes on
chemical equilibria.
The increase of pressure on a chemical equilibrium shifts it in that direction in which the number of molecules
decreases and vice-versa.
Examples

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EFFECT OF CHANGE OF TEMPERATURE
Chemical reactions consist of two opposing reactions. If the forward reaction proceeds by the evolution of
heat (exothermic), the reverse reaction occurs by the absorption of heat endothermic).
Both these reactions take place at the same time and equilibrium exists between the two. If temperature of
a reaction is raised, heat is added to the system. The equilibrium shifts in a direction in which heat is
absorbed in an attempt to lower the temperature. Thus the effect of temperature on an equilibrium reaction
can be easily predicted by the following version of the Le
Chatelier‟s principle.
When temperature of a reaction is increased, the equilibrium shifts in a direction in which heat is absorbed.
Let us consider an exothermic reaction

In an endothermic reaction

the increase of temperature will shift the equilibrium to the right as it involves the absorption of heat.
This increases the concentration of the product Z.
In general, we can say that the increase of temperature favours the reverse change in an exothermic reaction
and the forward change in an endothermic reaction.

Formation of Ammonia from N 2 and H2

The synthesis of ammonia from nitrogen and hydrogen is an exothermic reaction.

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When the temperature of the system is raised, the equilibrium will shift from right-to-left which absorbs heat
(Le Chatelier’s principle) This results in the lower yield of ammonia. On the other hand, by lowering the
temperature of the system, the equilibrium will shift to the right which evolves heat in an attempt to raise the
temperature. This would increase the yield of ammonia. But with decreasing temperature, the rate of
reaction is slowed down considerably and the equilibrium is reached slowly. Thus in the commercial
production of ammonia, it is not feasible to use temperature much lower than 500°C. At lower temperature,
even in the presence of a catalyst, the reaction proceeds too slowly to be practical.

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