Unit

Elementary Thermochemistry, Rates of reaction,

Equilibrium and Thermodynamics

Content
1.0 Introduction
2.0 Learning Objectives
3.0 Learning Content
4.0 Thermochemistry
5.0 Rates of reactions
6.0 Chemical Equilibrium
7.0 Chemical Thermodynamics
8.0 Conclusion
9.0 Summary
10.0 Tutor-marked assignment
11.0 References/Further reading

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1.0 Introduction

This unit is a field of chemistry that gives attention to other sides of chemical reactions
which include energetics, the heat produced as well as the rate and how far of chemical
ations. The chemistry field is organized into sections under
thermochemistry, rates of reaction, equilibrium and thermodynamics in basic and
elementary details.

2.0 Objectives
After studying this unit, you should be able to:
i. Define thermochemistry
ii. Express thermochemical equations
iii. Explain the term of
iv. Demonstrate the rate of reaction expressions
v. Describe chemical equilibrium
vi. Express equilibrium reactions
vii. Define thermodynamics
viii. Express thermodynamics equations

3.0 Learning Content

3.1 Thermochemistry

Thermochemistry is the branch of science dealing with heat changes during a chemical
reaction. In this unit, we shall deal with heat change accompanying a chemical reaction
when it is carried out under constant volume or constant pressure. We shall define
standard enthalpy of formation and enthalpy changes in different chemical reactions.

3.1.1 Relationship between and

In thermochemistry, the enthalpy change accompanying a chemical reaction is called the
reaction enthalpy and is denoted by the symbol H, similarly, the internal energy change
accompanying a chemica action can be
carried out in two ways:

i) In a closed vessel, so that there is no volume change.

ii) In a pressure regulated vessel, so that there is no pressure change.

Accordingly, the heat change accompanying a chemical reaction can also be measured
in two ways, viz., heat change at constant volume (qv) and at constant pressure (qp).

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 qv qp =.
Since most reactions are carried out at constant pressure H is more commonly use than

Self-Assessment Exercise
1. In which two ways chemical reactions can be carried out?

3.1.2 Thermochemical Equations

Thermochemical equation is an expression of chemical equations showing how heat

energies and state of chemical spicie are involved along with reaction progress.

Examples of thermochemical equations:

H2(g) + ½O2(g) H2O(l) = -285.8 kJ mol (1)

GraphiteC(s) + O2(g) CO2(g) = -393.5 kJ mol-1 (2)

The symbols: s, I and g, refer to solid, liquid and gaseous states, respectively. If a
substance can exist in various allotropic forms, the particular form must be mentioned.

3.1.3 Enthalpy Changes

1. The standard enthalpy of formation of a compound is the enthalpy change
accompanying the formation of one mole of the compound from its elements in their
most stable state, all substances being in their standard state of pressure (1
Atmosphere) and temperature (298.15 K).
The standard enthalpy of formation is denoted by o f.

o f CO2 is expressed as:

Graphite C(s) + O2(g) CO2(g) = -393.5 kJ mol-1 (2)

2. The standard enthalpy of formation of solution (by dissolution of a solute in a

solvent) is the enthalpy change accompanying the complete dissolution of one mole
of solute in a definite amount of the solvent so as to give a solution of a specified
concentration. It is also the integral enthalpy of solution (or integral heat of solution).
These heat changes are dependent not only on the nature of the solute and solvent
but also on the composition of the solution. As an example, consider the dissolution
of 1 mol. Of NaCl in 200 mol. Water as represented by the equation,

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NaCl (s) + 200 H2O (l) (200 H2O) 0Soln = 5.36 kJ mol-1 (3)

Where 0Soln = 5.36 kJ mol-1 represents the integral enthalpy of solution.

In general, it can be positive or negative depending on the nature of the solute and solvent.
A special case of enthalpy of solution arises when a sufficiently large amount of solvent
is used so that further dilution does not bring any heat changes. This is defined as the
enthalpy of solution at infinite dilution.
For aqueous solution, this reaction is represented by,

Urea(s) + H2O(l) Urea(aq) (4)

The symbol (aq) is used to represent an aqueous solution which is so dilute that additional
dilution is not accompanied by any heat changes. In contrast to integral enthalpy of
solution, we define a quantity called differential enthalpy of solution. This is the enthalpy
change when 1 mol of solute is dissolved in a sufficiently large volume of solution of
concentration, c, so that the final concentration remains almost unchanged. The
differential enthalpy of solution depends on the concentration of the solution. It can be
calculated from the integral enthalpy of solution.

Another type of enthalpy term often used in solutions is the enthalpy of dilution, dil. This
is defined as the enthalpy change when a solution containing one mole of solute at
concentration Cl is diluted by the addition of solvent so that the final concentration is C2 It
is obvious that the enthalpy of dilution depends on both Cl and C2.

3. The standard enthalpy of formation of neutralisation of an acid is the enthalpy

change which accompanies the complete neutralization of a dilute aqueous solution of an
acid containing one mole of H+ ions by a dilute aqueous solution of a base containing one
mole of OH ions.

An example is given below:

HCl(aq) + NaOH (aq) (aq) + H2O 0neut = - 57.3 kJ mol-1 (5)

It is observed experimentally that the enthalpy of neutralization of strong acids or bases

(with strong bases or acids, respectively) is essentially the same (i.e., -57 kJ/mol). This is
because of the fact that strong acids and bases are completely dissociated in their
aqueous solutions, and the process of neutralization of strong acids and bases is
represented by

H+(aq) + OH-(aq) H2O o = -57.3 kJ mol-1 (6)

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Hence, the enthalpy of neutralization of strong acids and bases is the enthalpy of
formation of one mole of water from one mole each of H + and OH- ions. When a weak
acid or base is neutralised, the enthalpy of neutralisation deviates from the value of -57.3
kJ mol-1. This is due to the low dissociation of weak acids and bases; a portion of the
energy is utilised in the process of dissociation of the weak acids and bases.

4. The standard enthalpy of atomisation is the enthalpy change accompanying a

reaction in which a molecule is shattered into its component atoms. When a molecule
decomposes into atoms, the bonds are broken and the enthalpy increases. This is also
defined as the enthalpy of atomisation, 0atm, and is always positive. For example, the

enthalpy of the following reaction is the enthalpy of atomization of ethane gas:

C2H6(g) 2C(g) + 6H(g) atm = -2828.38 kJ mol-1 (7)

On analysis of atm for a large number of such reactions, it has been found that specific
values of bond enthalpies may be assigned to different types of bonds. These bond
enthalpies correspond to the decomposition of a molecule in the gaseous state to atoms
in the gaseous state. Enthalpy of atomization of graphite is useful in the calculation of
standard enthalpy of formation of organic compounds

Certain substances in the solid state when sublimed are converted into gaseous atoms.
Thus, graphite when heated is converted into gaseous atoms, and the heat required for
one mole can be called the molar enthalpy of atomization of graphite which is equal to
717 kJ mol-1. If graphite is considered the reference state for carbon, then the atomisation
can be written as follows

C(graphite) C(g) atm =717 kJ mol-1 (8)

3.1.4 Experimental Determination of Enthalpy of Combustion

Calorimeters are used for determining the enthalpy changes in various processes. As a
matter of fact, calorimetry is the most important experimental technique in
thermodynamics and a lot of attention has been devoted to make it very sensitive. At
present calorimeters are available which can measure heat and temperature changes
accurately. Let us explain here the experimental determination of the enthalpy of
combustion.
The enthalpy of combustion is determined using a Bomb Calorimeter (Fig. 1).

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 Fig. 1: Bomb Calorimeter.

The method consists of the combustion of a definite amount of the substance in an inner
vessel called the 'bomb'. The bomb is placed inside a definite quantity of water taken in
an outer vessel. The outer vessel is thoroughly insulated. The temperature readings of
the water kept in it are measured before and after the combustion using a sensitive
thermometer. From the heat capacity of the calorimeter, the amount of the substance
taken and the temperature readings, the enthalpy of combustion can be calculated. In
general, using adiabatic calorimeters, the enthalpies of reactions can be determined.

3.2 Rate of Reaction

The rate of chemical reactions are studied under chemical kinetics. Chemical kinetics
study also includes mechanisms of chemical reactions as well. The rate of a reaction
depends on many factors such as the concentration of the reactants, temperature,
catalyst, etc. Some of these factors shall be examined in this unit. We shall study thermal
reactions in this unit. We shall be defining the terms such as rate equation, rate law and
order of a reaction.

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3.2.1 Concentration and the rate of reaction
The rate of reaction or the velocity of reaction at a specified time is defined as the
decrease in the concentration of a reactant or the increase in the concentration of a
product per. unit time. The rate of reaction at a specified time is also known as the
instantaneous rate of reaction; it can be generally defined as the rate of change of
concentration of a specified species at a particular instant. While specifying the reaction
rate, we must mention the component with respect to which it is stated.

Let us consider a simple reaction,

As per the reaction stoichiometry, one molecule of B is formed for every molecule of A
consumed.

The reaction rate can be specified in the following ways:

i. We can measure the concentration of the reactant A at various time intervals.

From these values, we can specify the decrease in concentration of A with
respect to time at any particular instant. The reaction rate thus obtained is the
rate of consumption of A

Rate of consumption of A = Decrease in the concentration of A

ii. [A] means change in the concentration of A and -[A] means the decrease in
the concentration of A. While writing a rate expression with respect to a
reactant, there is a preceding negative sign (since jt is customary to express
the rate of a reaction as a positive quantity).
iii. We can measure the concentration of the product B at various time intervals.
From these values, we can arrive at the rate of formation of B at any particular
instant

Rate of formation of B

The rates of consumption of reactants and the rates of formation of products are related
through their stoichiometric coefficients.

For example, consider the decomposition of

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NO2, 2 NO2 (g) 2 NO (g) + O2 ( g )

We can write the relationship between the rates of consumption of NO2 and the rates of
formation of NO and O2 as follows:

(Rate of consumption of NO2) (Rate of formation of NO

Rate of formation of O2

Reaction rate

You can understand the above relationship if you bear mind that if two molecules of NO2
are consumed, two molecules of NO and one molecule of 0 2 are formed.

In other words, the reaction rate is equal to:

(i) half the rate of consumption of NO2
(ii) haIf the rate of formation of NO, and
(iii) the rate of formation of O2

Throughout this unit, the phrase rate of reaction means instantaneous reaction rate.

We shall shortly study the method of arriving at the reaction rates from the values of
concentrations of a component at different time intervals. The symbol is to be read as
delta. It denotes change in a property. In order to obtain a single value for the reaction
rate, it is necessary to divide the rate of consumption' of a reactant or the rate of formation
of a product by, the stoichiometric coefficient of the respective species.

To illustrate this, let us consider the reaction: aA + bB + dD,

In this reaction, A and B are reactants, and C and D are products; a, b, c and d are the
stoichiometric coefficients. The reaction rate is related to the rates of consumption of the
reactants and the rates of formation of the products as follows:

( )=

= ( )=

The number preceding the formula of a substance in the balanced equation is its
stoichiometric coefficient.

3.2.2 Calculation of Reaction Rate

Take for instance the following reaction:

2NO2(g) 2NO(g) + O2(g).

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In figure 2 below as well as table 1, we can see concentration (c) against time. (t) plots for
NO2, NO and O2.

The graphical method of calculation of the reaction rates for the consumption of NO2 and
for the formation of NO and O2 are illustrated. The reaction rate at any particular instant
is obtained by calculating the slope of a line tangent to the curve at that point.

Table 1: Concentrations of NO2 NO and O2 at Different Time Intervals at 673K.

Figure 2.: Concentration against time plot

3.2.3 Rate Law and Rate Constant

A rate law is an equation expressing the relationship between the instantaneous reaction
rate and the concentrations of the reactants in a reaction.

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The rate law for a simple reaction with one reactant may be of the following type:

Reaction rate = k [Reactant]

where k is called the rate constant or rate coefficient or the specific rate 'of the reaction.

Thus by definition, the rate constant is independent of concentration, but it may depend
on other factors.

In this equation, n refers to the order of the reaction;

The order with respect to a component is the power to which the concentration of that
component is raised in the rate law.

For example:
i) Decomposition of N2O5, It was found that the rate law is, is a first order reaction because
n=1.

Rate = k [N2O5] = k [N2O5]n

The k is the first order rate constant. Rate = k [Reactant].

The significance of this statement is that the reaction rate is proportional to the first power
of
concentration of N2O5.

It can be seen that if [reactant] = 1, such as above, then k = rate. For this reason. k is
called the specific rate.

If the n = 2 as was found in the decomposition of HI, then the decomposition of HI is a

second-order reaction. Again this means that the decomposition rate of HI is proportional
to the second power or square of the concentration of HI.

i.e., Rate = k [HI]2

Here k is the second-order rate constant.

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3.2.4 Order of Reaction and Stoichiometry
The rate laws as well as the order of the reaction must be determined experimentally;
these cannot be predicted from the stoichiometry of the reaction. The stoichiometry of
the reaction gives the relationship between the amounts of the reactants and the amounts
of the products. The stoichiometry of a reaction must be differentiated from the order of a
reaction.

Let us consider the following examples.

Example 1
The gas-phase decomposition of N2O5 yields NO2 and O2 at a particular temperature. The
experimentally observed rate law for the reaction rate.
Q: Comment on the order and the stoichiometry of the reaction.
A: It can be seen that the stoichiometric coefficient of N2O5 is 2 whereas the order of
reaction is 1.

Example 2
The balanced equation for the decomposition of nitrous oxide is given below:
2N2O(g) 2N2(g) + O2(g)
The rate law is, rate = k [N2O5]
Q: Comment on the order of the reaction and the stoichiometry.
A: Again the stoichiometric coefficient of N is 2 whereas the order of reaction is 1. In the
above two examples, the order of reaction and the stoichiometry are not identical. But
there are cases where the order and stoichiometric coefficient are identical. One of the
examples can be seen in the following reaction:
2HI (g) 2(g) + I2(g)

Rate = k [HI]
In the decomposition of HI, the order of reaction is two. The stoichiometric coefficient of
HI is also 2. From the above' examples, you can see that the stoichiometric coefficient
and the order of
the reaction need not be the same.

In general, for a reaction,

A + B + C products
if the rate law is experimentally found to be,
rate = k [A]m [B]n [C]p
The overall order of the reaction = m + n +p.

For example in the following reaction,

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 BrO-3 (aq) + 5 Br- (aq) + 6 H+ r2 ( aq ) + 3H2O(l)
Rate = k[ BrO3] [Br-] [H]2

The overall rate of the reaction is four, being first order in BrO3, first order in Br- and second
order in H+ The rate laws discussed so far are called differential rate laws. Such rate laws
describe the dependence of reaction rate on concentration. From these differential rate
laws, we can obtain the integrated rate laws through integration. The integrated rate laws
help us in relating the concentration of a substance to time. In other words, using the
integrated rate laws, we can calculate the concentration of a substance at any specified
time.

3.2.5 Experimental Methods of Rate Studies

Many physical and chemical methods are available for studying the reaction rates. Some
of them are listed below:

i) Volume or Pressure Measurement

When one or more of the components are gases, the reaction rate can be followed by
measuring the volume or pressure change. The partial pressures of the species are to be
calculated using the reaction stoichiometry.

ii) Titrimetry
Using acid-base or oxidation-reduction titrations, the reaction course can be followed if at
least one of the components in the reaction is an acid or a base and oxidizing agent or a
reducing agent.

iii) Conductometry or Potentiometry

If one or more of the ions are present or produced in the reaction, suitable methods can
be designed based on conductivity or potentiometric measurements.

iv) Spectrophotometry
When a component of the reaction has a strong absorption band at a particular
wavelength region, spectrophotometers could be used for measuring the reaction rate.
Photoelectric colorimeters are cheaper instruments and are mainly useful for reaction rate
studies in visible regions.

v) Polarimetry
When at least one of the components of a reaction is optically active, the reaction rate can
be studied from the measurements of optical rotation. Depending on the reaction under
study, the concentration of a reactant or a product is followed at various time intervals
using any of the methods mentioned above. These values are then used for

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calculating the rate constant. Examples are worked out in the next section to illustrate the
rate constant calculation. Before studying these examples, we shall discuss the method
of arriving at the integrated forms of rate laws.

3.3 Chemical Equilibrium

The chemical equilibrium of reactions is about the existence of constant reversibility of

reaction direction. In equilibrium, both forward and backward reactions coexist. At this
point, it is termed dynamic equilibrium.

In general, chemical reactions can be divided into two types - reversible and irreversible.
The reversible reactions are those in which the products can combine back to form the
reactants. However, in irreversible reactions, the same reactants cannot be formed back
from the products under a normal set of experimental conditions.

The idea of reversibility of chemical reactions was first realised by Berthollet in 1799. He
was trying to explain the cause for substantial amount of deposits of sodium carbonate
around some salt lakes of Egypt. He proposed that these deposits are formed due to high
concentration of sodium chloride in lake water which reacted with the carbonates present
on the shores. Normally, in a laboratory experiment, we find that calcium carbonate is
precipitated by the reaction of sodium carbonate with calcium chloride as represented by
the equation:

Na2CO3 +CaCl2 CaCO3 + 2NaCl

What Berthollet proposed was indeed a reverse reaction of the above and the cause for
reversibility was in some way connected to the high concentration of dissolved sodium
chloride.
Thus, it was realised that a chemical reaction such as given above .can proceed in both
the directions-from left to right or vice-versa-depending on the experimental conditions.
Further, experimental studies by Gilles and coworkers on the reaction between acetic
acid and ethyl alcohol giving ester and water, showed that the amount of ester formed
varied with the initial concentrations of the reactants at a fixed temperature and pressure.

CH3COOH + C2H5OH CH3COOC2H5 + H2O

In 1864, Guldberg and Wagge showed experimentally that there exists an equilibrium
between the reactants and products in a chemical reaction and that this equilibrium can
be reached from either direction (starting either from reactants or the products).

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Furthermore, the relation between the concentrations of the reactants and the products
can be expressed by a simple mathematical expression.

Let us consider two reactions to clarify these points. van't Hoff, in 1877; studied the
hydrolysis of ethyl acetate.

CH3COOC2H5 + H2O CH3COOH + C2H5OH

ester water acid alcohol

He observed that the ratio of the product of concentrations of the products to the product
of concentrations of the reactants is always constant at equilibrium and is independent of
the initial concentrations of the ester. Expressed mathematically,

K = [C2H5OH] x [CH3COOH]

[CH3COOC2H5] x [H2O]

Where
[ ] represents the molar concentration of a species. The constant, K, in the above
expression, has a fixed value for a particular reaction at a constant temperature and
pressure and is a measure of the extent of the reaction. A large value of K means the
numerator, is greater than the denominator.
This indicates the presence of a larger concentration of products as compared to the
concentration of reactants at equilibrium.

3.3.1 Determination of Equilibrium Constants

It is now clear from the above examples that if the initial concentrations and the extent of
the reaction are known, equilibrium constants can be calculated. The following two criteria
confirm the presence of an equilibrium condition:

1) The value of the equilibrium constant should be the same' when the equilibrium is
approached from either side.

2) The value of t h e equilibrium constant should be t h e same when the

concentrations of the reacting substances are varied greatly.

Once it is established that an equilibrium has been reached, the next step is to find out
the equilibrium concentration of at least one of the reactants or products in order to
calculate the extent of the reaction. This can be achieved either by chemical analysis or
by measurement of some physical property. The difficulty with the chemical analysis is
that the concentration will change during the course of the analysis.

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 Hence, only when the reaction can be stopped at equilibrium by some means (like
sudden cooling), can this method be used. Physical methods are more convenient since
they do not require stopping of the reaction. The physical properties commonly used for
this purpose are density, refractive index, electrical conductivity, light absorption etc.

3.3.2 Applications of Equilibrium Studies

i. Homogeneous Systems

When all the reactants and products are present in the same phase (i.e., gaseous or
liquid) we call it a homogeneous system.

Let us consider a few examples:

Example 1
At 298 K. it was found that Kp =7.13, for the reaction:2NO2 (g) 2O4 (g)What is o

for the reaction?

Solution
It is worth noting that Kp is given as a dimensionless quantity
o = -RTlnKp, = 2.303 RT log Kp

Substituting the values of R. T and Kp in the above equation, we get,

o = (- 2.303 x 8.314 x 298 log 7.13) J mol-1 = - 4.868 kJmol-1

ii. Heterogeneous Systems

Chemical reactions may also involve reactants or products in different phases. The most
common examples are found where solids and gases are present together at equilibrium.
Recall that at standard pressure of 1 bar, the activity of pure solid is unity. Hence, in

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writing the expression for equilibrium constant the activity or partial pressure terms for
solids can be eliminated. Thus, for the reaction,

CaCO3 (s) CaO (g) +CO2 (g)

Kp = PCaO. PCO2 / PCaCO3

= PCO2 [since PCaO= PCaCO3 = 1]

Also for the reaction,

C (s)+ H2O (g) CO (g) + H2 (g)
Kp = PCO . PH2 PC .= 1, carbon being in the solid form.
PH2O

Let us illustrate the heterogeneous systems with another example.

Example 2
NH4S(s) evaporates in an evacuated container at 298 K according to the equation.

NH4 3(g) +H2S(g), Find the pressure of each gas at equilibrium if Kp = 1.10 x
9 2
10 Pa at 298 K.

Solution
We can write for the above reaction, ..
Kp = PNH3 . PH2S (since PN4HHS = 1)
Since the two gases produced in the reaction are in equimolar quantities,
PNH3=PH2S
or Kp = P2NH3 = 1.10 x 109 Pa2
PNH3= PH2S = 3.32 x 104 Pa

iii. Liquid Solutions

So far we have discussed the reactions which take place in gaseous state or those
involving gaseous and solid phases. But the majority of reactions are carried out in liquid

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solutions. For example, you have already seen hydrolysis of an ester which can be written
as:

Ester + Water = Acid + Alcohol

Let us arrive at an expression useful in calculating the equilibrium constants of such

reactions.
In an ideal solution, the concentration of each component can be conveniently expressed
in terms of molarity. We can express K; of a general reaction (given below) which takes
place in a liquid solution; of course, the solution has to exhibit ideal behaviour.

aA + bB + ... pr + qQ + ...

In this reaction, A, B, ... etc., and P, Q, ... etc., are the reactants and products; a, b, ...
etc., and p, q... etc., are the stoichiometric coefficients.
We can write K; for the above reaction as,

Kc = Cpp . CqQ
CaA . CbB

Kc = mpP . mqQ = [P]p[Q]q

maA . mbB [A]a[B]b

The mp, mq, etc., are the molarities of substances. The square brackets denote
the concentrations of the species within the brackets.

Example
Calculate the equilibrium constant for the reaction,

CH3COOH (l) +C2H5OH (l) CH3COOC2H5 (l) +H2O (l)

at 298 K if 1.00 mol of acetic acid and 1.00 mol of ethyl alcohol are mixed together. At the
equilibrium point, the amount of water is 0.333 mol.

Solution
The concentrations of substances are given below assuming the total volume to be V
dm3:

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 [CH3COOC2H5] [H2O] [CH3COOH] [C2H5OH]
Concentration at equilibrium 0.333/V 0.333/V (1 - 0.333)/V (1 - 0.333)/V
(mol dm-3)

K = (0.667/V) (0.6671V) = 4.01

(0.333/V) (0.333/V)

Note that Kc tion is equal to zero. In

cases such as this, volume need not be known as it cancels out in the final expression. If
vi is not equal to zero, the final expression would contain volume term
and Kc will have suitable dimensions.

3.4 Chemical Thermodynamics

Thermodynamics is an incidence of transfer of energy between a system and its

surroundings through heat and work. However, it does not tell us anything about the
feasibility and direction of flow of energy.

3.4.1 First law of thermodynamics

The first law of thermodynamics can be stated as any increase in the energy of a system
must be accompanied by an equal decrease in the energy of the surroundings and vice
versa.

According to the first law of thermodynamics, all processes in which energy is conserved
are possible. For example, if a cup of hot tea is left on a Table then according to the first
law, it may be cooled by transferring energy to the surroundings or be heated by absorbing
energy from the surroundings. But we all know from daily experience that the cup of tea
will always cool till it acquires the temperature of the surroundings. Similarly, if a bottle of
perfume is opened in a room, the perfume spreads throughout the room. The reverse
process in which all the perfume vapours are collected in the bottle does not take place.

These are examples of what are known as spontaneous processes which are irreversible
and proceed only in one direction. Again, according to the first law, there exists a direct
relationship between heat and work. But it does not tell us whether heat can be completely
transformed into work and if so, what is the effect on the system and the surroundings.

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3.4.2 Second law of thermodynamics

The second law of· thermodynamics can be generalised to obtain the three statements:

1. The entropy of an isolated system tends to increase and reaches a maximum. This
implies that the most stable state of an isolated system is the state of maximum entropy.
Since the universe may be considered as an isolated system, it follows that the entropy
of the universe always increases.

2. It is impossible to transfer heat from a cold body to a hotter body without doing some
work. This was postulated by Clausius.

3. According to Kelvin, it is not possible to take heat from a source (i.e., a hot reservoir)
and convert all of it into work by a cyclic process without losing some of it to a colder
reservoir.

3.4.3 Entropy Changes in Chemical Reactions

The entropy is a measure of randomness or disorderliness in a system. The entropy

the total entropy of the reactants. The entropy change accompanying a general chemical
reaction of the type,

aA + bB+ .... cC + dD +

Thus, if SA, SB are the entropies of one mole of reactants, A, B, etc., and SC, SD......... of
the products, C, D, etc., then

= (cSc+dSD + .....) - (aSA + bSB +

where c, d, a, b, ... etc., are the stoichiometric coefficients .The variation of entropy change
for a reaction with temperature can therefore, be readily deduced.

4.0 Conclusion
We have discussed the heat change accompanying a chemical reaction when it is carried
out under constant volume or constant pressure. We have also defined standard enthalpy
of formation and enthalpy changes in different chemical reactions.

5.0 Summary

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In this unit, some of the aspects of thermochemistry have been discussed. The
relationship between and has been derived and its use in the calculation of internal
energy change and enthalpy change has been indicated. Standard enthalpy of formation
has been defined; the relationship between standard enthalpies of formation of
substances and standard enthalpies of reactions has been explained with an example.
6.0 Tutor-Marked Assignments
1. The standard enthalpy of formation of H2O(1) at 298 K is -285.8 kJ/mol. Calculate the
o(H2O)] for the formation of water at 298 K.

2. Calculate the standard enthalpy of formation of PCl5(s), using the following data:
P(s) + 1.5 Cl2 = -318kJ
PCl3(1) + Cl2(g) PCls(s) = -137kJ
.
7.0 References/Futher Reading
Principles of Physical Chemistry, Samuel H. Maron and Carl F. Prutton, Oxford and IBH
Publishing Co., New Delhi, 4th ed., 1985.
Physical Chemistry, Gilbert W. Castellan, Narosa Publishing House, Addison-
Wesley/Narosa (Indian Student Edition), Delhi, 3rd ed., 1983.
Physical Chemistry, P.c. Rakshit, Sarat Book House, Calcutta, 5th ed., 1988.
Physical-Chemistry through Problems, S.K. Dogra and S. Dogra, Wiley Eastern Ltd., New
Delhi, 1984.
Physical Chemistry-Principles and Problems, D.V.S. Jain and P. Jauhar, Tata McGraw-
Hill Pub. Company Ltd., New Delhi. 1990.

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