Chemical Thermodynamics MODULE - 4

Chemical Energetics

9
Notes

CHEMICAL
THERMODYNAMICS

When a chemical reaction occurs, it is accompanied by an energy change which

may take any of several different forms. For example, the energy change involved
in the combustion of fuels like kerosene, coal, wood, natural gas, etc., takes the
form of heat and light. Electrical energy is obtained from chemical reactions in
batteries. The formation of glucose, C6H12O6 by the process of photosynthesis
requires the absorption of light energy from the sun. Thus, we see that the energy
change that accompanies a chemical reaction can take different forms. In this
lesson, you shall study the reactions in which heat is either evolved or absorbed.

OBJECTIVES
After reading this lesson, you will be able to:
z define the commonly used terms in thermodynamics;
z differentiate between exothermic and endothermic reactions;
z explain the first law of thermodynamics;
z explain internal energy;
z define enthalpy and enthalpy change;
z state the relationship between enthalpy change and internal energy change;
z define enthalpies of formation, combustion, neutralisation, atomisation,
transition, solution and ionisation;
z state the relationship between enthalpy of reaction and enthalpies of formation
of reactants and products;

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z solve numerical problems based on the enthalpy changes;
z state Lavoisier-Laplace law and Hess’s law;
z calculate enthalpy of a reaction using Hess’s law;
z define bond enthalpy and bond dissociation enthalpy and
z calculate enthalpy of a reaction using bond enthalpy data.
Notes
9.1 SOME COMMONLY USED TERMS
In this lesson you would come across some frequently used terms. Let us
understand the meaning of these terms first.

9.1.1 System and Surrounding

If we are studying the reaction of two substances A and B kept in a beaker, the
reaction mixture of A and B is a system and the beaker and the room where it is
kept are surroundings as shown in figure 9.1

Surrounding System
A+B

Fig 9.1 : System and surroundings

System is the part of the physical universe which is under study, while the
rest of the universe is surroundings.
You know that hot tea/milk (let us call it a system) kept in a stoppered thermos
flask remains hot for a couple of hours. If this flask is made of perfect insulating
material, then there would be no exchange of matter or energy between the system
and the surroundings. We call such a system an isolated system.
Isolated system is a system which can exchange neither matter nor energy
with the surroundings.
If we keep hot tea/milk in a stoppered stainless steel flask, it will not remain hot
after some time. Here energy is lost to the surroundings through the steel walls,
but due to stopper, the matter will not be lost. We call this system a closed system.
Closed system is a system which can exchange energy but not matter with
the surroundings.

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If we keep stainless steel flask or thermos flask open, some matter will also be
lost due to evaporation along with energy. We call such a system an open system.
Plants, animals, human beings are all examples of open systems, because they
continuously exchange matter (food, etc) and energy with the surroundings.
Open system is a system which can exchange both energy and matter with
surroundings.
Notes
9.1.2. State of a System
We describe the state of a system by its measurable properties. For example, we
can describe the state of a gas by specifying its pressure, volume, temperature
etc. These variable properties are called state variables or state functions. Their
values depend only on the initial and final state of the system and not on the path
taken by the system during the change. When the state of a system changes, the
change depends only on the initial and the final state of the system (Fig 9.2).
B (p2 , T2 )
Final State

I
II
III

A (p1 , T1 )
R Initial State

T
Fig. 9.2 : Change of state from initial state to final state through three paths I, II and
III. The difference p2 – p1 and T2 – T1 are independent of the path since pressure and
temperature are state functions.
State functions are those functions which depend only on the state of the
system.
Change in state of a system is defined by giving the initial and the final state of the
system. We can understand it by considering another example. We travel from
one point to another. The distance travelled depends on the path or the route we
take. But the separation between these two points on the earth is fixed. Thus,
separation is a state function, but not the distance travelled.

9.1.3 Properties of a System

As stated earlier, the measurable properties of a system are called state variables.
They may be further divided into two main types.

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(i) Extensive property (variable) is one whose value depends upon the size
of the system. For example, volume, weight, heat, etc.
(ii) Intensive property (variable) is one whose value is independent of the size
of the system. For example, temperature, pressure, refractive index,
viscosity, density, surface tension, etc.
You may note that an extensive property can become an intensive property by
Notes specifying a unit amount of the substance concerned. For example, mass and
volume are extensive properties, but density (mass per unit volume) and specific
volume (volume per unit mass) are intensive properties.

9.1.4 Types of Processes

Let us first understand what do we mean by a process. Suppose we want to raise
the temperature of the system. We may do it by heating it. Here, heating is the
process.
The method of bringing about a change in state is called process.
Processes could be of different types. The different types of processes are explained
below.
(i) Isothermal process: Ice melts at 273 K and 1 atm pressure. The temperature
does not change as long as the process of melting goes on. Such processes
are examples of isothermal process. We can define isothermal process as
followes.
When the temperature of the system remains constant during various
operations, then the process is said to be isothermal. This is attained either
by removing heat from the system or by supplying heat to the system.
(ii) Adiabatic Process: If an acid is mixed with a base in a closed thermos
flask, the heat evolved is retained by the system. Such processes are known
as adiabatic processes because the thermos flask does not allow exchange
of heat between the system and the surroundings. Adiabatic process can
be defined as follows:
In an adiabatic process there is no exchange of heat between the system and
the surroundings. Thus, in adiabatic processes there is always a change in
temperature.
(iii) Reversible Process: In a reversible process, the initial and the final states
are connected through a succession of equlibrium states. All changes
occuring in any part of the process are exactly reversed when it is carried
out in the opposite direction. Thus both the systems and its surroundings
must be restored exactly to their original state, when the process has been
performed and then reversed.

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Let us understand it by an example. Imagine a liquid in equlibrium with its vapour
in a cylinder closed by a frictionless piston, and placed in a constant temperature
bath as shown in figure. 9.3. If the external pressure on the piston is increased by
an infinitesimally small amount, the vapours will condense, but the condensation
will occur so slowly that the heat evolved will be taken up by the temperature
bath. The temperature of the system will not rise, and the pressure above this
liquid will remain constant. Although condensation of the vapor is taking place,
the system at every instant is in the state of equilibrium. If the external pressure is Notes
made just smaller than the vapour pressure, the liquid will vaporize extremely
slowly, and again temperature and pressure will remain constant.

Cylinder with piston

Vapour

Liquid

Constant temperature bath

Fig 9.3 : Reversible process

Reversible processes are those processes in which the changes are carried
out so slowly that the system and surroundings are always in equilibrium.
(iv) Irreversible Processes: In the above example rapid evaporation or
condensation by the sudden decrease or incease of the external pressure,
will lead to non-uniformity in temperature and pressure within the system
and the equilibrium will be disturbed. Such processes are called as
irreversible processes.

9.1.5 Standard States

You have seen that a system is described by the state variables. In order to compare
the energies for different compounds, a standard set of conditions is chosen. This
refers to the condition of 1 bar pressure at any specified temperature, with a
substance in its most stable form.

9.2 EXOTHERMIC AND ENDOTHERMIC REACTIONS

(i) Add a few cm3 of dilute hydrocholoric acid in a test tube containing a few
pieces of granulated zinc and observe the evolution of a gas. Feel the test
tube. It would be hot.

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(ii) You must have observed that when some water is added to quick lime to
prepare white wash, a lot of heat is evolved.
(iii) When a fuel like cooking gas or coal is burnt in air, heat is evolved besides
light. Many chemical reactions lead to release of energy (heat) to the
surroundings. We call these type of rections as exothermic reactions.
Exothermic reactions are those reactions which proceed with the evolution
Notes of heat.
Let us now consider the following reactions:
(i) Add a small amount of solid ammonium chloride in a test tube half-filled
with water. Shake and feel the test tube. It will feel cold.
(ii) Similarly repeat this experiment with potassium nitrate and feel the test
tube, it will feel cold.
(iii) Mix barium hydroxide with ammonium chloride in small quantities in water
taken in a test tube. Feel the test tube. It will be cold.
In all the above processes we see that heat is absorbed by the system from the
surroundings. Such reactions are called endothermic reactions.
Endothermic reactions are those reactions which proceed with the absorption
of heat from the surroundings.

9.3 THERMOCHEMICAL EQUATIONS

You are familiar with equations for chemical reactions. Now we shall write the
chemical equations which will specify heat energy changes and states of the
reactants and products. These are called the thermochemical equations. For writing
these equations, we follow the conventions listed below:
(i) The heat evolved or absorbed in a reaction is affected by the physical state
of the reacting substances. Therefore, gaseous, liquid and solid states are
represented by putting symbols (g), (l), and (s) along side the chemical
formulae respectively.
For example, to represent burning of methane in oxygen, we write
CH4(g) + 2O2 (g) → CO2 (g) + 2H2O (l) + heat
In writing thermochemical reactions, we denote the amount of heat evolved
or absorbed by a symbol ΔH. The amount of heat evolved or absorbed is
written after the equation followed by semicolon. ΔH is negative for
exothermic reactions and it is positive for endothermic reactions.
For example:
An exothermic reaction is written as
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l) ; ΔH = – 891 kJ

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Whereas an endothermic reaction is written as
H2 (g) + I2 (g) → 2HI (g) ; ΔH = 52.2 kJ
(ii) In case of elements which exhibit allotropy, the name of allotropic
modification is mentioned. For example,
C (graphite), C (diamond), etc.
(iii) The substances in aqueous solutions are specified using the symbol (aq). Notes
For example NaCl (aq) stands for an aqueous solution of sodium chloride.
(iv) Thermochemical equations may be balanced even by using fractional
coefficients, if so required. The coefficients of the substances of the chemical
equation indicate the number of moles of each substance involved in the
reaction and the ΔH values given correspond to these quantities of substances.
(v) In case the coefficients are multipied or divided by a factor, ΔH value must
also be multiplied or divided by the same factor. In such cases, the ΔH value
will depend upon the coefficients. For example, in equation.

H2 (g) + 1
2 O2 (g) → H2O (g) ; ΔH = – 242 kJ

If coefficients are multiplied by 2, we would write the equation

2H2 (g) + O2 (g) → 2H2O (g) ; ΔH = 2 (– 242) = – 484 kJ

9.4 THE FIRST LAW OF THERMODYNAMICS

You have learnt that chemical reactions are accompanied by energy changes.
How do we determine these energy changes? You know that we cannot create or
destroy energy. Energy only changes from one form to another. This is the
observation made by many scientists over the years. This observation has taken
the form of first law of thermodynamics. It has been found valid for various
situations. We state this law as follows:
Energy can neither be created nor destroyed. The total energy of the universe
or an isolated system is constant.
Mathematically the first law of thermodynamics is stated as:
ΔU = q + w (9.1)
where ΔU = change in internal energy, q = heat absorbed by the system, and w =
work done on the system. These terms are explained as:

9.4.1 Internal Energy (U)

Every system has a definite amount of energy. This amount is different for different
substances. It includes translational, vibrational and rotational energies of
molecules, energy of electrons and nuclei.

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The internal energy may be defind as the sum of the energies of all the
atoms, molecules or ions contained in the system.
It is a state variable. It is not possible to measure the absolute values of internal
energy. However, we can calculate the change in internal energy. If the internal
energy of the system in the initial state is U1 and that in the final state is U2, then
change in internal energy Δ U is independent of the path taken from the intial to
Notes the final state.
We can write this change as:
Δ U = U2 – U1
The internal energy of the system can be changed in two ways :
(i) either by allowing heat to flow into the system or out of the system; and
(ii) by work done on the system or by the system

9.4.2 Heat(q) and Work(w)

Heat and work are not state functions. This is because the values of both q and w
depend upon the way in which the change is carried out.
Since the law deals with the transfer of heat and work, we assign some signs to
these quantities. Any thing which increases the internal energy of a system is
given a positive sign.
Heat given to the system (q) and work done on the system (w) are given positive
signs. Let us illustrate this with an example.
If a certain change is accompanied by absorption of 50 kJ of heat and expenditure
of 30 kJ of work,
q = + 50 kJ
w = – 30 kJ
Change in internal energy ΔU = (+ 50 kJ) + (– 30 kJ) = = + 20 kJ
Thus the system has undergone a net increase in the internal energy of –20 kJ.
Change in the internal energy of the surroundings wll be 20 kJ.

9.4.3 Work of Expansion

Let us assume that pressure p is constant and the volume of the system changes
from V1 to V2. The work done by a system is given as
w = – p (V2 – V1) = – p Δ V (9.2)

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(Here we have taken minus sign, because the work is done by the system). Let us
substitute the expression given for w in equation 9.1.
We get
ΔU=q–pΔV (9.3)
If the process is carried ot at constant volume, i.e. Δ V = 0, then
Notes
Δ U = qv (9.4)
The subscript v in qv denotes that volume is constant.
The equation 9.4 shows that we can determine internal energy change if we
measure the heat gained or lost by the system at constant volume. However, in
chemistry, the chemical reactions are generally carried out at constant pressure
(atmospheric presure). What do we do then? Let us define another state function,
called, enthalpy.

9.4.4 Enthalpy (H)

For measuring heat lost or gained at constant pressure, we define a new state
function called enthalpy. It is denoted by the symbol H and is given by
H=U+pV (9.5)
Enthalpy change, Δ H, is given by
Δ H = Δ U + Δ(pV) (9.6)
or Δ H = Δ U + p Δ V + V Δ p
If the change is carried out at constant pressure, then Δ p = 0. The equation 9.6
will become
Δ H = Δ U + p Δ V (at constant pressure) (9.7)
Substituting the value of Δ U from equation 9.3 in equation 9.7, we get
ΔH=q–pΔV+pΔV
= q (at constant pressure)
We denote q at constant pressure by qp hence
Δ H = qp (9.8)
Equation 9.8 shows that by measuring heat lost or gained at constant pressure,
we can measure enthalpy change for any process.

9.4.5 Relation between ΔH and ΔU

For liquids and solids, the difference between ΔrH and ΔrU is not significant but
for gasses, the difference is significant as we will see here.

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Let VA be the total volume of the gaseous reactants,
VB the total volume of the gaseous products,
nA the number of moles of gaseous reactants,
and nB the number of moles of gaseous products, at constant pressure and
temperature.
Notes Then, using ideal gas law, we can write
p VA = nA RT (9.9)
p VB = nB RT (9.10)
Subtracting equation 9.9 from equation 9.10, we get
p VB – pVA = nB RT – nA RT = (nB – nA) RT
p (VB – VA) = p Δ V = Δ ngRT
At constant pressure
ΔH=ΔU+pΔV
Therefore Δ H = Δ U + Δ ng RT
Here Δ ng = (number of moles of gaseous products) - (number of moles of gaseous
reactants)
Thus we can find the value of Δ H from Δ U or vice versa.
For solids and liquids Δ V is very small. We can neglect the term p Δ V, hence Δ H
is nearly the same as Δ U.

INTEXT QUESTIONS 9.1

1. Which of the following is false ?
(a) The reaction
H2(g) + Cl2(g) → 2HCl (g) + 185 kJ
is endothermic.
(b) Enthalpy change is a state function.
(c) Standard state condition for a gaseous system is 1 bar pressure at a
specified temperature.
2. For the reaction at 298 K,

1 3
N2(g) + H2 (g) → NH3(g) ; Δ H = - 46 kJ
2 2

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(a) What is the value of Δng ?
(b) Calculate the value of Δ U at 298 K?
3. Which of the following will increase the internal energy of a system?
(a) Heat given to the system
(b) Work done by the system
Notes

9.5 STANDARD ENTHALPY OF REACTIONS

Let as denote total enthalpy of reactants as Hreactants and total enthalpy of products
as Hproducts. The difference between these enthalpies, Δ H, is the enthalpy of the
reaction
Δ rH = Hproducts – Hreactants
When Hproducts is greater than H reactants then Δ H is positive and heat is absorbed in
the reaction, and the reaction will be endothermic. For example,
H2(g) + I2(g) → 2HI (g); ΔrH = 52.5 kJ
When Hproducts is less than Hreactants then Δ H is negative and heat is evolved in the
reaction, and the reaction will be exothermic. For example,
CH4(g) + 2O2(g) → CO2(g) + 2Η2Ο (l); ΔrH = – 890.4 kJ
Enthalpy of a reaction changes with pressure and temperature. It is convenient to
report enthalpies of the reactions in terms of standard state of substances as we
have defined earlier. When substances are in their standard states, we call the
enthalpy of reaction as standard enthalpy of reaction. It is defined as the enthalpy
change for a reaction, when the reactants and the products are in their standard
states. It is donoted by Δr H 0.

Δf H°)
9.5.1 Enthalpy of formation (Δ
The enthalpy change when one mole of a pure compound is formed from its
elements in their most stable states is called the enthalpy of formation and is
denoted by Δf H0.
When the reacting elements and the products formed are all in their standard
states, the enthalpy change accompanying the chemical reaction is called the
standard enthalpy of formation and is denoted by Δf H 0. By convention, we take
the standard enthalpy of formation of an element in its most stable state as zero.
For example:
C(Graphite) + O2(g) → CO2 (g) ; Δf H0 = – 393.5 kJ mol–1

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This means that carbon dioxide is formed from its elements in their most stable
states. Carbon in the form of graphite and at room temperature and gasesous O2
and CO2 being at 1 bar.

Δcomb H°)
9.5.2 Enthalpy of Combustion (Δ
Enthalpy of combustion is the enthalpy change (heat evolved) accompanying
the complete combustion of 1 mole of a substance in oxygen at a given
Notes
temperature and 1 bar pressure.
For example :
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l) ; Δcomb H 0 = – 1365.6 kJ
Enthalpy of combutsion of C2H5OH(l) is – 1365.6 kJ mol–1

Δneut Hº)
9.5.3 Enthalpy of Neutralization (Δ
Enthalpy of neutralization is the enthalpy change (heat evolved) when one mole
of hydrogen ions (H+)is neutralized by one mole of hydroxyl ions (OH-) in dilute
aqueous medium to form water.
For example:
H+ (aq) + OH– (aq) → H2O (l) ; Δneut H = –57 kJ/mol
Enthalpy of neutralization of a strong acid with a strong base is always constant
having a value of –57 kJ. However, enthalpy of neutralization of strong acid with
a weak base or weak acid with a strong base will be different, because of varying
degree of ionization of weak acids and bases.

ΔaH0)
9.5.4 Enthalpy of atomisation (Δ
It is the change in enthalpy when one mole of a substance is converted into its
atoms in gaseous state at a given temperature and 1 bar pressure
Examples:
(i) C(graphite) ⎯→ C(g) Δa H 0 = 716.68 kJ mol–1
In case of elements in solid state, it is equal to the enthalpy of sublimation.
(ii) CH4(g) ⎯→ C(g) + 4H(g) Δa H 0 = 1660 kJ mol–1
(iii) Hg(l) ⎯→ Hg(g) Δa H 0 = 61.32 kJ mol–1
For elements in liquid state, it is equal to the enthalpy of vaporization.

ΔtrsH0)
9.5.5 Enthalpy of transition (phase transformation) (Δ
It is the change in enthalpy when one mole of substance changes from one phase
to another at a constant temperature and under 1 bar pressure. Phase transition/
transformation is a general term that includes the following:

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Name of Process Process Specific symbol

(i) Sublimation: Solid ⎯→ Gas Δsub H 0

(ii) Vaporisation: Liquid ⎯→ Gas Δvap H 0

(iii) Fusion: Solid ⎯→ Liquid Δfus H 0

Notes
(iv) Transition Solid (one crystalline Δtrs H 0

form) ⎯→ Solid
(another crystalline form)
Examples:

(i) Hg(l) ⎯→ Hg(g) Δtrs H 0 /Δvap H 0 = 61.32 kJ mol–1

(ii) H2O(l) ⎯→ H2O(g) Δtrs H 0 /Δvap H 0 = 4079 kJ mol–1

(iii) H2O(s) ⎯→ H2O(g) Δ trs H 0 /Δsub H 0 = 6.01 kJ mol–1

(iv) C(graphite) ⎯→ C(diamond) Δtrs H 0 = 1.90 kJ mol–1

ΔsolH0)
9.5.6 Enthalpy of Solution (Δ
It is the change in enthalpy when one mole of a solute is dissolved in a specific
amount of a solvent at a constant temperature and under 1 bar pressure. It is
also known as integral enthalpy of solution. The amount of solvent is mentioned
as its of moles in which one mole of solute is dissolved.
Examples

(i) HCl(g) + 10H2O(l) ⎯→ HCl .10 H2O Δsol H 0 = –69.5 kJ mol–1

(ii) HCl(g) + 25H2O(l) ⎯→ HCl .25 H2O Δsol H 0 = –72.2 kJ mol–1

ΔionH0)
9.5.7. Enthalpy of ionization (Δ
It is the change in enthalpy when one mole of a weak electrolyte ionizes
completely in its solution at a constant temperature and under 1 bar pressure
Example:

HCN(aq) ⎯→ H+(aq) + CN–(aq) Δ ion H 0 = 43.7 kJ mol–1

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9.6 LAWS OF THERMOCHEMISTRY
There are two laws of thermochemistry : The Lavoisiter–Laplace law and the
Hess’s Law of Constant Heat Summation.
Lavoisier – Laplace Law : When a chemical equation is reversed, the sign of
ΔrH is changed. For example,
Notes N2 (g) + O2 (g) → 2NO (g); ΔrH = 180.5 kJ
2NO (g) → N2 (g) + O2 (g); ΔrH = –180.5 kJ
Hess’s Law of constant heat summation: Hess’s law states that the enthalpy of
reaction is independent of the number and the nature of the intermediate steps.
You have learnt that standard enthalpy change of the reaction
C (graphite) + O2(g) → CO2(g)
is equal to – 393.5 kJ mol–1. This value can be determined with the help of a
calorimeter. However, there are some reactions for which the direct measurement
of enthalpy in the laboratory is not possible. For example the standard enthalpy
change for the reaction,

1
C (graphite) + O (g) → CO (g)
2 2

cannot be to determined with the help of calorimeter because the combustion of

carbon is incomplete unless an excess of oxygen is used. If excess of oxygen is
used, some of the CO is oxidized to CO2. How can then we determine the enthalpy
change for such reactions when direct measurement is not possible?
Since Δ H is a state function, it is not dependent on the way the reactions are
carried out. Let us carry out the reactions as follows.
(1) First carry out the following reaction and let ΔrH10 be the enthalphy change
of the reaction.

C (graphite) + O2 (g) → CO2 (g); ΔrH10 = –393.5 kJ/mol.

(2) Now let us write the reaction for which we have to determine the enthalpy
change of the reaction and let it be ΔrH2º
1
C (graphite) + O (g) → CO(g); ΔrH20 = ?
2 2
(3) Let us carry out the following reactions and let ΔrH30 be the enthalpy change
of the reaction
1
CO(g) + O (g) → CO2(g); ΔrH30 = – 283.0 kJ
2 2

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We have obtained the products CO2(g) from carbon and oxygen through two
routes, namely first as in step (1) and second as in step (2) + (3).
According to Hess’s Law
Δr H10 = Δr H20 + Δr H30
or Δr H20 = Δr H10 – Δr H30
Notes
Fig 9.4 shows alternate paths for the conversion of carbon and oxygen to carbon
dioxide.
Reactants = C (graphite) + O2(g)

D,H°2 1
C(graphite) + 2 O2(g) ® CO(g)
C (graphite) + O2(g)

1
D,H°1 CO(g) + 2 O2(g)
Path I D,H°3
Path II

Products = CO2(g)

Fig 9.4 : Alternate paths for the conversion of carbon and oxygen to carbon dioxide

The result of Hess’s law is that thermochemical equations can be added and
substracted just like algebraic equations to get the desired reaction. A useful
practical application of this law is that we can calculate enthalpy changes for the
reactions which cannot be studied directly as in the above case.
To obtain the enthalpy change for the reactions, we algebraically combine the
known values of Δr H0 in the same way as the reactions themselves,
Thus C(graphite) + O2 (g) → CO2 (g) ; ΔrH10 = –393.5 kJ/mol
1
– [CO(graphite) + O (g) → CO2 (g)]; Δr H30 = – 283.0 kJ/mol
2 2

1
C(graphite) + O (g) → CO(g) ; Δr H20 = [ (−393.5) − (−283.0)]
2 2
= –110.5 kJ/mol
Example 9.1 The heat evolved in the combustion of glucose is shown in the
following equation:
C6H12O6 (s) + 6O2(g) → 6CO2 (g) + 6H2O(l); ΔcombH = – 2840 kJ/mol
How much energy will be required for the production of 1.08 g of glucose?
Soluton: Glucose will be prepared by the reverse reaction.

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6CO2(g) + 6H2O (l) → C6H12O6 (s) + 6CO2 (g) ; Δ H = 2840 kJ.
This equation refers to 1 mol of glucose (180 g of glucose).
Production of 180 g of glucose requires 2840 kJ of energy. Therefore, production
of 1.08 g will require;

2840 kJ
Notes 180 g × 1.08 g = 17.04 kJ

Example 9.2 Calculate the standard enthalpy of formation of ethane, given that
C(graphite) + O2(g) → CO2 (g) ; Δf H0 = – 394 kJ mol-1

1
H2(g) + O (g) → H2O(l); Δ fH0 = – 286 kJ mol-1
2 2

7
C2H6(g) + O (g) → 2CO2(g) + 3H2O (l); Δr H0 = – 1560 kJ mol-1
2 2

Solution: Given that

C(graphite) + O2(g) → CO2(g) ; ΔrH01 = –394 kJ/mol (1)

1
H2(g) + O2(g) → H2O(l) ; ΔrH02 = – 286 kJ/mol (2)
2

7
C2H6(g) + O2(g) → 2CO2(g) + 3H2O(l) ; ΔrH03 = –1560 kJ/mol (3)
2

The required equation is

2C(graphite) + 3H2(g) → C2H6(g) ; Δf H0 = ? (4)
To obtain the above equation, mulitply equations (1) by 2 and equation (2) by 3
and then add both the equations we get

7
2C(graphite) + 3H2(g) + O (g) → 2CO2(g) + 3H2O(l) ; ΔrH05 = –1656 kJ/mol (5)
2 2

(where ΔrH05 = 2ΔrH01 + 3ΔrH02 = 2 × (–394) + 3 × (–286) = –1656 kJ/mol)

Subtract equation (3) from equation (5) to get the equation (4)
2C(graphite) + 3H2(g) → C2H6(g) ;
where Δf H0 = –1656 – (–1560) = –96 kJ/mol
Thus, standard enthalpy of formation of ethane is –96 kJ/mol

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INTEXT QUESTIONS 9.2

1. Which of the following is true?
(a) Enthalpy of formation is the heat evolved or absorbed when one gram
of a substance is formed from its elements in their most stable states.
(b) When one mole of H+ (aq) and 1 mole of OH— (aq) react, 57.1 kJ of Notes
energy is absorbed.
(c) In the thermochemical equation,
C(graphite) + O2 (g) → CO2(g) ; Δf H0 = –394 kJ mol–1
Δ fH0 is known as enthalpy of formation of CO2(g)
2. Calculate the enthalpy change for complete combustion of 29.0 g of butane,
if
3
C4H10(g) + O (g) → 4CO2 (g) + 5H2O (l) ; Δcomb H0 = – 2658 kJ
2 2

3. Calculate the standard enthalpy of the reaction

2H2S(g) + SO2(g) → 3S (s) + 2H2O (l)
given that
Δf H0 (H2S) = – 20.6 kJ mol–1
Δf H0 (SO2) = – 296.9 kJ mol–1
Δf H0 (H2O) = – 289.9 kJ mol–1

9.7 BOND ENTHALPIES

In a chemical reaction, you have seen that energy is either absorbed or evolved.
Do you know the origin of this change in energy? You know that bonds are
broken and new bonds are formed in chemical reactions. Energy changes take
place in breaking some bonds of the reactants and in forming new bonds of the
products. So the energy changes in a chemical reaction are a result of energy
changes in breaking and forming of bonds. Let us consider the gaseous reactions,
because in these, we encounter the energy changes due to breaking and forming
of bonds only.
At high temperature, hydrogen molecules dissociate into atoms as
H2(g) → H (g) + H(g) ; ΔrH = 435 kJ/mol
The heat absorbed in this reaction is used to break the chemical bonds holding the
hydrogen atoms together in the H2 molecules. For a diatomic molecule like H2(g),

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we define bond dissociation energy as the enthalpy change of the reaction in
which one mole of the gaseous molecules are dissociated into gaseous atoms.
Now, let us consider a polyatomic molecule like H2O(g). The dissociation may
involve fragmenting the molecules into an atom and a group of atoms, called a
radical, as in
H2O (g) → H (g) + OH (g) ; ΔrH0 = 502 kJ/mol
Notes
OH(g) → O(g) + H (g) ; ΔrH0 = 427 kJ/mol
In the first reaction, one of the two OH bonds in H2O (g) dissociates with an
enthalpy change of 502 kJ/mol and in the second reaction, second OH bond
dissociates with an enthalpy change of 427 kJ/mol. It is clear that the dissociation
energy of the O – H bond is sensitive to its environment. However, the difference
is not very large. We take the average value (464.5 kJ/mol in this case) in case of
polyatomic molecules and call it bond enthalpy.
Bond enthalpy is defined as the average amount of enthalpy change involved
in the dissociation of one mole of bonds present in different gaseous
compounds.
Now you know the distincton between bond dissociation enthalpy and bond
enthalpy. Bond dissociation enthalpy refers to breaking a particular bond in a
particular molecule whereas bond enthalpy is the average value of bond dissociation
energies for a given type of bond. The bond enthalpies of some bonds are listed in
table 9.1.
By using bond enthalpies (B.E.) it is possible to estimate the energy released
when a gaseous molecule is formed from its gaseous atoms. For example, the
energy released at constant pressure for the reaction (ΔrH),
3H(g) + C(g) + Cl(g) → CH3Cl(g)
is the sum of the energies of three C – H bonds, and one C – Cl bond, all taken
with a negative sign because energy is released. Using the values of bond enthalpies
(B.E.) from table 9.1 we get,
ΔrH = – 3 × B.E. (C – H) – B.E. (C – Cl)
= (–3 × 415 – 335) kJ mol–1
= (–1245 – 335) kJ mol–1
= – 1574 kJ mol–1
We will now show you how to use bond enthalpy data to estimate the enthalpy of
a reaction, when direct calorimetric data are not available. Note that in section
9.7 we used enthalpy of formation data to estimate enthalpy of a reaction. In

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principle, bond enthalpy data can be used to calculate ΔrH for a chemical reaction
occuring in gaseous state by making use of difference in energy absorbed in
breaking the bonds in reactants and energy released in formation of bonds in
products.
ΔrH = Σ B.E. (reactants) – Σ B.E. (products) (9.10)
Table 9.1 : Average Bond enthalpies
Notes
-1
BOND BOND ENTHALPY /(kJ mol )
H–H 435
C–H 415
C – Br 284
C–C 356
C=C 598
Br – Br 193
Cl – Cl 242
C – Cl 339
F–F 155
H – Cl 431
H–O 462
H–N 390
H–F 563
H – Br 366
H–I 296
C–O 355
C=O 723
C–N 391
C=N 619
C ≡ N 878
C ≡ C 832

Example 9.3: Use bond enthalpy data given in table 9.1 to calculate the enthalpy
of the reaction.
CH3 (g) + Cl2 (g) → CH3Cl (g) + HCl (g)
Solution: 1. Write the equation using structural formula

H H

H – C – H + Cl – Cl ® H – C – Cl + H – Cl

H H

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2. List the bonds broken and bonds formed under the equation as shown
H H

H – C – H + Cl – Cl H – C – Cl + H – Cl

H H
number of bonds broken number of bonds formed
Notes
C–H=4 C – Cl = 1
Cl – Cl = 1 H – Cl = 1
C–H=3
3. Look up the values of bond enthalpies for the bonds in the reactants and
products and list them as shown
Reactants Products
–1
B.E. (C – H) = 435 kJ mol B.E. (Cl – C) = 339 kJ mol–1
B.E. (Cl – Cl) = 242 kJ mol–1 B.E. (H – Cl) = 431 kJ mol–1
B.E. (C – H) = 435 kJ/mol
4. Use equation 9.10,
Enthalpy of the rection Δr H = Σ B.E. (reactants) - Σ B.E. (products)
= 4[B.E. (C – H) + B.E. (C – Cl)] – [B.E. (C – Cl) + B.E.
(H – Cl) + 3 B.E. (C – H)]
= [4 × 435 + 242] – [339 + 431 + 3 × 435] = – 93 kJ
Now let us take one example in which we calculate the enthalpy of a reaction
using
(i) Enthalpy of formation data
(ii) Bond enthalpy data.

Example 9.4: Calculate Δr H° for the reaction

Cl2 (g) + 2HF (g) → 2HCl (g) +F2 (g)
(a) Using enthalpy of formation data
Δf H° (HCl) = – 92.5 kJ
Δf H° (HF) = – 269 kJ
(b) Using bond enthalpy data
B.E. (H – Cl) = 431 kJ mol–1
B.E. (F – F) = 155 kJ mol–1

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B.E. (H – F) = 563 kJ mol–1
B.E. (Cl – Cl) = 242 kJ mol–1
Solution :

(a) Using enthalpy of formation of compounds,

ΔrH = [2ΔfH0 (HCl) + ΔfH (F2)] – [2ΔfH0 (HF) + ∆fH0(Cl2)]
Notes
= [2x (– 92.5) + 0] – [2x – (269) + 0] kJ

= – 185 kJ + 538 kJ

= + 353 kJ

(b) Using bond enthalpies

ΔrH0 = ∑ B.E. (reactants bonds) – ∑ B.E. (products bonds)

= [B.E. (Cl – Cl) + 2B.E. (H – F)] – [2 B.E. (H – Cl) + B.E. (F – F)]

= [242 + 2 (563)] kJ – [2 × 431 + 155] kJ

= 1368 kJ – 1017 kJ
Δr H0 = 351 kJ

Δr H0 calculated by these two different methods are nearly the same.

INTEXT QUESTIONS 9.3

1. Write True or false
(a) Enthalpy of a reaction is equal to the sum of the enthalpy of formation
of products minus the sum of the enthalpy of formation of the
reactants.
(b) Enthalpy of formation of any elementary substance is equal to zero.
(c) If a reaction can be carried out in several steps, the enthalpy change
for the overall reaction is equal to enthalpy change in the last step.
(d) Bond enthalpy and bond dissociation energy are same for polyatomic
molecules.
2. Calculate the bond enthalpy of N – H in NH3 (g), given
1 3
N2 (g) + H2 (g) → NH3(g) ; Δf H0 = – 46 kJ mol-1
2 2

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1
H (g) → H (g); Δr H0 = 218 kJ mol–1
2 2

1
N (g) → N(g); Δr H0 = 973 kJ mol–1
2 2

3. Calculate the enthalpy of the reaction

Notes
H2 (g) + Cl2 (g) → 2HCl (g)
given;
Bond enthalpy (H - H) = 435 kJ mol-1
Bond enthalpy (Cl - Cl) = 242 kJ mol-1
Bond enthalpy (H - Cl) = 431 kJ mol-1

WHAT YOU HAVE LEARNT

z System is the part of the physical universe which is under study, while the
rest of the universe is surroundings.
z Isolated system is a system which can exchange neither matter nor energy
with the surroundings.
z Closed system is a system which can exchange energy but not the matter
with the surroundings.
z Open system is a system which can exchange both energy and matter with
the surroundings.
z State functions are those functions which depend only on the state of the
system.
z Extensive properties depend upon the size of the system whereas intensive
properties do not depend upon the size of the system.
z When the temperature of the system is kept constant during various operations
then the process is said to be isothermal.
z In an adiabatic process there is no exchange of heat between the system and
the surroundings.
z Reversible processes are those processes in which the changes are carried
out so slowly that the system and surrounding are always in equilibrium.
z Exothermic reactions are those reactions which proceed with the evolution
of heat.

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z Endothermic reactions are those which proceed with absorption of heat from
the surroundings.
z First law of Thermodynamics states that energy can neither be created nor
destroyed.
z Internal energy is the sum of the energies of all the atoms, molecules or ions
contained in the system.
Notes
z The state function enthalpy (H) is given by the relation H = U + PV.
z When a chemical equation is reversed, the sign of Δ H is also reversed.
z The enthalpy of reaction is independent of the number and nature of the
intermediate steps.
z Bond enthalpy is the average amount of bond dissociation enthalpies for a
given type of bond present in different gaseous compounds, when one mole
of bonds is broken in the gaseous state.

TERMINAL EXERCISE
1. Enthalpy of combustion of ethyl alcohol, C2H5OH, is – 950 kJ mol–1. How
much heat is evolved when one gram of ethyl alcohol burns?
2. Given :

5
C2H2(g) + O (g) → 2CO2 (g) + H2O(l) ; ΔcombH = – 1299 kJ/mol
2 2

C(graphite) + O2 (g) → CO2(g) ; ΔfH = – 393 kJ/mol

1
H2(g) + O (g) → H2O (l) ; ΔfH = – 285.5 kJ/mol
2 2

Calculate enthalpy of formation of C2H2(g)

3. Calculate the enthalpy of combustion of propane
C3H8 (g) + 5O2(g) → 3CO2(g) + 4H2O (l)
Given the following:
1
H2(g) + O (g) → H2O (l); ΔfH = – 285.5 kJ/mol
2 2

C(s) + O2(g) → CO2(g); ΔfH = – 393 kJ/mol

3C (s) + 4H2(g) → C3H8(g); ΔfH = – 104 kJ/mol

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4. When two moles of H2 and one mole of O2 react to produce two moles of
gaseous water at 373 K and 1 bar pressure, a total of 484 kJ are evolved.
What are (a) Δ H and (b) Δ U for the production of a single mole of H2O (g).
5. Calculate enthalpy of the reaction:
2Na2O2 (s) + 2H2O (l) → 4NaOH (s) + O2 (g)
Notes Enthalpies of formation of NaOH (s), Na2O2 (s) and H2O (l) are - 426.4
kJ mol–1, 504 kJ mol–1 and - 285 kJ mol-1 respectively.
6. Calculate the heat of formation of gaseous ethyl alcohol,
1
2C(graphite) + 3H2(g) + O (g) → C2H5OH (g)
2 2
given that enthalpy of sublimation of graphite is 714 kJ/mol and bond
enthalpies of H – H, O = O, C – C, C – H, C – O and O – H are respectively
435 kJ/mol–1, 498 kJ/mol–1, 347 kJ/mol–1, 415 kJ/mol–1, 355 kJ/mol–1 and
462 kJ/mol–1 respectively.

ANSWERS TO INTEXT QUESTIONS

9.1
1. (a)
1 3
2. (a) Δn = 1 – – =–1
2 2

(b) ΔU = ΔH – ΔnRT
= 46000 (J mol–1) – (– 1) (8.314 Jk–1 mol–1) × (298 K)
= – 46000 (J mol–1) + 2247.6 (J mol–1)
= – 43.5 kJ mol–1
3. (a)

9.2
1. (c)
2. – 1329 kJ
3. Δr H0 = 2 Δf H0 (H2O) – 2ΔfH0 (H2S) – ΔfH0 (SO2)
= – 241.7 kJ

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9.3
1. (a) T
(b) T
(c) F
(d) F
Notes
2. ΔrH = ∑ B.E. (reactant bonds) – ∑ B.E. (products bonds)
0

or – 46 (kJ mol–1) = 3 × 218 (kJ mol–1) + 973 (kJ mol–1) – B.E. (NH3(g)
Bonds)
B.E. (NH3(g) Bonds) = 1673 kJ mol–1
B.E. (N – H) = 557.7 kJ mol–1
3. Δr H0 = – 185 kJ mol–1

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