CHAPTER -06

THERMODYNAMICS

It is a branch of chemistry which deals with energy changes taking place

during various physical and chemical reactions. It is also known as
energetics.

Thermodynamic terms:

System: is the specific part of the universe in which energy changes take
place. It is separated by a definite boundary.

Surroundings: represents the rest of the universe which surrounds the

system which is not under study is called surroundings.

e.g.: A chemical reaction in a glass tube, then the tube is the system and
the rest of the universe is surroundings. The glass walls of the tube
represents boundary.

Types of systems: system and surroundings can exchange both mass and
energy. They are classified into

1. Open system: a system is said to be open if both matter and energy can
be exchanged with the surrounding.

e.g.: Na2CO3 + HCl → NaCl + CO2 + H2O; ΔH= - ve

Both CO2 and heat evolved are transferred to the surroundings.

2. Closed system: a system in which there is only exchange of energy with

the surroundings and not matter

e.g.: Na2CO3 + HCl → NaCl + CO2 + H2O ; ΔH= -ve

Reaction is carried in a closed vessel. Only the heat escapes to the

surroundings but not CO2.

3.Isolated system: A system is said to be isolated if there is neither

exchange of energy nor mass with the surroundings.

e.g.: Hot coffee or tea in a thermos flask represents an isolated system.

4.Macroscopic system: This consists of large number of atoms, ions &

molecules. The measurable properties associated with it are called as
macroscopic properties.

Macroscopic properties are divided into two types:

1. Intensive properties: These depend upon the nature of the substances
in a system.

e.g.: Temperature, concentration, pressure, surface tension, viscosity,

specific heat.

2. Extensive property: These depend upon the amount of substances in a

system.

e.g.: Mass, Volume, energy, internal energy, enthalpy, entropy, heat

capacity etc.

Thermodynamic process: is defined as a process or operation in which a

thermodynamic state changes from one state to the other.

1) Isothermal process: is a process in which temperature of the system

remains constant during various process. dt = 0

2) Adiabatic process: is a process in which there is no exchange of heat

between the system and surrounding, i.e. the system is completely isolated.

3) Isobaric process: process carried out at constant pressure. dp = 0.

4) Isochoric process: process carried at constant volume dv = 0.

5) Reversible process: which is carried out infinitesimally slowly so that all

changes occurring in direct process can be exactly reversed by reversing the
conditions.

6) Irreversible process: is that which cannot be reversed by reversing the

conditions.

7) Cyclic process: is a process in which a system undergoes a series of

changes and eventually returns to its initial state.

Difference between Isothermal and adiabatic process:

Isothermal process adiabatic process

Temperature remains constant Temperature does not remain

dt = 0 constant. dt ≠0

Heat is exchanged between the Heat is not exchanged between

system and surrounding q ≠ 0 system and surrounding q = 0

Internal energy does not change.u= 0 Internal energy changes. Δu ≠ 0

It is a closed system It is an isolated system

Internal energy (U): It is the sum of different kinds of energies possessed

by a system. It may be of different types like electronic energy, nuclear
energy, bond energy, energies of atoms, ions and molecules.

It is also called as intrinsic energy and has a unit of joule (J). Its absolute
value is not measurable but change (U) is measurable.

State of a system: are the fundamental properties like pressure, volume

and temperature which determine the state of a system.

State variables or state functions: It is the property of a system which

depends on the initial and final state of the system but not the path
followed by it.

e.g.: internal energy, enthalpy, entropy etc.

Standard state: State of a system at 298k and 101.3 Kpa pressure is

known as standard state of a system.

First Law of Thermodynamics: Energy can neither be created nor

destroyed but can be transformed from one form to another.

Mathematically it can be represented as

ΔU = q+W

ΔU is the change in internal energy

q = heat absorbed by the system

W = work done on the system

The sign convention according to IUPAC. Heat absorbed by the system.

Heat absorbed by the system (endothermic) q = +ve

Heat liberated by the system (exothermic) q = -ve

Work done on the system W = + ve

Work done by the system W = -ve

Mathematical expression for isothermal reversible process:

Isothermal reversible process: For an isothermal reversible process the
temperature and internal energy is constant because internal energy
depends upon the temperature.

According to l law ΔU = q + W dt = 0, therefore ΔU = 0

The equation becomes q = -W

Hence work done by the system in an isothermal reversible process is equal

to the heat absorbed by the system.

Mathematical expression for adiabatic reversible process:

In an adiabatic reversible process there is no exchange of energy between

the system and surroundings.

According to l law ΔU = q + W Therefore q = 0

The equation becomes ΔU = W

Work done on the system in an adiabatic reversible process is equal to
change in internal energy of the system.

Mechanical work done in an Isothermal reversible process:

For an isothermal process internal energy depends upon temperature.

ΔU = 0

q = -W

Hence mechanical work done during isothermal process is equal to quantity

of heat absorbed.

Mechanical work done in a reversible adiabatic process: In an adiabatic

process no heat is exchanged between the system and surroundings.

ΔU = W

W = nCv (T2 – T1)

Cv = molar heat capacity of a gas at constant volume.

T1 = Initial temperature T2 = final temperature

n = n moles of gas.
Thermochemistry: It is a branch of physical chemistry that deals with heat
energy changes during a physical & chemical reaction.

Thermochemical Equation: is a balanced chemical equation which

indicates the amount of heat absorbed or liberated during a chemical
reaction and also the physical state of the reaction.

e.g.: C(s) + O2 (g) CO2 (g), ΔH = - 393.5KJ

When 1 mole of graphite burns with 1 mole of O2, 1 mole of CO2 is formed
with 393.5 kJ of heat is liberated.

Or C + O2 CO2, ΔH = -393.5KJ (exothermic reaction)

ΔH = +ve heat is absorbed

ΔH = -ve heat is liberated

Internal energy (U): It is the sum of the stored energy or fixed amount of
energy stored in a definite mass of a substance at and given temperature
and pressure. Its absolute value cannot be measured but change in internal
energy is a measurable quantity (ΔU).

Change in internal energy (ΔU): It is the quantity of heat energy

exchanged between the systems and surrounding at constant temperature
and volume. It is the difference in energy between the products and
reactants.

ΔU = U products – U reactants

ΔU = Up – Ur

Enthalpy or Heat content: Is defined as the sum of the internal energies,

pressure and volume of the system at constant temperature. It is denoted
by a letter H.

H = U + PV, H = Enthalpy, U = Internal Energy, P = pressure, V = Volume.

Absolute value of enthalpy cannot be determined. But change in enthalpy is

a measurable quantity.

Enthalpy change or change in Heat content (ΔH): is defined as the

amount of heat energy exchanged by the system and surroundings at
constant temperature and pressure. It is equal to difference in heat content
or enthalpy between the products and reactants.

ΔH = H (products) - H (Reactants)

Or ΔH = Hp - HR
This is known as energy equation since it defines the energy changes in a
chemical reaction.

Exothermic and endothermic reactions:

Exothermic reaction: A chemical reaction in which a certain amount of

energy is liberated from the system to the surroundings.

N2(g) + 3H2(g) 2NH3(g) ; ΔH = -92.3KJ

C(s) + O2(g) CO2(g) ; ΔH = -393.5KJ

In exothermic Reaction the reactants contain more energy than the

products therefore heat is liberated. Enthalpy of the system decreases.

ΔH = HP – HR = -ve

Endothermic Reaction: A chemical reaction in which a certain amount of

heat is absorbed by the system from the surroundings.

N2 (g) + O2(g) 2NO2(g) ; ΔH = 180KJ

In endothermic reaction the reactants contain less energy than products

therefore heat is absorbed. Enthalpy of the system increases.

ΔH = HP – HR = +ve

Enthalpy of a reaction or Heat of a Reaction: is defined as the change in

enthalpy that occurs when the numbers of moles of the reactants indicated
in a balanced chemical equation have completely reacted to give products
under the given conditions.

C(s) + O2 (g) CO2(g) ΔH = -393.5KJ

Factors effecting heat of a reaction:

1. Physical state of the reactants and products: Enthalpy of reaction

changes with the change in physical state of the reactants and products.

Enthalpy of a reaction when one mole of steam is formed is different from

the enthalpy of a reaction when one mole of liquid water is formed.

e.g.: H2 (g) + ½ O2(g) H2O(g) ; ΔH = -241.9KJ

H2 (g) + ½ O2(g) H2O(d) ; ΔH = -286.KJ

2. Allotropic forms: The enthalpy of a reaction is different for different
allotropic forms.

e.g.: C(graphite) + O2(g) CO2(g) ; ΔH = -393.5KJ

C(diamond)+ O2(g) CO2(g) ; ΔH = -395.4KJ

3. Amount of reactants and products: increase or decrease in the

quantity of reactants and products also increases or decreases the enthalpy
associated with it.

e.g.: C(s) + O2(g) CO2(g) ; ΔH = -393.5 KJ

2C(s) + 2O2(g) 2CO2(g) ; ΔH = -393.5KJ x 2

4.Temperature : enthalpy of a reaction changes by varying the

temperature.

e.g.: N2 + 3H2 2NH3 ; ΔH = -91.17kJ at 300K

N2 + 3H2 2NH3 ; ΔH = -92.87KJ at 323K

Different types of enthalpies:

1. Enthalpy of combustion (ΔHc): is defined as the change in enthalpy

when 1 mole of a substance is completely burnt in excess of air or oxygen.

e.g.: C(g) + O2(g) CO2(g) ; ΔH = -393.5kJ

Applications:

Used in the calculation of calorific value of fuels and foods.

Used in the calculation of enthalpy of transition.

2. Enthalpy of formation or heat of formation (ΔHf): is defined as the

enthalpy change on forming one mole of a compound from their elements in
standard physical state.

If the enthalpy of formation is less, greater is the stability of compounds.

e.g.: CO2, ΔH = -393.5KJ

NO, ΔH = +90KJ

H2SO4 ΔH = -75.2KJ

Standard state: It is the physical state of an element at 298K or 250C and

101.325 Kpa pressure.
3. Standard enthalpy of formation (ΔHf0): is defined as change in
enthalpy when 1 mole of a compound is formed from elements in the
standard physical state, at standard condition of 298K or 250C and 1 atmp
or 101.325 KPa pressure. Lower the enthalpy value greater is the stability of
the compound.

C(g) + O2(g) CO2(g) : ΔHf0 = -393.5KJ

Note: ΔHf0 for elements in their most stable form is considered as zero.

4. Enthalpy of solution: (ΔHsol): is defined as the change in enthalpy that

occurs when 1 mole of a substance is completely dissolved in excess of
solvent or water so that further dilution of the solution does not produce
any heat exchange.

H2SO4 + (aq) H2SO4 (aq) ΔH = -75KJ

KCl (aq) + KCl (aq) ΔH = 18.5KJ

5. Enthalpy of transition or heat of transition: is defined as the change

in enthalpy that occurs when one mole of an element undergoes change
from one allotropic form to another or polymorphic change at transition
temperature.

P white P red ΔH = -18kJ

6. Enthalpy of Neutralisation (ΔHn): is defined as the change in enthalpy

when 1gm equivalent weight of an acid is neutralized by 1 gm equivalent
weight of a base in dilute aqueous solutions.

Eg: HCl (aq) + NaOH(aq) NaCl + H2O ; ΔH = -57.3kJ

Heat of Neutralization of a strong acid and strong base:

This fact is explained by Arrhenius theory of ionizations. According to this

theory strong acids and strong bases are strong electrolytes and are
completely ionisable. When 1gm equivalent of acid contain 1 mole of H+
ions and one gm equivalent of base contain 1 mole of OH- ions. During the
reaction:

HCl (aq) + NaOH(aq) NaCl(aq) + H2O

H+ + Cl- Na+ + OH- Na+ +Cl-+H2O

H+ + OH- H2O; ΔH = -57.3KJ

The heat liberated is the heat of Neutralization or heat of formation of H2O.
Hence heat of neutralization is always constant ΔH = -57.3KJ or -13.7Kcal.

Heat of Neutralization of strong acid and weak base or weak acid &
strong base: According to ionization theory all weak acids and weak bases
are weak electrolytes and feebly or partially ionized in the solutions.

The heat liberated is either absorbed by acid or base for further ionization.
Therefore heat of neutralization is always less than -57.3KJ

Eg: HCOOH + NaOH HCOONa + H2O; ΔH2 = -56.07KJ

HCOO- + H++ Na+ +OH- HCOO- +Na++ H2O

H+ + OH- H2O; ΔH1 = -57.3KJ

ΔH = ΔH2 – ΔH1

ΔH = -56.07-(-57.3)
QKJ = -56.07+57.3 = 1.23KJ

ΔH enthalpy of ionization = +1.23KJ

Enthalpy of atomisation: enthalpy change takes place when one mole of a

substance completely breaks into its constituents atoms in the gaseous
state.

The heat of atomisation of a diatomic molecule is equal to its heat of

dissociation.

H2 (gas) → 2H ; ∆H Dissociation = ∆H Atomisation = + 436KJ/mol

Bond dissociation enthalpy or enthalpy of bond association: The change

in enthalpy that occurs when one mole of covalent bonds of a particular
type are dissociated into gaseous atoms.
The bond energy of H-H is equal to the bond dissociation enthalpy of H2
molecule to produce gaseous H atoms.

Enthalpy change for phase transition:

1. Enthalpy of fusion: the enthalpy change that occurs when one mole of a
solid is melted at constant temperature and standard pressure is called of
fusion.

H2O (solid) → H2O (liquid), ∆H(fusion)= 6 KJ/mol

2. Enthalpy of vaporization: the enthalpy change that occurs when one
mole of a liquid is converted into vapour at constant temperature and
standard pressure.

H2O(liquid) H2O(gas)∆H(vap)= 40.8KJ/mol

3. Enthalpy of sublimation: the enthalpy change that occurs when one

mole of a solid is converted into vapour at constant temperature and
standard pressure.

CO2(S) CO2 g) ∆H(sub)= 25.2 KJ/mol

MEASUREMENT OF ΔU BOMB CALORIMETRY OR DETERMINATION OF

HEAT OF COMBUSTION OF A SUBSTANCE AT CONSTANT VOLUME

Principle: The measure in energy changes associated with chemical or

physical processes by an experimental technique called calorimetry. The
process is carried out in a vessel called calorimeter, which is immersed in a
known volume of a liquid. Knowing the heat capacity of the liquid in which
calorimeter is immersed and the heat capacity of calorimeter, it is possible
to determine the heat evolved in the process by measuring temperature
changes.

Procedure: The heat absorbed at constant volume, is measured in a bomb

calorimeter. A steel vessel (the bomb) is immersed in a water bath called as
calorimeter. The steel vessel is immersed in water bath to ensure that no
heat is lost to the surroundings. Beckman’s thermometer which can read
up to 0.010C and a stirrer is introduced in the outer vessel. A combustible
substance is burnt in presence of pure dioxygen at 20-25 atm, supplied in
the steel bomb. Heat evolved during the reaction is transferred to the water
around the bomb and its temperature is monitored. Since the bomb
calorimeter is sealed, its volume does not change i.e., the energy changes
associated with reactions are measured at constant volume. Temperature
change of the calorimeter produced by the completed reaction is then
converted to qV, by using the known heat capacity of the calorimeter.

Calculations:

Mass of the substance = w gm

Rise in temperature = (T2 –T1) K

Heat capacity of calorimeter system = Cv J/K

Amount of heat liberated when w/M mole of substance is burnt= Cv (T 2-T1)

Amount of heat liberated when 1 mole of substance is burnt= Cv (T 2-T1) x
M/w J

Heat of a reaction at constant volume,

ΔU = - Cv (T2-T1) x M/wJ (-sign shows that heat is released during the

reaction).

Laws of Thermo chemistry: 1 Law of thermo chemistry

Lavoisier–Laplace law: The amount of heat liberated in a chemical reaction

is equal to the amount of heat absorbed.

e.g.: C (g) + O2(g) CO2 ; ΔH = -393.5KJ

CO2(g) C(s) + O2(g) ; ΔH = +393.5KJ

The quantity of heat supplied for the decomposition of compounds to

elements is equal to the quantity of heat required for the formation of
compounds from the elements.

II Law of thermo chemistry:

Hess’s Law of constant heat summation: The enthalpy change that occurs
during a chemical reaction is always constant whether the reaction takes
place in one step or number of steps.

i.e. ΔH in a chemical reaction is independent the path followed by the

reaction.

ΔH1 = ΔH2 + ΔH3 (formation of CO2)

e.g.: C(s) + O2 (g) CO2 (g); ΔH1 = -393.5KJ

e.g.: C + ½ O2 CO (g); ΔH2 = -110KJ

e.g.: CO + ½ O2 CO2 (g) ΔH3 = -283.5KJ

According to Hess law

ΔH1 = ΔH2 + ΔH3

-393.5 = - 110 + (- 283.5)

-393.5 = - 393.5KJ

Whether CO2 is formed from 1 step or 2 and 3 step the enthalpy change
remains constant.

Applications:
 Thermo chemical equations can be added subtracted multiplied or
divided. Also fractional numbers can be used.

Helps in evaluating change in enthalpy of a reaction which cannot be

determined experimentally.

Calculation of Lattice energy:

Sublimation of sodium atom.

Step l: Na(s) sublimation Na (g)

Ionization of sodium atom into sodium ion.

Step 2: Na (g) ionization Na+ (g) + e- ; H = +495.8kJ

Dissociation of chlorine molecule into chlorine atom.

Step 3: 1/2Cl2 (g) dissociation Cl (g); H = +121.0kJ

Addition of electron to chlorine atom to form chloride ion.

Step 4: Cl (g) + e-electron affinity Cl-(g) ; H = -348.7kJ

Combination of sodium & chloride ions to form sodium chloride

Step 5: Na+ (g) + Cl-(g) NaCl (s); Lattice energy (U).

The sum of the two is 147.1kJ is more compensated for by the enthalpy of
lattice formation of NaCl(s) (-788kJ).

Lattice energy: The energy released when 1 mole of ionic crystal is formed
by close packing of gaseous cations and anions or the lattice enthalpy of an
ionic solid is defined as the energy required to separate one mole of a solid
ionic compound into gaseous atom or ions.

Spontaneous process:
The process which takes place by itself without any external aid is called
spontaneous process.

1. Reaction between acid and base to produce salt and water.

2. Flow of water from a higher to lower level.

3. Flow of electricity from a higher to lower potential.

4. Movement of gas molecules from the region of higher pressure to region

of lower pressure.

5. Melting of ice
6. Rusting of iron

Non-spontaneous process:

The process which does not takes place on its own and requires the help of
external energy is called non-spontaneous process.

Eg: 1) Movement of water from lower to higher level.

2) Decomposition of water into H2 and O2

Criteria for spontaneity:

If a system is at equilibrium, then a spontaneous process cannot take place.

All natural process is spontaneous and irreversible.

When a spontaneous process takes place, it is found that disorder increases

and the total energy of the system decreases.

Entropy:

It is a measure of disorder or randomness in a system at constant

temperature.

It is denoted by symbol ‘S’

i) In a crystal, the particles are arranged in an ordered manner in the

lattice. When the crystal melts, lattice breaks and disorder increases.
Therefore entropy of the system increases.

ii) During spontaneous changes like expansion of gas, diffusion of a gas,

disorder increases, thus entropy also increases.

iii) Entropy is highest in the gaseous state and least in the solid state.

Change in entropy: (∆S)

Absolute entropy of a system is not measurable. However change in entropy
can be measured.

Change in entropy is defined as the difference between the entropies of

products and reactants at a given constant temperature. Entropy is an
extensive property.

i.e. ∆S = Sp - SR

S can be calculated by,

ΔS = ΔH/T

Where ΔH = change in enthalpy.

 T= Absolute temperature.

Entropy is expressed in Joule / Kelvin.

If the reaction takes place under standard conditions,

i.e.

If ∆S = +ve, the process is spontaneous

∆S = -ve, the process in non- spontaneous

∆S = O, the process is under equilibrium

In reversible reaction, positive sign indicates that the forward reaction is

more favourable, negative sign indicates that backward reaction more
favourable.

ll law of thermodynamics:
The II law of thermodynamics can be stated in many ways:

i) All spontaneous process are irreversible and tend to attain equilibrium.

ii) The total energy of the universe remains constant while the total entropy
of the universe increases.

Gibb’s free energy:

It is the difference between total enthalpy of the system and the product of
absolute temperature and entropy.

Gibb’s free energy is given by ∆G = ∆H-T∆S

Where G = Gibb’s free energy

H = Enthalpy

T = Absolute temperature

S = Entropy

In a process A B, if G1, is the initial free energy, G2 is the final free

energy, then,

G1 = H1 – TS1 (1)

G2 = H2 – TS2 (2)
Where H1 and H2 represent initial and final enthalpies and S1 and S2
represents initial and final entropies respectively.
Therefore free energy change is given by:

G2 – G1 = (H2 – H1) –T (S2 –S1)

ΔG = ΔH- TΔS

This equation is called Gibb’s Helmholtz equation.

∆G = Change in free energy

∆H = Change in enthalpy

T = Absolute temperature

∆S = Change in entropy

The conditions for the spontaneity of a process is:

i) ∆G = –ve, the process is spontaneous

ii) ∆G = +ve, the process is non – spontaneous

iii) ∆ G = O, the system has attained equilibrium.

Predicting the spontaneity of exothermic and endothermic reactions using

Gibb’s Helmholtz’s equation:

Case 1: For an exothermic reaction:

For an exothermic reaction ∆H = –ve, ∆S = +ve

∆G =∆ H – T∆S

= (–ve) –T (+ve)

∆G = –ve

The reaction is spontaneous.

Case 2: For an endothermic reaction:

For an endothermic reaction, ∆H = +ve, ∆S = +ve

∆G =∆H – T∆ S

= (+ve) – T (+ve)

∆G = +ve

The reaction is non - spontaneous.

Note: 1. ∆G is positive, if ∆H > T∆S

 ∆G is negative, if ∆H < T∆S

∆G = 0 if ∆H = T∆S

2. If GP< GR, in a reaction, then ∆G has negative value. Hence, the reaction
will be spontaneous.

3. If GP> GR, in a reaction, then ∆G is +ve, Hence the reaction is non-

spontaneous.

Dependence of spontaneity of a reaction on ∆H and ∆S

∆H ∆S ∆G Conclusion

-ve +ve -ve Spontaneous at all temperature

+ve +ve -ve Spontaneous at high temperature

-ve -ve -ve Spontaneous at low temperature

+ve -ve +ve never takes place

Standard free energy change (∆G): Standard free energy change of a reaction
is the difference between total standard free energies of all the products and
total standard free energies of all the reactants at a standard temperature
298K and 101.3 Kpa.

Standard free energy of all elements is always taken as zero.

∆G0 = G0p - G0R

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