Prof.

Piyush Singh

M.Sc. B.Ed, IIT-KGP(Adv.Polymer)

Page 2 of 25

Basic concepts in Thermodynamics:-

1) System:- The part of universe which is under thermodynamic

study is called system.

2) Surrounding:- The remaining part of universe excluding

system is surroundings.

3) Boundery:- The real or imaginary surface separating the

system from the surroundings.

Boundary
Types of system:-

Open system Closed system Isolated system

1) Open system:- A system that can exchange both the matter and energy with its surroundings
is called an open system.
Eg. Hot tea in an open cup.

A system that can exchange only energy but not matter with its surroundings
2) Closed system:- is called a closed system.

Eg. Hot tea in a cup covered with saucer.

3) Isolated system:- A system that cannot exchange either energy or matter with its surroundings
is called an isolated system.
Eg. Hot tea in thermos flask.
 Page 3 of 25

Properties of system:-

Extensive Property:- Intensive Property:-

The property which depends upon the quantity The property which depends upon the quantity
of matter is known as Extensive Property. of matter is known as intensive Property.

Eg. Mass, Volume, Work, Entropy, Enthalpy, Eg. Temperature, Pressure, Concentration, Specific
Surface area, Internal energy etc. gravity etc.

Note. (1) Extensive Properties are additives. (2) Intensive Properties are not additives. (3) The ratio
of two Extensive Properties is an intensive property.

A known set of measurable properties like temperature, pressure,

State and state function:- volume define a state of system.
When these variables are changes, then system is said to be in different state.

i.e Change in state

P1 , V1 , T1 P2 , V2 , T2

State- I State- II

Any property of the system whose value depends only on the current state of
State function:-
system and does not depend on the path fallowed by system is called state function.

Consider a system at point ‘A’ P = P1 , V = V1

After condition pressure and volume are changed, A (P1 ,V1 )

at point ‘B’ P = P2 , V = V2

The change in pressure ∆P = P2 — P1 and The P

∆P

change in volume ∆V = V2 — V1 does not depend

upon the path fallowed by system from point ‘A’ to
‘B’.
B(P2 ,V2 )

Hence ∆P and ∆V are state function. ∆V

Thermodynamic Equilibrium:- A system is said to be in thermodynamic equilibrium when

the state functions of the system do not change with time.

1) Thermal Equilibrium 2) Chemical Equilibrium 3) Mechanical Equilibrium

Temperature constant Chemical composition constant Mechanical properties (or Pressure) constant
 Page 4 of 25

Types of processes:-
Process: - The transition from one state to another state is called process.

Isothermal process:-

A process in which temperature of the system remain constant throughout the process is
called an isothermal process.

For isothermal process, ∆T = 0 , ∆U = 0 U = internal energy

Isobaric process:-

A process in which pressure of the system remain constant throughout the process is
called an isobaric process.

For isobaric process, ∆P = 0 This process is carried out in open vessel.

Isochoric process:-

A process in which volume of the system remain constant throughout the process is called
an isochoric process.

For isochoric process, ∆V= 0 This process is carried out in closed vessel.

Adiabatic process:-

A process in which no heat can exchange between system and surroundings is called an
adiabatic process.

For adiabatic process, q = 0

Isothermal process Adiabatic process

A process in which temperature of the system A process in which no heat can exchange between
remain constant throughout the process is called system and surroundings is called an adiabatic
an isothermal process. process.

Temperature of the system remains constant. Temperature of the system remains changes.
Ie ∆T = 0 Ie ∆T ≠ 0
Exchange of heat between system and No exchange of heat between system and
surroundings. surroundings.
Internal energy of the system remains constant. Internal energy of the system remains changes.
Ie ∆U = 0 Ie ∆U ≠ 0
System is not thermally isolated. System is thermally isolated.

Eg. Fusion of ice. Eg. Expansion of gas in vacuum.

 Page 5 of 25

Reversible process:-

A process in which the driving force is infinitesimally greater than the opposing
force and direction of the process can be reversed by slight increase in the opposing force
is called Reversible process.

Features of Reversible process:-

(1) Driving force and opposing force are slight different from each other. (2) It takes infinite time.

(3) It takes place in infinite number of steps. (4) The process can be reversed at any point.

(5) Reversible process is occurs at a very slow rate. (6) Maximum work is obtained.

Nature of heat and work:- Change of energy in closed system occur (1) by transfer of energy as
work and (2) by transfer of energy as heat

Work (W):- In mechanics, work is product of force and displacement, W=f×d

where f = force in the direction of displacement d = displacement

Pressure – volume work

Work

Maximum work

Pressure – volume work:-

The work is done due to expansion or compression of a gas against an external
opposing pressure P is called Pressure – volume work.
Pext
Expression:-

Consider a gas having pressure( P), Volume (V1 ) and

Temperature (T) enclosed in a cylinder fitted with frictionless

A
Piston having area (A) as shown in fig.

As gas expand against external pressure Pext , the

Piston moves in upward direction through a distance ‘d’ P

Then work done (W) by gas is,

Ideal Gas
W = Opposing force × displacement W = — f × d …... (1)
 Page 6 of 25

Pressure is force per unit area

Pext = f / A ===> f = Pext × A …….…. (2)

From eq. (1) and (2), W = — Pext × A × d ………… (3)

But, A × d = ∆V = V2 — V1 V1 = initial volume V2 = final volume

Eq. (3) becomes,

W = — Pext × ∆V Or W = — Pext × (V2 — V1 ) ……….. (4)

Free Expansion:- Expansion against zero opposing force is called Free Expansion.

When gas expand in vacuum, there is no opposing force i.e Pext = 0

W = — Pext × ∆V  W = 0 × ∆V  W=0

Hence, no work is done when gas expand in vacuum.

Note= For getting work done opposing force is necessary.

Maximum Work:- When work is done there are two forces [1] acting force (driving force)(P)
and [2]Opposing force ( Pext )

When opposing force is zero, no work is done and the opposing force is increased more,
more work will be obtained. Ie. W = — Pext × ∆V  W = 0 × ∆V  W = 0

If opposing force = driving force, Pext = P then ∆V = 0.

Ie. W = — Pext × ∆V  W = — Pext × 0  W=0

Maximum work done is obtained, when driving force is slightly greater than opposing force.
Ie. P > — Pext

If P— Pext = ∆P  Pext = P—∆P

W = — Pext × ∆V

W = — (P—∆P) × ∆V = (∆P—P) × ∆V Work is maximum when ∆P is smallest.

Condition for maximum work:

Maximum work is obtained when-

(1) Process is thermodynamic ally reversible. (2) Change takes place in infinite number of steps.
(3) Driving force is slightly greater than opposing force. (4) System is in mechanical equilibrium with
its surrounding.
 Page 7 of 25

Expression for Maximum Work:- ( Isothermal reversible expansion )

Fig. P—dP

dv

V + dV

V P n

Cylinder

Consider ‘n’ moles of an ideal gas enclosed in a Cylinder fitted with frictionless Piston
having area (A). Let, P = pressure, V = volume and T = temperature of the gas. Let the gas
expand isothermally and reversibly. The opposing pressure ( Pext ) is slightly less than
pressure of gas (P) hence, Pext = P — dP ………(1)

Suppose gas expand by a small volume dV, then work done dW Is given by

dW = — Pext × dV

= — (P — dP) × dV

= — P.dV + dP . dV

dP . dV isvery small hence neglected

dW = — P.dV ………….. (3)

Now, total work done when gas expand from initial volume V1 to final volume V2 is
obtained by integrating eq. (3) between limits V1 and V2

Wmax = ∫ = ∫ — P. dV …………….(4)

For ‘n’ moles ideal gas eq. is PV = nRT ===> P = nRT / V

Wmax = ∫ —

= — nRT ∫ —

= — nRT [loge V]
 Page 8 of 25

= — nRT [loge V2 — loge V1 ] = — nRT loge

Wmax = — 2.303 nRT log10

According to Boyle’s law, P1 V1 = P2 V2  =  Wmax = — 2.303 nRT log10

A (V1 )
Path function:- 3

Work (W)and heat (q) are path functions 1

2

A) Path dependence nature of work

1. When gas expand in vacuum work done is zero B (V2 )

2. When gas expand from V1 to V2 work done is W = — Pext × (V2 — V1 )

3. When gas expand isothermally and reversibly, work done is Wmax = — 2.303 nRT log10

B) Path dependence nature of heat A

1. For adiabatic process q=0 Adiabatic q = 0

Isothermal q ≠ 0
2. For isothermal process q≠0

Unit of energy and work:- Joule (J)

1 J = 1 kgm3 /s2 1 atm = 101.3 × 10—3 kgm3 /s2

1 J = 1 pa.m3 1 L.atm = 101.3 kgm3 /s = 101.3 J

1 J = 107 ergs 1 J = 0.239 cal. 1 cal. = 4.184 J 1 kcal. = 4.184 J

Sign convention of work done, heat and energy:

+W work done on system System heat absorbed +q

—w work done by system heat released —q

+ q : heat is absorbed by system from surrounding.

— q: heat is released by system from surrounding.

+ w: work is done on system by surrounding. — w: work is done by system on surrounding.

 Page 9 of 25

Internal Energy (U):-

“The energy associated with a substance or system is called internal energy.”

(1) Internal energy is a sum of kinetic energy and potential energy.

(2) Internal energy is a state function. (3) Internal energy is an extensive property.

(4) Internal energy depends on temperature hence for isothermal process, (∆T = 0) ∆U = 0

(5) Change in Internal energy ∆U = U2 — U1

(6) —∆E = energy is evolved by system, +∆E = energy is absorbed by system.

U = Utran. + Urot. + Uvibr. + Uele. + Uintra. + Uinter.

Note:- Kinetic energy = Translation + Rotational + Vibrational + Electronic

Potential energy = Intramolecular + Intermolecular

First law of thermodynamics:- It is simply law of conservation of energy.

Statements

1. Energy can neither be created nor destroyed, although it can be converted from one form to
another

2. The total internal energy of an isolated system is constant.

3. The total quantity of energy of the universe is constant.

4. Whenever a one form of energy disappears, exactly an equivalent amount of other form must
appear.

5. It is impossible to construct perpetual motion machine which produce work continuously without
consuming energy.

Mathematical equation of First law of thermodynamics:-

Consider U1 = initial internal energy. Suppose ‘q’ amount of energy supplied to system
which produce ‘W’ amount of work done.

Thus, final internal energy U 2 is given by, U2 = U1 + q + W ==> U2 — U1 = q + w

∆U = q + w ………… (A)

∆U = increase in internal energy of system.

Eq. (A) represents equation of First law of thermodynamics.

For infinitesimal change eq. (A) becomes dU = dq + dW

 Page 10 of 25

Modified First law of thermodynamics:-

According to Einstein theory, mass can be covered into energy. (ie. Energy produced due to
loss of mass.)

Einstein eq. is E = mC2

Where E = energy produced by loss of mass ‘m’. C = velocity of light = 3 × 108 m/s

Hence modified First law of thermodynamics is stated as, “total mass and energy of an isolated
system (or universe) remain unchanged.”

First law of thermodynamics for various processes:-

We have ∆U = q + w …….. (A)

1) For isothermal process:- ∆T = 0 and ∆U = 0

Eq. (A) becomes, 0=q+W
Ie. q = — W or — q = W
+ W : work done by system on surroundings. — W : work done by surroundings on system.

2) For isobaric process:- ∆P = 0

∆U = qp + W
= qp + ( — Pext × ∆V )
∆U = qp — Pext × ∆V or qp = ∆U + Pext × ∆V
Heat used to increase internal energy of system.

3) For isochoric process:- ∆V = 0

∆U = qV + W
= qV + ( — Pext × ∆V )
∆U = qV + (0) or ∆U = qV
Change in internal energy of system is due to heat transfer.

4) For adiabatic process:- q=0

Eq. (A) becomes, ∆U = 0 + W
Ie. ∆U = W or — ∆U = — W
1. work done by system, internal energy increases.
2. Work done by surroundings internal energy decreases.
 Page 11 of 25

Second law of thermodynamics:-

Statements

1) “The spontaneous flow of heat is always unidirectional from higher temperature to lower
temperature.”

2) “Heat cannot be completely converted into an equivalent amount of work without

producing permanent changes either in the system or its surroundings.”

3) “No machine has yet been made that has an unit efficiency.”

4) “The entropy of the system is constantly increasing.”

Enthalpy (H):- It is defined as “the sum of internal energy of the system and PV energy.”
(PV energy is energy related with the pressure and volume.)

Mathematically, the enthalpy is defined as H = U + PV ………… (1)

Since P, V and U are state functions, H is also state function.

Hence change in enthalpy (∆H) is given by ∆H = H2 — H1 …………(2)

If H1 = U1 + P1 V1 and H2 = U2 + P2 V2

Then from eq. (2) we have ∆H = U2 + P2 V2 — ( U1 + P1 V1 )

= ( U2 — U1 ) + ( P2 V2 — P1 V1 )

= ∆U + ( P2 V2 — P1 V1 )

At constant pressure i.e P1 = P2 = P then

∆H = ∆U + ( P V2 — P V1 ) = ∆U + P ( V2 — V1 )

∆H = ∆U + P∆ V ………… (3)

Hence, for isobaric process enthalpy of system is the sum of increase in internal energy the
work of expansion.

Also we have, qp = ∆U + Pext × ∆V

If Pext = P then qp = ∆U + P∆V ……….. (4)

From eq. (3) & (4) we write ∆H = q p since, qP is state function.

Hence, for isobaric process enthalpy change is the heat absorbed by system.

Note:- Enthalpy is Heat content of the system. Heat evolved or absorbed at constant
pressure is expressed in terms of enthalpy.
 Page 12 of 25

Relation between ∆H and ∆U for chemical reaction:-

Que. Obtain relationship betn ∆H and ∆U for chemical reaction.

Ans. We have, ∆H = ∆U + P∆ V …………. (1)

For solid and liquid, ∆V = 0 then ∆H = ∆U + P(0)

∆H = ∆U ………………… (2)

For gas, ∆V is not neglected.

∆H = ∆U + P ( V 2 — V1 )

= ∆U + PV2 — PV1 …………… (3)

V1= initial volume (volume of gaseous reactant) , V2 = final volume (volume of gaseous
product)

According to ideal gas eq. PV = nRT

Suppose, n1 = moles of gaseous reactant. n2 = moles of gaseous product.

PV1 = n1 RT and PV2 = n2 RT

From eq. (3) ∆H = ∆U + ( n2 RT — n1 RT )

= ∆U + RT ( n 2 — n1 )

∆H = ∆U + RT.∆n

Work done in chemical reaction:-

We have W = — Pext . ∆V ……… (1)

Suppose Pext = P then W = — P . ∆V = — P ( V2 — V1 )

= — PV2 + PV1 …………….. (2)

According to ideal gas eq. PV = nRT

If n1 = moles of gaseous reactant. n2 = moles of gaseous product.

Then PV1 = n1 RT and PV2 = n2 RT

Eq. (2) becomes, W = — n2 RT + n1 RT = — RT ( n2 — n1 )

W = — RT . ∆n
 Page 13 of 25

Condition under which ∆H = ∆U

1) When reaction is carried out in a closed vessel ∆U = 0, ∆H = ∆U + P∆V  ∆H = ∆U

2) When reaction involves solid and liquid ∆V = 0, ∆H = ∆U + P∆V  ∆H = ∆U

3) When reaction in which n 1 = n2 , ∆n = 0 ∆H = ∆U + RT∆n  ∆H = ∆U

Sign conventions of ∆H

1) When heat is absorbed by system (ie. for endothermic reaction) ∆H is positive.

2) When heat is evolved by system (ie. for exothermic reaction) ∆H is negative.

Enthalpies of physical changes:-

A) Enthalpy of phase transition:-

Whenever there is a change in the state of matter, the process is called phase transition or
change.

It is accompanied by the change in enthalpy (Heat content) of the system.

Commonly observed phase transitions are:-

Solid liquid fusion (melting)

Liquid vapour vaporization

Solid vapour sublimation

1) Enthalpy of fusion (Heat of fusion):- ( ∆fus. H)

The enthalpy change when one mole of a solid substance is converted into liquid at
its melting point at constant pressure is called its enthalpy of fusion.

H2 O (s) H2 O (l) ∆fus. H = + 6.01 kJ/mol at 00 C

¤ The reverse of fusion is freezing of liquid.

2) Enthalpy of vaporization:- ( ∆vap. H)

The enthalpy change when one mole of a liquid is converted into vapour at its
boiling point at constant pressure is called its enthalpy of vaporization.

H2 O (l) H2 O (g) ∆vap. H = + 40.7 kJ/mol at 100 0 C

¤ The reverse of vaporization is condensation of vapour.
 Page 14 of 25

3) Enthalpy of sublimation:- ( ∆sub. H)

The enthalpy change when one mole of a solid is directly converted into vapour at
constant temperature and pressure is called its enthalpy of sublimation.

H2 O (s) H2 O (g) ∆sub. H = + 51.08 kJ/mol at 00 C

Gas
Relationship between ∆fus. H , ∆vap. H and ∆Sub. H
Vaporization
∆sub. H = ∆fus. H + ∆vap. H
Liquid
Eg for water,
Sublimation
51.08 = 6.01 + 45.07 Fusion
Solid

B) Enthalpy of atomic or molecular changes:-

1) Enthalpy of ionization:- (∆ion. H)

The enthalpy change when removal of an electron from each atom or ion in one
mole of a gaseous atom or ion called enthalpy of ionization.

Na (g) Na+ (g) + e— ∆ion. H = 494 kJ/mol

# 494 kJ / mol of heat is required to ionize one mole of Na atom.

Note:-
Ca (g) Ca+ (g) + e— ∆ion. H = 590 kJ/mol …… first ionization enthalpy

Ca+ (g) Ca++ (g) + e— ∆ion. H = 590 kJ/mol …… second ionization enthalpy

The reverse of ionization is electron gain process. Hence electron gain enthalpy is defined as,

“The enthalpy change when one mole of a gas phase atom of an element accept electron so
as to form gaseous anion.”

Cl (g) + e— Cl— (g) ∆ eg. H = — 349 kJ/mol

2) Enthalpy of atomization:- (∆atm. H)

The enthalpy change when the dissociation of all the molecule in one mole of a gas
phase substance into gaseous atoms is called enthalpy of atomization.

OR The enthalpy change when one mole of a gas phase substance dissociates into its
gaseous state constituent atoms is called enthalpy of atomization.
Cl2 (g) Cl (g) + Cl (g) ∆atm. H = 242 kJ/mol

CH4 (g) C (g) + 4 H (g) ∆atm. H = 1660 kJ/mol

 Page 15 of 25

3) Enthalpy of solution:- ( ∆sol. H )

The enthalpy change when one mole of a substance is dissolved in a specified

quantity of solvent at a given temperature is called enthalpy of solution.

NaCl (s) + H2 O (l) 1 dm3 NaCl (aq.) ∆sol. H = + 4 kJ/mol

Note:- The ∆sol. H is the sum of three kinds of interactions.

i) Solute – solute interaction (ie crystal lattice energy) ∆L H

ii) Solvent – solvent interaction

ii) Solute – solvent interaction (ie enthalpy of hydration) ∆hyd. H

1) Lattice enthalpy:- ( ∆L H )

The enthalpy change when one mole of a ionic solid breaks down into its ions is
called Lattice enthalpy.

XY (s) X+ (g) + Y— (g) or X+ (g) + Y— (g) XY (s) ∆L. H = + ve kJ/mol

2) Enthalpy of hydration :-( ∆hyd. H )

The enthalpy change involved in the hydration of one mole of a gaseous ions is
called enthalpy of hydration .

X+ (g) + Y— (g) X+ (aq.) + Y— (aq.)

So,

∆sol. H
XY X+ (aq.) + Y— (aq.)

Ie. ∆sol. H = ∆L H + ∆hyd. H

∆L H
∆hyd. H

X+ (g) + Y— (g)
 Page 16 of 25

Born – Haber cycle:-

Maw Born & Fritz Haber proposed the method to calculate lattice enthalpy.

Eg. Formation of NaCl. Na (s) + Cl2 NaCl (s) ∆f H

1) Sublimation of Na metal:- Na (s) Na (g) ∆sub H

2) Ionization of Na atom:- Na (g) Na+ (g) + e— (g) ∆ion H

3) Dissociation of mole Cl2 :- Cl2 (g) Cl (g) ∆a H

4) Electron gain by Cl atom:- Cl (g) + e— Cl— (g) ∆ eg. H

5) Combination of Na+ and Cl— atom:- Na+ (g) + Cl— (g) NaCl (s) ∆L. H

∆f H = ∆sub H + ∆ion H + ∆a H + ∆ eg. H + ∆L H

4) Enthalpy of dilution:-

The enthalpy change that occurs when a solution of one concentration is diluted to
form the solution of another concentration.

HCl (g) + 50 H2 O (finite amount) HCl (50 H2 O ) ∆s. H1 = — 73.26 kJ

HCl (g) + H2 O (infinite amount) HCl (aq. ) ∆s. H2 = — 75.14 kJ

∆H = ∆ H2 — ∆ H1 = (— 75.14 )— (— 73.26 ) = — 1.88 kJ enthalpy of dilution.

Thermochemistry:- Thermochemistry deals with the study of enthalpy changes in

chemical reactions.

Enthalpy of chemical reactions (Heat of reaction):-

The enthalpy change occur by chemical reaction is called Enthalpy reaction.

Consider a rean aA + bB cC + dD

The enthalpy change for rean is ∆H = (c HC + d HD ) — (a HA + b HB )

Where HA , HB , HC and HD are the enthalpies of A, B, C and D respectively.

∆H = ∑ HProduct — ∑ HReactant
Hence enthalpy of chemical reaction is the difference between the sum of enthalpies
of product and sum of enthalpies of reactant.
 Page 17 of 25

Exothermic and Endothermic reactions:-

Exothermic reactions Endothermic reactions

1. The reaction in which heat released in the 1. The reaction in which heat absorbed from
surrounding is called Exothermic reaction. surrounding is called Endothermic reaction.

2. Exothermic reactions are occurs by evolution 2. Endothermic reactions are occurs by

of heat. absorption of heat.

3. ∑ HProduct < ∑ HReactant 3. ∑ HProduct > ∑ HReactant

4. ∆H is negative 4. ∆H is positive
5. Products are more stable than reactants. 5. Reactants are more stable than Products.
6. i) C (s) + O2 CO2 ∆H = — 393.5 kJ/mol 6. i) N2 + 2O2 2NO2 ∆H = + 66.4 kJ/mol
ii)Making ice cubes, iii) condensation of water ii) Melting of ice, iii) Evaporation of water.
vapour

Standard Enthalpy of chemical reactions:- (∆H0 )

“The standard Enthalpy of chemical reactions is the enthalpy change for a reaction
when all the substances involved are in their standard states.”

Note: The standard state of substance is the pure form in which it is most stable at pressure
1 atm & 25 0C temperature.

Standard states of element = H2 (g) , Hg (l) , Na (s) , C (S)

Standard states of substance = C2 H5 OH (l), H2 O (l) , CaCO3 (S) , CO2

Thermochemical equation:-

1) The equation must be balanced

2) The physical state of reactants and products are indicated by placing the letters (s) for
solid, (l) for liquid and (g) for gas.

3) The numerical value and appropriate sign of enthalpy change must be shown on right
hand side of equation.

4) A thermodynamic eq. can be reversed, if the sign of ∆H is changed.

C (s) + O2 CO2 ∆H = — 393.5 kJ/mol CO2 C (s) + O2 ∆H = + 393.5 kJ/mol

5) The enthalpy of excess of water shown by (aq) is taken as zero.

NH4 Cl (s) + aq. NH4 Cl (aq) ∆H0 = + 15.1 kJ

 Page 18 of 25

Standard Enthalpy of formation:- (∆fH0 ) (Standard heat of formation ):-

The Standard Enthalpy of formation of a compound is defined as, the enthalpy
change that take place when one mole of pure compound under standard condition is
formed from its constituent elements which is in their standard states.

Eg. Formation of one mole of liquid water, H2 (g) + ½ O2 (g) H2 O (l) ∆fH0 = —286 kJ

Calculation of Standard Enthalpy of reaction from Standard Enthalpy of

formation:-
Consider the reaction aA + bB cC + dD

Standard Enthalpy of reaction is given by ∆H0 = ∑ ∆f — ∑ ∆f

= {c ∆fH0 (C)+ d H0∆ fH0 (D)} — {a ∆fH0 (A) + b ∆ fH0 (B)}

Where a, b, c and d are stiochiometric coefficient.

Eg. Formation of CO2 (g) C (s) + O2 CO2 ∆fH = — 393.5 kJ/mol

∆H0 = ∑ ∆ f — ∑ ∆f = { ∆fH0 (CO2 )} — { ∆fH0 (C) + ∆ fH0 (O2 )}

By convention enthalpies of C (s) and O2 (g) is zero

∆H0 = ∆fH0 (CO2 ) — {0 + 0} = ∆fH0 (CO2 )

Hence enthalpy of CO2 is equal to its enthalpy.

Standard Enthalpy of combustion:- (∆CH0 )

The Standard Enthalpy of combustion of a substance is the enthalpy change that
takes place when one mole of pure substance in the standard state reacts completely with
oxygen.

Eg. Complete combustion of 1 mole of CO is,

CO (g) + ½ O2 (g) CO2 (g) ∆cH0 = —283 kJ

Combustion of ethyne C2 H2 (g) + 5/2 O2 (g) 2CO2 (g) + H2O (l) ∆cH0 = — 1300 kJ
 Page 19 of 25

Bond Enthalpy (Bond energy):- (D)

“The amount of energy required to break a particular covalent bond in 1 mole of

gaseous molecule to produce gaseous atom or radical is called bond enthalpy.”

# Bond energy is always positive because energy is always needed to break the bond.

Eg. 1) H2 (g) H (g) + H (g) ∆H0 = + 436.4 kJ

Ie. to break H—H bond in H2 , 436.4 kJ energy is required. Ie. DH—H = 436.4 kJ or
∆H0 (H—H)= + 436.4 kJ

2) HCl (g) H (g) + Cl (g) ∆H0 = + 431.9 kJ Ie ∆H0 (H—Cl) = + 431.9 kJ

# The bond enthalpy for diatomic molecule is the same as enthalpy of atomization.

# In polyatomic molecule, every covalent bond has its own specific bond enthalpy. Hence
average bond enthalpy has to be considered.

Eg. Dissociation of water  Step i) H2 O (g) OH (g) + H (g) ∆H0 = 499 kJ

Step ii) OH (g) O (g) + H (g) ∆H0 = 428 kJ

Overall Rean H2 O (g) 2H (g) + O (g) ∆H0 = 927 kJ

Average bond enthalpy of O—H bond = = 463.5 kJ hence ∆H0 (O—H) = 463.5 kJ

Reaction enthalpy from bond enthalpy:-

Que. Define bond enthalpy. How is it useful to calculate reaction enthalpy?

Ans.

In a chemical reaction, in reactants bonds broke while in product bond formed. For
enthalpy calculation we assume all the bonds are identical and bond enthalpy independent
of nature of substance.

The enthalpy of chemical reaction is the difference between the sum of bond
enthalpies of reactants and the sum of bond enthalpies of product.

∆H0 (Reaction) = ∑ ∆H0 (Reactants broken bonds) — ∑ ∆H0 (Product formed bonds)

Eg. H2 (g) + I2 HI (g) ∆H0 ={ [ ∆H0 (H—H) + ∆H0 (I—I) ] — 2∆H0 (H—I) }
 Page 20 of 25

Hess’s Law of constant heat summation:-

The law states that, “the enthalpy change for a reaction is the same whether the
reaction takes place in one step or a series of steps.” OR

“The enthalpy change for a reaction is same regardless of the path of the reaction.”

Proof / illustration:- Consider, a conversion of A to C

B
i) Conversion of A to C in single step

A C ∆H0 = ∆H1 ………. (1)

∆H3
∆H2
ii) Conversion of A to C in two steps

A B ∆H0 = ∆H2

B C ∆H0 = ∆H3
A C
0
Overall A C ∆H = ∆H2 + ∆H3 ……. (2) ∆H1

According to Hess’s Law, ∆H1 = ∆H2 + ∆H3

Eg. Formation of CO2 from C and O2

1) Formation of CO2 in single step C (s) + O2 (g) CO2 ∆H1 = — 394 kJ

2) Formation of CO2 in two step C (s) + O2 (g) CO ∆H2 = — 83 kJ

CO (g) + O2 (g) CO2 ∆H3 = — 311 kJ

According to Hess’s Law, ∆H1 = ∆H2 + ∆H3  — 394 =— 83 — 311  — 394 = — 394

Thus heat evolved in both methods is same. Hence Hess’s Law is proved experimentally.

Application of Hess’s Law:-

1) The thermodynamic equations can be added, subtracted or multiplied by numeral like

simple algebraic equation.

2) It can be used to calculate enthalpy of reaction which does not occurs directly.

3) The enthalpy of formation of any compound from its elements can be calculated.

4) It can be used to calculate enthalpy of formation, combustion, neutralization etc.

5) Enthalpy of formation of slow reaction can be calculated.

6) Enthalpy of reaction which is not possible to determine experimentally can be calculated.

 Page 21 of 25

Spontaneous Process (Irreversible process):-

The process that takes place on its own accord without any external influence is
called spontaneous process. It is also called natural process.

Eg. (1) All natural process are spontaneous i) cliff jumping, ii)

(2) Flow of gas from higher pressure to lower pressure. (3) Flow of heat from hot body to
cold body

(4) Flow of water from higher level to lower level

(5) Dissolution of KCl in water KCl (s) + H2O KCl (aq.)

(6) Acid – Base neutralization reaction

NaOH (s) + HCl NaCl + H2O

Note:- Spontaneity:- The tendency of process to occur naturally is called spontaneity.

Criteria for spontaneity:-

(1) A spontaneous change is one-way or unidirectional. Ie. for reverse change work is required.

(2) A spontaneous change is time is no factor. Ie. Spontaneous reaction may be slow or rapid.

(3) A spontaneous process is continuing till the system attains the equilibrium state.

(4) Once system in equilibrium, it does not undergo any further spontaneous change.

Energy and Spontaneity:-

Generally Spontaneous process are exothermic (∆H0 = — ve) ie. Exothermility favors
Spontaneity. But there are many processes that are endothermic but Spontaneous.

Eg. 1) Melting of ice Ice H2O ∆H = + 4 kJ

2) Dissolution of NaCl in water NaCl (s) + H2O (aq) Na+ (aq) + Cl— (aq)
∆H = + 3.9 kJ

3) Conversion of N2O4 to NO2 above 400 k N2O4 (g) NO2 (aq) ∆H = + 57 kJ

From above example it is evident that energy is not only criteria for spontaneity.
Hence with energy there must be another factor which governs spontaneity. That factor is
entropy. 2nd law of thermodynamics introduces entropy (S).
 Page 22 of 25

The thermodynamic property which measures the molecular disorder

Entropy (S):- or randomness is called entropy.

Disordered State
Ordered State

Highly disordered State

Greater the disorder of a system, higher is the entropy and vice versa. Hence solid
state (ice) has lowest entropy while gaseous state (steam) has highest entropy.

Entropy is a state function. Hence change in entropy ∆S is ∆S = Sfinal — Sinitial

1) I2 (s) (ordered state) I2 (aq) (disordered state ) ∆S is +ve

H2 O

2) 2 H2 (g) + O2 2 H2 O (l) ∆S is —ve

More disordered state disordered state

Quantitative definition of entropy:-

The entropy change (∆S) of a system in a process is the ratio of amount heat
transferred in a reversible manner to the temperature at that heat transfer (T).

∆S = (qrev /T)

Unit of ∆S SI unit = J/k or J/mol.k CGS unit = cal/k or cal/mol.k

Entropy and spontaneity:- (2nd law of thermodynamics)

A process occur by an increase in entropy tend to be spontaneous.

Consider two spontaneous process 1) 2H2O2 (l) 2 H2O (l) + O2 (g) ∆S = +ve

2) 2H2 (g) + O2 (g) 2 H2O (l) ∆S = —ve

From above two examples it is clear that in spontaneous process the entropy may
increase or decrease. This discrepancy is explained by second law of thermodynamics.
 Page 23 of 25

2nd law of thermodynamics:-

“The total entropy of the system and surroundings increases in a spontaneous process.”

Thus, ∆Suniverse = ∆STotal = ∆Ssys. + ∆ Ssurr. > 0 , for spontaneous process

OR The total entropy of the system is constantly increasing.
(1) ∆STotal > 0 , the process is spontaneous. (2) ∆STotal < 0 , the process is non-spontaneous.

(3) ∆STotal = 0 , the process is at equilibrium.

Gibbs Energy (Gibbs Function):- (G)

For most of the chemical reactions there are changes in both enthalpy and entropy.
Hence to decide the spontaneity of process in terms of both enthalpy and entropy change
we define new thermodynamic function, called Gibbs energy (G).

Gibbs free energy is defined as , G = H — TS

Where, H is enthalpy and S is entropy of system. T is absolute temperature.

H, S and T are state functions, G is also state function. Hence change in Gibbs Energy (∆G)is
defined as , ∆G = ∆H — T∆S

Unit of ∆G SI unit = J or kJ or kJ/mol CGS unit = cal. Or k.cal or k.cal/mol

Gibbs Energy and spontaneity:-

We have ∆STotal = ∆Ssys. + ∆ Ssurr.  ∆STotal = ∆S + ∆ Ssurr. ……… (1)

If + ∆H is the enthalpy change of system, then enthalpy change of surrounding is —∆H.

∆S = qrev. / T = qsur. / T = — ∆H / T …….. (2)

∆
From eq. (1) & (2), total entropy ∆STotal is, ∆STotal = ∆S —

Multiplying above eq. by — T — T∆STotal = — T∆S + ∆H

Ie — T∆STotal = ∆H— T∆S ……… (3)

The change in Gibbs Energy (∆G)is ∆G = ∆H — T∆S .……… (4)

From eq. (3) & (4) ∆G = — T∆STotal

Ie. ∆G = T ( —∆STotal ) because T is always positive.

Hence if ∆STotal > 0 then ∆G < 0

(1) ∆G < 0, the process is spontaneous (2) ∆G > 0, the process is non-spontaneous

(3) ∆G = 0, the process is at equilibrium.

 Page 24 of 25

¤ The spontaneity of reaction with respect to sign dependence of ∆H, ∆S and ∆G

∆H ∆S ∆G Spontaneity of reaction
— + — Reactions are spontaneous at all the temperatures.
(Exothermic)
— — — Or + Reactions become spontaneous at low temperatures. When
(Exothermic) ІT.∆SІ<І∆HІ
+ + — Or + Reactions become spontaneous at high temperatures. When
(Endothermic) T.∆S > ∆H
+ — + Reactions are non-spontaneous at all the temperatures.
(Endothermic)

Temperature of equilibrium:- We have ∆G = ∆H — T∆S ………….. (1)

At equilibrium, ∆G = 0 Ie. process is neither spontaneous nor non-spontaneous.

∆
Eq. (1) becomes, 0 = ∆H — T∆S ie. ∆H = T∆S T=
∆

∆G and equilibrium constant:-

The change in Gibbs Energy (∆G) of a reaction is related to standard Gibbs Energy
change (∆G0 ) by the relationship

∆G = ∆G0 + RT lnQ = ∆G0 + 2.303 RT log10 Q ………..(A)

Where, ∆G0 = Standard Gibbs energy change R = Gas constant (8.314 kJ/mol)

Q = Reaction quotient T = Temperature

For Q consider a reaction aA + bB cC + dD

[ C ]c [ D ]d OR ×
QC = QP=
[ A ]a [ B ]b ×

Where [] indicate concentration and P indicate partial pressure

At equilibrium Q = k and ∆G = 0 K = equilibrium constant

Eq. (A) becomes 0 = ∆G0 + 2.303 RT log10 k Ie. ∆G0 = — 2.303 RT log10 k
 Page 25 of 25

Third law of thermodynamics:-

It states that, “at absolute zero temperature, the entropy of perfectly ordered
crystalline substance is zero.”

Thus, S = 0 at T = 0 for perfectly ordered crystalline substance. Substance contain impurities

S >0

# The entropy of solid greater than zero (S > 0) at T = 0 & is called residual entropy of
substance.

Importance of 3rd law of thermodynamics:-

(1) It gives absolute starting place from which to measure entropy.

(2) It allows determining the absolute entropy of any substance at any desired temperature.

(3) The standard molar entropy (S0 ) of pure substance can be measured.

(4) Standard entropy change ∆S0 for a reaction can be calculated.

(5) Spontaneity of reaction can be predicted.

Que. How is absolute entropy measured for a pure crystalline substance at high
temperature? Or why is it impossible for any substance to have an absolute entropy zero
at temp. greater than 0 k?

Ans:- For perfectly ordered crystalline substance at absolute zero temperature, the
entropy of is zero S0 = 0. When this substance is heated to the temp. T its entropy will
increase to ST then increase in entropy is given by

∆S = ST — S0 since S0 = 0 then ∆S = ST

Thus the value of absolute entropy at different temperature can be calculated. Hence
at temp. greater than absolute zero, it is impossible for any substance to have an absolute
entropy zero.
.
Note: ST is determined by ST = ∫ Where CP is heat capacity of solid.

Standard molar entropy (S0 ):-

The absolute entropy of one mole of pure substance at 1 atm. Pressure and 25 0C
temperature is called Standard molar entropy of the substance.

Usefulness of Standard molar entropy:-

(1) To determine the ∆ S0 for a reaction. (2) It is used to compare entropies of different
substance under same condition of temperature and pressure. (3) Spontaneity of the
process can be predicted.