THERMODYNAMICS

SYLLABUS

Concepts of System and types of systems, surroundings, work, heat, energy, extensive
and intensive properties, state functions.
First law of thermodynamics -internal energy and enthalpy, heat capacity and specific
heat, measurement of ΔU and ΔH, Hess's law of constant heat summation, enthalpy
of bond dissociation, combustion, formation, atomization, sublimation, phase
transition, ionization, solution and dilution.
Second law of Thermodynamics (brief introduction) Introduction of entropy as a state
function, Gibb's energy change for spontaneous and non- spontaneous processes,
criteria for equilibrium.
Third law of thermodynamics (brief introduction).
 In Thermodynamics, we will learn

How to determine the energy changes occurring during a chemical

reaction?
Will a chemical reaction occur or not?
What is the driving force behind a chemical reaction?
 Pre-assessment
1. The units of heat are:
(a) Degree and calorie (b) calorie and joule
(b) Degree and joule (d) watt and joule
2. A reaction will be spontaneous at all temperatures when:
(a) ΔH < 0 , Δ S =0 (b) Δ H > 0, Δ S >0
(c) Δ H < 0 , Δ S > 0 (d) Δ H = 0, Δ S = 0
3. In which of the following cases will entropy decrease?
(a) Melting of ice (b) Crystallisation of salt from water
(c) Dissolution of sugar in water (d) Burning of coal
4. In an adiabatic process:
(a) Δ q = 0 (b) Δ S = 0 (c) Δ U = 0 (d) ΔH = 0
 Thermodynamics

The branch of science that deals with the study of different forms of energy and
the quantitative relationship between them.
Basic Terms Used In Thermodynamics
1. System and Surroundings
Universe = System + surroundings
System: The part of universe under our investigation
Types of System
 Terms In Thermodynamics

2. State of a System
 Basic Terms Used In Thermodynamics

2. State of a System
State of a system is the condition of the system when its measurable
properties(like T, P, V) have definite values.

MEASURABLE PROPERTIES/STATE VARIABLES

The properties like T, P, V , n which are required to describe the state of a system.
 Basic Terms Used In Thermodynamics

3. State function
Properties of a system whose value depends only upon the initial and
final state of a system and is independent of the path by which state is
reached.
Eg : T, P, V, U, H, S, G
 Basic Terms Used In Thermodynamics

4. Extensive and Intensive properties

Extensive: The macroscopic properties that depends on quantity of matter
contained in the system.
Ex: Mass, V, heat capacity, U, H, S,G
Intensive: The macroscopic properties that are independent of quantity of matter
contained in the system.
Ex: T, P, density, melting point, boiling point, surface tension, viscosity, emf etc.
 Basic Terms Used In Thermodynamics

5. Thermodynamic Equilibrium:
A system is said to be thermodynamic equilibrium if its measurable
properties does not change with time
 Basic Terms Used In Thermodynamics

6. Types of Processes
1. Isothermal Process
2. Isobaric Process
3. Isochoric Process
4. Adiabatic Process
5. Reversible and irreversible Process
6. Cyclic
 Basic Terms Used In Thermodynamics

6. Internal Energy of a system

The sum of all forms of energies stored within a system is called its
INTERNAL ENERGY.
INTERNAL ENERGY changes when
1. Heat enters or leaves the system.
2. Work is done by the system or on the system.
3. Matter enters or leaves a system
INTERNAL ENERGY CHANGE (ΔU)
ΔU = U2 – U1
For a chemical reaction R → P
ΔU = UP – UR

IMP POINTS
U is a state function.
U is an extensive property.
U is a function of T.
For an isothermal process, ΔT = 0 , ΔU = 0
How can we bring about a change in the state of a system?
Change of state of a system can be brought about by
1. Doing work
2. Transfer of heat.
 Change in internal energy(ΔU) can be expressed as

Heat absorbed at constant volume is equal to the change in Internal

energy.
Δ U = qv
For an adiabatic process, work done on the system is equal to the change
in Internal energy.
Δ U = wad
 First Law of Thermodynamics

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

“The energy of an isolated system is a constant”.

OR
The total energy of the universe remains constant, although it may undergo transformation
from one form to another.

Mathematical expression: ΔU = q + w
 Questions

1. In a process, 701 J of heat is absorbed by a system and 394 J of work is done by

the system. What is the change in internal energy for the process?
For an ideal gas undergoing isothermal change……
ΔT = 0
ΔU = 0
q= -w
Work done, w = P Δ V
Work done during expansion , w = - P Δ V
Question:
What will be the heat absorbed by an ideal gas while undergoing an isothermal expansion
in vacuum( free expansion)?
 ENTHALPY – H (heat content)

Most of the reactions are carried out at atmospheric pressure.

ΔU = q + w
For expansion of a gas at constant P
ΔU = qp - P ΔV -----------(1)
Enthalpy: Heat absorbed by a system at constant pressure.
ΔH = qp ------------------(2)
From (1) and (2)
ΔH = ΔU + P ΔV
 TRUE OR FALSE

1. Enthalpy and internal energy are state functions.

2. Enthalpy and internal energy are intensive properties.
3. Internal energy change is heated evolved or absorbed at constant pressure.
4. Enthalpy change is heated evolved or absorbed at constant pressure.
5. For reaction involving solids and liquids, ΔH = ΔU
 Relation between qp and qv

ΔH = ΔU + P ΔV
When ΔH = +ve, reaction is said to be endothermic.
When ΔH = -ve, reaction is said to be exothermic.
For solids and liquids , there will be no change in volume on heating.
Therefore for solids and liquids, P ΔV = 0 or ΔH = ΔU

For gases
ΔH = ΔU + P ΔV
qp = qv + P ΔV
qp = qv + ΔngRT
 NUMERICAL

• When NH4NO2(s) decomposes at 100oC, it forms nitrogen and steam. The heat change
for the decomposition at constant pressure is -223.6 kJ/mol. What is the value of heat
change for the reaction at constant volume?
•
• The reaction of cynamide, NH2CN(s) with dioxygen was carried out in a bomb
calorimeter and ΔU was found to be -742.7 kJ/mol at 298K.
Calculate the enthalpy change for the reaction at 298K.
NH2CN(s) + 3/2 O2 (g) → N2 (g) + CO2(g) + H2O(l)
 NUMERICAL

• The reaction of cynamide, NH2CN(s)

with dioxygen was carried out in a
bomb calorimeter and ΔU was found to
be -742.7 kJ/mol at 298K.
Calculate the enthalpy change for the
reaction at 298K.
NH2CN(s) + 3/2 O2 (g) → N2 (g) + CO2(g)
+ H2O(l)
 THERMOCHEMISTRY

The branch of chemistry that deals with the heat changes during
chemical reactions.
Thermochemical Equation:
A balanced chemical equation which indicates the amount of heat
absorbed or evolved in a chemical reaction.
Example 1:
CH4 (g) + 2 O2 (g) → CO2 (g) + 2H2O(l) ΔrH = - 890.4 kJ/mol
 THERMOCHEMISTRY

Thermochemical Equation:
Example 2:
H2 (g) + ½ O2 (g) → H2O (l) ΔrH = - 285.8 kJ/mol
H2 (g) + ½ O2 (g) → H2O (l) + 285.8 kJ/mol
2H2 (g) + O2 (g) → 2 H2O (l) ΔrH = - 571.6 kJ/mol
 ENTHALPY OF REACTION

Enthalpy of a reaction/Reaction Enthalpy:

The amount of heat absorbed or evolved in a chemical reaction.
a (Reactants ) → b (Products)
ΔrH = Σ b (H products)- Σ a (H reactants)
Example 1:
C(s) + O2(g) → CO2 (g) ΔrH = -393.5 kJ/mol
C(s) + O2(g) → CO2 (g) + 393.5 kJ/mol

Example 2:
CaCO3(s) → CaO (s) + CO2(g) ΔrH = + 177.8 kJ/mol
CaCO3(s) + 177.8 kJ/mol → CaO (s) + CO2(g)
 STANDARD ENTHALPY OF REACTION

Standard enthalpy of reactions (ΔrHƟ)

The enthalpy(heat) change for a reaction when all the reactants and
products are in the standard state.
Standard state:
Most stable state and purest form of a substance.
T = 25oC or 298 K
P = 1 bar
n = 1 mole
 ENTHALPY CHANGES DURING PHASE
TRANSFORMATIONS

1. Standard enthalpy of Fusion (ΔfusHƟ) :

The enthalpy change that accompanies melting of 1 mole of a solid at its
melting point.
Ex: H2O(s) → H2O(l) ΔfusHƟ = + 6 kJ/mol
ΔfusHƟ is always endothermic, hence has positive values.
What will be the value for standard enthalpy of freezing of water?
 ENTHALPY CHANGES DURING PHASE
TRANSFORMATIONS

2. Standard enthalpy of Vapourisation (ΔvapHƟ) :

The amount of heat required to convert 1 mole of a liquid into its vapour
state at its boiling point.
Ex: H2O(l) → H2O(g) ΔvapHƟ = + 40.79 kJ/mol
 ENTHALPY CHANGES DURING PHASE
TRANSFORMATIONS

3. Standard enthalpy of Sublimation(ΔsubHƟ) :

The enthalpy change that accompanies when 1 mole of a solid is directly
changed into its vapour state at a constant temperature and standard
pressure(1 bar)
Ex: I2 (s) → I2 (g) ΔsubHƟ = + 62.39 kJ/mol
 OTHER STANDARD ENTHALPY OF REACTION

Standard Enthalpy of Atomisation (ΔaHƟ):

The enthalpy changes during the breaking of 1 mole of bonds in a
substance into atoms.
Ex: H2(g) → 2H(g) ΔaHƟ = 435 kJ/mol

O2(g) → 2O(g) ΔbondHƟ = 505 kJ/mol

 OTHER STANDARD ENTHALPY OF REACTION

Mean Bond enthalpy for polyatomic molecules

CH4(g)→CH3(g)+H(g) ΔbondHƟ = + 427 kJ /mol
CH3(g) →CH2 (g)+H(g) ΔbondHƟ = + 439 kJ/ mol
CH2 (g) → CH(g) + H(g) ΔbondHƟ = + 452 kJ/mol
CH(g) → C(g) + H(g) ΔbondHƟ = + 347 kJ/ mol

CH4 (g) → C (g) + 4H(g) ΔaHƟ = 1665 kJ/mol

Mean bond enthalpy = ¼ (ΔaHƟ ) = 1665/4 = 416 kJ/mol
The standard enthalpy of reaction is related to bond enthalpies of
reactants and products in gas phase reaction as:
ΔrHƟ = Σ bond enthalpies (reactants)- Σ bond enthalpies (products)
 OTHER STANDARD ENTHALPY OF REACTION

Standard Enthalpy of combustion(ΔcHƟ) :

The enthalpy changes during the combustion of 1 mole of a substance is
completely burnt or oxidised in oxygen.
CH4 (g) + 2 O2 (g) → CO2 (g) + 2 H2O(l)
ΔcHƟ = - 890.4 kJ/mol
 OTHER STANDARD ENTHALPY OF REACTION

Standard Enthalpy of Solution(ΔsolHƟ) :

The enthalpy change during the dissolution of 1 mole of a solute in a
definite amount of solvent.
Ex: KCl (s) → KCl (aq) ΔsolHƟ= + 18. 6 kJ/mol
 OTHER STANDARD ENTHALPY OF REACTION

The dissolution of an ionic compound in water takes place in two steps:

• Dissociation of ionic solid into free ions. The energy required for
this process is Lattice enthalpy.
• Hydration of ions known as solvation of ions. The energy released
in this process is called energy of hydration.
• Therefore, ΔsolHƟ= ΔlatticeHƟ + ΔhydHƟ
• ΔsolHƟ is found to be +ve ( endothermic ) for most of the ionic
compounds. Hence, dissolution increases with increase in
temperature.
 OTHER STANDARD ENTHALPY OF REACTION

Standard Enthalpy of Formation(ΔfHƟ) :

The enthalpy change during the formation of 1 mole of a substance from
its constituent elements.
Ex: C(s) + O2(g) → CO2 (g) ΔfHo = - 393.5 kJ/mol
All elements in their standard state have standard enthalpy of formation
equal to zero.
 NUMERICAL
1. The enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are -110, -393, 81 and
9.7 kJ/mol respectively. Find the value of ∆rHo for the reaction:
N2O4(g) + 3CO(g) → N2O(g) + 3CO2(g)
2. Calculate the heat of reaction(enthalpy change) of the following reaction:
CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l)
Given that: ∆fHo CH4(g) = -74.8 kJ/mol ∆fHo CO2(g) = -393.5 kJ/mol
∆fHo H2O(l) = -285.8 kJ/mol
3. Calculate the bond enthalpy of Cl-Cl bond from the following data:
CH4(g) + Cl2(g) → CH3Cl(l) + HCl(l)
∆rHo = -100.3kJ/mol
Given bond enthalpies of C-H, C-Cl and H-Cl bonds are 413, 326, and 431 kJ/mol resp.
 NUMERICAL
3. Calculate the bond enthalpy of Cl-Cl bond from the following data:
CH4(g) + Cl2(g) → CH3Cl(l) + HCl(l)
∆rHo = -100.3kJ/mol
Given bond enthalpies of C-H, C-Cl and H-Cl bonds are 413, 326, and 431 kJ/mol resp.