Lecture Notes Compiled by Dr.

Soundarajan Krishnan
THERMO-CHEMISTRY:
Thermo-chemistry is a science that deals with changes in energy
of a physical or chemical process.
Its ultimate aim is to determine the thermodynamic properties
such as heat of formation, enthalpy, etc.
All chemical reactions are accompanied by either absorption of
energy or release of energy.
Endothermic reaction:
When heat is absorbed in a reaction, it is called endothermic
reaction.
Exothermic reaction:
When heat is evolved in a reaction, it is called exothermic
reaction. Lecture Notes Compiled by Dr. Soundarajan Krishnan
Heat capacity:
Heat capacity of a substance is defined as the amount of heat required
to raise the temperature of 1 kg of substance by 1K.
For example, heat capacity of pure water is 4.1855 kJ/(kg.K) at
288K.
Heat capacity for solids and liquids are usually on mass (weight)
basis. (i.e.) kJ/(kg.K) or kcal/(kg.K).
Heat capacity for gases are usually on mole (molar) basis.
(i.e.) kJ/(kgmol.K) or kcal/(kg.K).

Specific heat:
Specific heat of a substance is the ratio of heat capacity of a
particular substance to that of water.
Lecture Notes Compiled by Dr. Soundarajan Krishnan
Enthalpy changes accompanying chemical reactions:
When chemical reactions take place, either heat is absorbed or released.
Three types of reactions formation, combustion and reaction of one or
more substances to form other compounds are of interest.
Standard heat of formation (ΔH⁰f):
A formation reaction is defined as a reaction which forms a single
compound from the elements contained in it.
For example, the formation reaction for Methanol (CH3OH) is:
C (s) + ½ O2 (g) + 2 H2 (g) → CH3OH (l)
The formation reaction for Carbon dioxide (CO2) is:
C (s) + ½ O2 (g) → CO2 (g)
However, H2O (g) + SO3 (g) → H2SO4 (g) is not a formation
reaction.
Lecture Notes Compiled by Dr. Soundarajan Krishnan
It is based on 1 mol of the compound formed. All equations should
include an indication of the physical state of each reactant and product,
whether it is gas, liquid or solid.
For instance, C (s) , O2 (g) , H2O (g), H2O (l), etc.
Standard heat of formation (ΔH⁰f):
A formation reaction is defined as a reaction which forms a single
compound from the elements contained in it.
For example, the formation reaction for Methanol (CH3OH) is:
C (s) + ½ O2 (g) + 2 H2 (g) → CH3OH (l)
The formation reaction for Carbon dioxide (CO2) is:
C (s) + ½ O2 (g) → CO2 (g)
However, H2O (g) + SO3 (g) → H2SO4 (g) is not a formation
reaction.
Lecture Notes Compiled by Dr. Soundarajan Krishnan
Standard heat of combustion (ΔH⁰C):

Combustion refers to oxidation of a substance with oxygen

or air.
The standard heat of combustion of a substance is the heat
effects resulting from combustion of the substance at 1 atm
and 298K (25⁰C), with the combustion reaction beginning
and ending at a temperature of 298K (25⁰C).
For eg.,
CH3OH(l)+3/2 O2(g) →CO2(g)+2H2O(l) ΔH⁰C= – 173.65 kcal/gmol

Lecture Notes Compiled by Dr. Soundarajan Krishnan

Standard heat of reaction (ΔH⁰R or ΔH⁰298):

The standard heat of reaction is the change in

enthalpy of a system resulting from chemical
reaction at 1 atm and 298K with reaction beginning
and ending at a temperature of 298K (25⁰C).

For eg., N2 + 3 H2 → 2 NH3 ΔH⁰298 = - 22.080 kcal

Lecture Notes Compiled by Dr. Soundarajan Krishnan

Material or Mass Balance:
Mass or Material balance is governed by law of Conservation of
Mass.

Lecture Notes Compiled by Dr. Soundarajan Krishnan

Energy Balance:
Energy balance is governed by law of Conservation of Energy.

Lecture Notes Compiled by Dr. Soundarajan Krishnan

Hess’ law of heat summation:
It states that the net heat released or absorbed in a chemical process
is the same irrespective of whether the reaction takes place in 1 or
several steps.

Lecture Notes Compiled by Dr. Soundarajan Krishnan

 Note: ΔH⁰f = Standard heat of formation
ΔH⁰C = Standard heat of combustion
ΔH⁰R or ΔH⁰298 = Standard heat of reaction
ΔH⁰f of all elements = 0
ΔH⁰C of completely oxidized substances = 0 (for eg., for H2O, CO2,
etc.)

1) Calculate the standard heat of formation of Methane gas

CH4 (g) using the following data:
CH4 (g) + 2O2 (g) → CO2 (g) +2H2O (l) ΔH⁰C = – 212.8 kcal
C (s) + O2 (g) → CO2 (g) ΔH⁰f = – 94.05 kcal
2H2 (g) + O2 (g) → 2H2O (l) ΔH⁰f = – 136.63 kcal
Lecture Notes Compiled by Dr. Soundarajan Krishnan
Solution:
C (s) + O2 (g) → CO2 (g) ΔH⁰f = – 94.05 kcal
2H2 (g) + O2 (g) → 2H2O (l) ΔH⁰f = – 136.63 kcal
CO2 (g) + 2H2O (l) → CH4 (g) + 2O2 (g) ΔH⁰C = + 212.8 kcal
C (s) + 2H2 (g) → CH4 (g) ΔH⁰f CH4 = – 94.05 – 136.63 + 212.8
= – 17.88 kcal

Ans: ΔH⁰f CH4 = – 17.88 kcal

Lecture Notes Compiled by Dr. Soundarajan Krishnan

Note: If data is available for ΔH⁰f , then ΔH⁰298 can be
evaluated using the following equation:
ΔH⁰298 = ∑ ΔH⁰f , products – ∑ ΔH⁰f , reactants

If data is available for ΔH⁰C , then ΔH⁰298 can be evaluated

using the following equation:
ΔH⁰298 = ∑ ΔH⁰C, reactants – ∑ ΔH⁰C, products

Lecture Notes Compiled by Dr. Soundarajan Krishnan

2. Calculate the standard heat of reaction at 298K (25⁰C)
for the following reaction:
4 HCl (g) + O2 (g) → 2H2O (g) + 2 Cl2 (g)
ΔH⁰f for HCl (g) = – 22,778 cal/gmol
ΔH⁰f for H2O (g) = – 57,798 cal/gmol

Lecture Notes Compiled by Dr. Soundarajan Krishnan

Solution:
ΔH⁰298 = ∑ ΔH⁰f , products - ∑ ΔH⁰f , reactants
Hence, ΔH⁰298 = 2 (– 57,798 ) – 4 (– 22,778)
= – 24,484 cal = – 24.484 kcal

Ans: ΔH⁰298 = – 24.484 kcal

Lecture Notes Compiled by Dr. Soundarajan Krishnan

 REFERENCE BOOKS
Main text 1. Richard M. Felder and Ronald W. Rousseau, “Elementary
Principles of Chemical Processes”, 3rd ed., John Wiley & Sons,
books Inc., 2000.
supporting the
course 2. David M. Himmelblau and James B. Riggs, “Basic Principles
and Calculations in Chemical Engineering”, 8th ed., Pearson,
U.S.A., 2013.

Additional 1. Luyben, W.L. and Wenzel, L.A., “Chemical Process Analysis:

Mass and Energy Balances”, Prentice-Hall, Englewood Cliffs,
references U.S.A., 1987.
supporting the
course 2. Bhatt, B. and Vora, S., “Stoichiometry”, Tata McGraw-Hill, 4th
ed., 2004.

Lecture Notes Compiled by Dr. Soundarajan Krishnan

THANK YOU

Lecture Notes Compiled by Dr. Soundarajan Krishnan