Thermochemistry

Lecture 2

ASHWANI TYAGI
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Thermochemistry
Factors on which the heat of reaction depends

1. Quantities of the reactants involved.

2. Physical state of reactants & products.
3. Allotropic modifications
4. Concentration of solutions
5. Temperature
6. Conditions of constant pressure or constant volume
Factors Affecting Heat of Reaction

Physical State of Reactants and Products

H2(g) + ½ O2(g) → H2O(g) ; △H = - 57.8 kcal

H2(g) + ½ O2(g) → H2O(l) ; △H = - 68.32 kcal

Allotropic Forms of The Element

C (diamond) + O2(g) → CO2(g) ; △H = - 94.3 kcal

C (graphite) + O2(g) → CO2(g) ; △H = - 97.6 kcal
 Factors Affecting Heat of Reaction

Temperature (Kirchhoff's Equation)

Example An ideal gas initially at 27°C and 1 bar pressure is heated under isobaric
condition until volume get double. The variation of molar heat capacity with
absolute temperature is given by Cp = 22 + 48 x 10-3 T
Where CP is in JK-1 mol-1. Calculate variation in ΔHM (approx.)

A. 15 kJ / mol
B. 14 kJ / mol
C. 16 kJ / mol
D. 13 kJ / mol
 Factors Affecting Heat of Reaction

Concentration of Solutions

Enthalpy change may occur when a solution is diluted from one

concentration to another concentration.

Conditions of constant pressure / constant volume

Example For the reaction,
C3H8 (g) + 5O2 (g) → 3CO2(g) + 4H2O (I) at constant temperature, △H - △E
is

A. -RT
B. RT
C. -3RT
D. +3RT
Standard Enthalpy of Reactions

The standard enthalpy of reaction is the enthalpy change for a reaction when
all the participating substances are in their standard states.

i
Standard Conditions

State Standard State

Gas Ideal gas at 1 atm and the given temperature

Liquid Pure liquid at 1 atm

i and the given
i temperature
Solid Stable crystalline form at 1 atm and given T (e.g., graphite form of
carbon, rhombic form of sulphur)
Substance Standard State Heat of Formation

Hydrogen gas 0.0 Kcal / mol defined

Oxygen gas 0.0 Kcal / mol defined

Chlorine gas 0.0 Kcal / mol defined

Bromine Liquidi 0.0 Kcal / mol defined

Carbon Solid (graphite) 0.0 Kcal / mol defined

Water Liquid -68.3 measured

Carbon -94.1 measured

gas
Dioxide

Methane gas -17.9 measured

Sodium -98.2
Solid (crystalline)
Chloride
Hess’s Law of constant heat summation
Different types of heats /enthalpies of reaction
Enthalpy of Combustion
The Enthalpy of Combustion of a substance is defined as the heat change
(usually the heat evolved) when 1 mole of substance burnt or oxidized in oxygen.
 Enthalpy of Combustion

C (s) + 1/2 O2(g) ⟶ CO (g), ΔH = - 110.5 KJ mol-1

C (s) + O2(g) ⟶ CO2(g), ΔH = -393.5 kJ mol-1

Standard Enthalpy of Combustion is the amount evolved when 1 mole of a

substance under standard conditions (298 K, 1 bar pressure) is completely burnt
to form the products also under standard conditions. It is represented by Δ C HO.

C4H10 (g) + 13/2 O2(g) ⟶ 4CO2 (g) + 5H2O (t), ΔcH0 = -2658.0kJ mol-1
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