Unit 1: Chapter 2: Thermochemistry

 The standard state of a substance at a specified temperature is its pure form at 1 bar.
 The conversion of one phase of a substance to another phase is called a phase
transition.
 (pure solid at 1 bar changing to pure liquid at 1 bar) is called the standard enthalpy
of fusion, (ΔfusH). the reverse of fusion (melting) is freezing.
 pure liquid at 1 bar changing to pure vapour at 1 bar) is called the standard enthalpy
of vaporization (ΔvapH). the reverse of vaporization is condensation.
 The direct conversion of a solid to a vapour is called sublimation. The reverse
process is called vapour deposition.
 ΔforwardH = −ΔreverseH
 The standard enthalpy of combustion, ΔcH , is the change in standard enthalpy per
mole of combustible substance.
 standard enthalpy of ionization, ionH, the standard molar enthalpy change
accompanying the removal of an electron from a gas-phase atom (or ion)
 The reverse of ionization is electron gain, and the corresponding molar enthalpy
change under standard conditions is called the standard electron gain enthalpy,
ΔegH.
 Note that the second ionization enthalpy is larger than the first: more energy is
needed to separate an electron from a positively charged ion than from the neutral
atom.
 exothermic process: ΔH < 0 endothermic process: ΔH > 0
 Hess’s law states that the standard enthalpy of an overall reaction is the sum of the
standard enthalpies of the individual reactions into which a reaction may be divided

Useful formulas for solving numerical problems

1. Enthalpy of phase transition, q = Ivt n △ H ❑vap=q p

Q1. Ethanol is brought to the boil at 1 atm. When an electric current of

0.682A from a 12.0 V supply is passed for 500 sec through a heating coil
immersed in the boiling liquid, it is found that the temperature remains
constant but 4.33g of ethanol is vaporized. What is the enthalpy of
vaporization of ethanol at its boiling point at 1 atm?
Answer: At constant pressure, heat supplied q = ∆H
q = Ivt
∆H = (0.682 A) × (12.0V) × (500s)
This is a change in the enthalpy of the sample.
The amount of ethanol molecules vaporized n = m/M = 4.33g/46.07gmol−1
change in the molar enthalpy is n △ H ❑vap=q p

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 q 0.682× 12.0 ×500
△ H ❑vap= △ H ❑vap= = 4.35 ×104 J mol−1
n 4.33 g /46.07
The value calculated is for the Boiling point of ethanol we indicate by ∆ vapH
(351K)= 43.5 kJ mol−1

2. Enthalpy of sublimation ∆H°sub = ∆H°fus + ∆H°vap

• Q1. Calculate the standard enthalpy of sublimation of ice at 0 oC from its

standard enthalpy of fusion at 0oC (6.01kJmol-1) and the standard enthalpy of
vaporization of water at 0oC (45.07kJmol-1)
Answer: ∆H°sub = ∆H°fus + ∆H°vap
= 6.01+45.07 = 51.08 kJ mol-1
Q2. Calculate the total heat required to melt 100g of ice at 0 oC, heat it to 100
o
C, and then vaporize it at that temp. (assume that the sample is heated at a
constant rate). ∆H°fus at 0 oC = 6.01 kJ/mol; + ∆H°vap at 0 oC = 45.07kJmol-1; and
heat capacity at 0oC = 75.291×10-3 kJ/mol
Answer:
∆H°fus q = n Cp T ∆H°vap
Ice at 0oC H2O (l) at 0oC H2O (l) at 100oCH2O (g) at 100oC

Total heat = n ∆H°fus + n Cp T + n ∆H°vap

= (5.56
mol×6.01 kJmol-1) + (5.56 mol ×75.291×10-3 kJ/mol × 100) +
(5.56 mol×45.07kJmol-1)
= 33.41 + 41.86 + 226.29 = 301.56 kJ

3. Enthalpy of ionization:
Q1. The standard enthalpy of sublimation of Mg at 25 oC is 148kJmol-1. How
much energy as heat (at const. temp. and pressure) must be supplied to1.00g
of solid Mg metal to produce a gas composed of Mg+2 ions and electrons. (The
enthalpy of sublimation, 1st ionisation and 2nd ionisation enthalpies are +148,
+738, and +1451 kJ, respectively)
Answer: The overall reaction is
Mg(s) Mg2+ (g)+2ē
This overall reaction involves sublimation, 1st ionisation and
2nd ionisation of Mg. As per the Hess’s law the overall reaction
is equals to the sum of individual reactions involves in it.

Sublimation : Mg(s) Mg (g) +148 kJ

1st Ionisation: Mg(g) Mg+ (g) +738 kJ
2nd Ionisation: Mg+(g) Mg+2 (g) +1451 kJ

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 The overall reaction is
Mg(s) Mg2+ (g)+2ē +2337 kJ

Molar mass ofMg is 24.31 gmol-1

nMg= 1.0g/24.31gmol-1 =1.0/24.31mol At constant pressure
q= n∆H =(1.0/24.3mol)×2337kJmol-1 = 96.1 kJ

4. Enthalpies of combustion
Combustion of organic compound results in the formation of CO 2 gas and
liquid water. If the compound contain nitrogen- N2 gas is formed
Enthalpies of combustion are measured using Bomb Calorimeter.
In which energy is transferred as heat at const. volume, ∆U=qv

Hess’s law
Q1. Calculate the standard enthalpy of combustion (H) of propene (C3H6)
from the given thermochemical equations?
C3H6(g) + 9/2 O2(g) 3 CO2(g) + 3 H2O(l)H=?

C3H6(g) + H2(g) C3H8(g) H = −124 kJ

C3H8(g) + 5 O2(g) 3 CO2(g) + 4 H2O(l) H = −2220 kJ
H2O (l) H2(g) + ½ O2 (g) H = +286 kJ

Answer: reorganise the given thermochemical equations so that the

reactants and products matches with the combustion reaction of propene
(Which is asked to find out). If the given reactions are opposite, the value of
given H must be changed accordingly.

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 C3H6(g) + H2(g) C3H8(g) H = −124 kJ

C3H8(g) + 9/2 5 O2(g) 3 CO2(g) + 3 4 H2O(l) H = −2220 kJ

H2O (l) H2(g) + ½ O2 (g) H = +286 kJ

C3H6(g) + 9/2 O2(g) 3 CO2(g) + 3 H2O(l)H= -2058 kJ

Q2. Calculate the standard enthalpy of the reaction

C6H6(l) + 3 H2(g) C6H12(l) from the standard enthalpies of
combustion of benzene (-3268 kJ mol−1) and cyclohexane (−3930 kJ mol−1)
and the standard enthalpy of formation of H2O is -286 kJ mol−1

C6H6(g) + 15/2 O2(g) 6 CO2(g) + 3 H2O(l) H- = −3268 kJ

C6H12(g) + 9 O2(g) 6 CO2(g) + 6 H2O(l) H- = −3930 kJ
H2 (g) + ½ O2 H2O (l) H- = −286 kJ

Answer: Reorganise the given thermochemical equations so that the

reactants and products match benzene's hydrogenation (Which is asked to be
found out). If the given reactions are opposite, the value of given H must be
changed accordingly.

C6H6(l) + 3 H2(g) C6H12(l) H=?

________________________________________________________________________________________

C6H6(g) + 15/2 O2(g) 6 CO2(g) + 3 H2O(l) H- = −3268 kJ

6 CO2(g) + 6 H2O(l) C6H12(g) + 9 O2(g) H- = + 3930 kJ

3 [H2 (g) + ½ O2 H2O (l)] H- = −286 kJ x 3 = -858 kJ

C6H6(l) + 3 H2(g) C6H12(l) H= -196 kJ

5. Standard enthalpies of reaction

Change in enthalpy of a reaction when the reactants in their standard

states(pure,1 bar) are completely converted into products in their standard
states.
∆rH =ΣvHm (products) − ΣvHm (Reactants)
v = stoichiometric coefficient

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  The standard enthalpies of formation of elements (O 2, H2, N2….) in
their reference states are zero
Q1. Calculate the standard enthalpy of combustion of liquid benzene from the
standard enthalpies of formation of the reactants and products.
Enthalpy of the formation of CO 2, Water, and Benzene are -393.51, -286, and
+49 kJ/mol-1.
C6H6(g) + 15/2 O2(g) 6 CO2(g) + 3 H2O(l)
Answer: ∆Hr ={6 ∆fH (CO2,gas)+3∆fH (H2O,l)} − {∆fH (C6H6,l)+15/2 ∆fH (O2,g)}
= {6(-393.51)+3(-286)} - {(49)+15/2(0)}
= - 3268 kJ mol-1

6. The variation of reaction enthalpy with temperature (Kirchhoff’s law)

as per the Kirchhoff’s law ∆rH ′ = ∆rH+∆rCp∆T

∆rCp=ΣvCp,m (products) − ΣvCp,m (Reactants)

∆rH′− ∆rH = (∆Cp)r ∆T

Q1. The standard enthalpy of formation of gaseous water at 25 oC is −241.82

kJmol−1. Estimate its value at 100 oC
• H2(g) +½ O2(g) H2O(g)
• The Cp,m values of H2O(g) and O2(g) and H2(g) are 33.58JK−1mol−1 and
29.37JK−1mol−1 & 28.84JK−1mol−1 respectively.

Answer:

∆rH = standard enthalpy of formation at 25 C

∆rH ′ = standard enthalpy of formation at 100 C =?
∆rCp = standard reaction heat capacity

∆rCp = Cp,m(H2O,g)−{Cp,m(H2,g)+ ½Cp,m(O2,g)}

= (33.58JK−1mol−1 −{(28.84JK−1mol−1) + ½×(29.37JK−1mol−1)}
= −9.95JK−1mol−1 = −9.95×10−3 kJ K−1mol−1
∆T = 100-25 = 75K

∆rH ′ = ∆rH+∆rCp∆T
= (−241.82 kJmol−1) + (−9.95×10−3kJ K−1mol−1) × (75K)

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= −242.58 kJmol−1

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