TUTORIAL 9: THERMOCHEMISTRY

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9.1 Concept of enthalpy

At the end of the topic, students should be able to:
a) Explain endothermic and exothermic reactions using the complete energy profile diagrams.
b) State the conditions of reaction and define the following terms:
i. Enthalpy
ii. Standard enthalpy
c) Define and write the thermochemical equation for each of the following enthalpies:
i. Formation
ii. Combustion
iii. Atomization
iv. Neutralisation
v. Hydration
vi. Solution(dissolution)

1. The following terms are often used in thermochemistry. Explain each one of them by
giving an appropriate example:
(a) Standard enthalpy change
(b) Exothermic process
(c) Endothermic process

2. Define and write an example of thermochemical equation for each of the following
terms:
(a) Standard enthalpy of formation
(b) Standard enthalpy of combustion
(c) Standard enthalpy of atomisation
(d) Standard enthalpy of neutralisation
(e) Standard enthalpy of hydration
(f) Standard enthalpy of solution (dissolution)

3. Consider the following reaction:

H2(g) + O2(g) H2O(g) H = 241.8 kJ
(a) Sketch the energy profile diagram of the above reaction.
(b) Which enthalpy is larger, that of the reactants or the product?
(c) For the reaction,
2H2O(g) 2H2(g) + O2(g)
what is the enthalpy change under the same conditions?

4. The following reaction occurs at room temperature and pressure:

2Cl(g) Cl2(g) H = -ve
State which has higher enthalpy under this condition, Cl(g) or Cl2(g)?

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5. From the following data,

2Fe(s) + 3
2 O2(g) Fe2O3(s) Hf = 822.2 kJ mol1
determine the enthalpy of combustion of iron.

9.2 Calorimeter
At the end of the topic, students should be able to:
a) Define heat capacity(C) and specific heat capacity(c).
b) Calculate the heat change in a
i. Constant-pressure calorimeter (simple calorimeter)
ii. Constant-volume calorimeter (bomb calorimeter)

6. Define heat capacity and specific heat capacity.

7. A bomb calorimetric experiment is performed with powdered xylose, C5H10O5 as the
combustible substance. The data obtained are:
Mass of xylose burned = 1.183 g
Heat capacity of calorimeter = 4.728 kJC-1
Initial calorimeter temperature = 23.29C
Final calorimeter temperature = 27.19C
i) Calculate the heat of combustion of xylose, in kJmol-1 .
ii) Write the thermochemical equation for combustion of xylose.

8. A quantity of 1.922 g of methanol (CH3OH) was burned in a constant-volume bomb

calorimeter. Consequently, the temperature of the water rose by 4.20C. If the quantity
of water surrounding the calorimeter was exactly 2000g and the heat capacity of the
calorimeter was 2.02 kJC-1, calculate the molar heat of combustion of methanol
[The specific heat of water is 4.18 J g1 C1].

9. When 200 mL of 1.00 M NaOH was mixed with 150 mL of 1.00 M HCl in a
styrofoam coffee cup calorimeter, the temperature rose from 25.00C to 30.00C.
Calculate the heat of neutralisation. Assume that the specific heat of solution is 4.18 J
g1 C1 and density of solution is 1 g mL1.

9.3 Hesss Law

At the end of the topic, students should be able to:
a) State Hesss Law
b) Apply Hesss Law to calculate the enthalpy changes using the algebraic method and the energy
cycle method.

10. (a) State Hesss Law

(b) The enthalpies of formation of ammonia, hydrogen chloride and ammonium
chloride are -46.1 kJmol-1, -92.3 kJmol-1, -14.4kJmol-1 respectively
i) Write the thermochemical equation for the formation of each of the
above substances

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ii) Calculate the enthalpy change for the reaction

NH3 (g) + HCl (g) NH4Cl

11. Nitrogen oxides undergo many interesting reactions. Calculate H for the overall
equation
2NO2 (g) + O2 (g) N2O5 (s)
From the following equations:
N2O5(s) 2NO(g) + O2(g) H = 223.7 kJ

NO (g) + O2 (g) NO2 (g) H = -51.7 kJ

12. Given:
S(s) + O2(g) SO2(g) H = 297 kJ
SO2(g) + O2(g) SO3(g) H = 99 kJ
Calculate H for the following reaction using energy cycle method:
S(s) + 3
2 O2(g) SO3(g)

9.4 Born-Haber cycle

At the end of the topic, students should be able to:
a) Define lattice energy and electron affinity.
b) Explain the following effects on the magnitude of lattice energy
i. Ionic charges.
ii. Ionic radius.
c) Explain the dissolution process of ionic solids.
d) Construct Born-Haber cycle for a simple ionic solids using energy cycle diagram.
e) Calculate enthalpy changes using Born Haber Cycle.

13. Acetylene, C2H2, is a gas used in welding torches. It is produced by the action of
water on calcium carbide, CaC2. Calculate H f for acetylene in kJ mol1 by using the
thermochemical equations given below.
CaO(s) + H2O(l) Ca(OH)2(s) H = 65.3 kJ
CaO(s) + 3C(s, graphite) CaC2(s) + CO(g) H = +462.3 kJ
CaC2(s) + 2H2O(l) Ca(OH)2(s) + C2H2(g) H = 126.0 kJ
C(s, graphite) + O2(g) CO(g) H = 220.0 kJ
2H2O(l) 2H2(g) + O2(g) H = +572.0 kJ
14. a) Define lattice energy.
b) Which substance in the following pairs has larger lattice energy? Explain.
KCl or RbCl

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15. Based on the data given below:

Hohydration Na+ = -390 kJmol-1
Hohydration Cl- = -380 kJmol-1
Hosolution NaCl = +6 kJmol-1
i) Construct an energy cycle diagram to represent the dissolution of NaCl.
ii) Calculate the lattice energy of NaCl.

16. Use a Born Haber cycle for KF and the following values to calculate a value for the
standard enthalpy of formation of KF(s)
K (s) K (g) Ho = 90kJ
K (g) K+ (g) + Ho = 419kJ
F2 (g) 2F (g) Ho = 160kJ
F (g) + F- (g) Ho = -336kJ
K+ (g) + F- (g) KF (s) Ho = -821kJ

17. Use the data below to construct a Born-Haber cycle for copper(II) oxide and
determine its lattice energy.
Enthalpy of atomisation of copper : +339 kJ mol1
First ionisation energy of copper : +745 kJ mol1
Second ionisation energy of copper : +1960 kJ mol1
Enthalpy of atomisation of oxygen : +248 kJ mol1
First electron affinity of oxygen : 141 kJ mol1
Second electron affinity of oxygen : +791 kJ mol1
Enthalpy of formation of copper(II) oxide : 155 kJ mol1

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OBJECTIVE QUESTIONS

1. Which of the following processes is endothermic?

A. H2O(s) H2O(l)
B. O2(g) + 2H2(g) 2H2O(g)
C. CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
D. 3O2(g) + 2CH3OH(g) 2CO2(g) + 4H2O(g)

2. Which of the following is an exothermic process?

A. ice melting
B. boiling soup
C. water evaporating
D. condensation of water vapour

3 A __________ H corresponds to an __________ process.

A. negative, endothermic
B. negative, exothermic
C. zero, endothermic
D. zero, exothermic

4. Consider the following reaction:

2Na2O2(s) + 2H2O(l) 4NaOH(s) + O2(g) H = 126 kJ.
The amount of heat released by the reaction of 25.0 g of Na2O2 with water is
A. 20.2 kJ
B. 40.4 kJ
C. 67.5 kJ
D. 80.8 kJ

5. A sample of aluminium metal absorbs 9.86 J of heat when its temperature increases
from 23.2C to 30.5C. If the specific heat capacity of aluminium is 0.90 J g1 C1,
the mass of the sample is
A. 1.5 g
B. 7.2 g
C. 8.1 g
D. 65 g

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6. Choose a substance with H f 0

A. I2(s)
B. Na(s)
C. Br2(l)
D. CO2(g)

Summary of options
A B C D

I only I and II only II and III only I, II, and III

7. Enthalpy of neutralisation is the heat released when

I. 1 mol of acid reacts with 1 mol of base.
II. 1 mol of aqueous H+ reacts with 1 mol of aqueous OH.
III. 1 mol of water is formed from the reaction of an acid and a base.

8. Choose the correct statement(s).

I. Ionisation energy is always positive.
II. Electron affinity is always negative.
III. Enthalpy of hydration can be positive or negative.

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