TUTORIAL 9 : THERMOCHEMISTRY

1.

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

2.

Define and write an example of thermochemical equation for each of the following terms: (a) (b) (c) (d) (e) (f) (g) (h) Enthalpy of formation. Enthalpy of combustion. Enthalpy of atomisation Enthalpy of neutralisation. Enthalpy of hydration. Enthalpy of solution Enthalpy of sublimation Lattice energy.

3.

Enthalpy of atomisation and enthalpy of sublimation are sometimes used to refer to the same thermochemical process. Explain in what way the two terms are different by giving suitable example.

4.

From the data given, A + B C + D C + D E H = + 100 kJ H = kJ 50

calculate the enthalpy change for each of the reactions below: (a) (b) (c) (d) (e) C + D A + B 2C + 2D 2E 2C + 2D 2A + 2B A + B E E A + B

TUTORIAL 9 : THERMOCHEMISTRY

5.

Consider the following reaction: H2(g) + O2(g) H2O(g) (a) (b) (c) H = 241.8 kJ mol-1 Sketch the energy profile diagram of the above reaction. Which enthalpy is larger, that of the reactants or the product? For the reaction, 2H2O (g) 2H2 (g) + O2 (g) what is the enthalpy change under the same conditions?

6.

(a)

The following reaction occurs at room temperature and pressure: 2Cl (g) Cl2 (g)

State which has higher enthalpy under this condition, Cl (g) or Cl2 (g)? (b) i. At a constant pressure, a complete combustion of acetic acid CH3COOH(l) releases 871.7 kJ mol-1 Write a balanced thermochemical equation for the reaction. Draw the energy profile diagram for the reaction.

ii.

7.

From the following data, 2Fe(s) +

2 O2(g)

Fe2O3(s)

Hf = 822.2 kJ mol-1

determine the enthalpy of combustion of iron.

8.

A 2.4 g sample of carbon is burnt in a calorimeter. Given that Hf for CO2 is -394 kJ mol-1 and the heat capacity of the calorimeter is 10 kJ C-1, calculate the temperature change of the calorimeter.

9.

0.1326 g of aluminium was completely combusted in a constant volume bomb calorimeter with the heat capacity of 1410 Jo C-1. The bomb calorimeter was surrounded by 800g of water. The temperature of the bomb and water increased by 1.726 oC. Calculate the heat of combustion of aluminium in kJ mol-1. [ The specific heat of water is 4.18 J g-1o C-1].

TUTORIAL 9 : THERMOCHEMISTRY

10.

The combustion of naphthalene, C10H8 can be used to calibrate the capacity of a bomb calorimeter. The heat of combustion of naphthalene is 5132.8kJmol -1. When 0.8210 g naphthalene was combusted in a calorimeter containing 1000g water, a temperature rise of 4.21 oC was observed. What is the heat capacity of the bomb calorimeter excluding the water? [The specific heat of water is 4.18 Jg-1oC-1].

11.

When 200 mL of 1.00M NaOH was mixed with 150 mL of 1.00M HCl, in a styrofoam coffee cup calorimeter, the temperature rose from 25.00 oC to 30.00oC. Calculate the heat of neutralisation. Assume that the spesific heat of solution is 4.18 Jg-1oC-1 and density of solution = 1gmL-1.

12.

A student wanted to boil 2.0 kg of water at 20 oC in a kettle. What is the mass of natural gas , CH4 must be burned to raise this quantity of water to 100 oC ? (Assume no heat loss to the surrounding) [Specific heat capacity of water = 4.18 J g-1 oC-1 and Hc of CH4 = -890 kJ mol-1].

13.

(a) (b)

State Hesss Law The enthalphy of combustion of carbon and carbon monoxide are given below : C (s) + O2 (g) CO2 (g) CO (g) + O2(g) CO2 (g) H = -393 kJ mol-1 H = -248 kJ mol-1

calculate the heat change for the following reactions : 2C(s) + O2(g) 2CO(g)

14.

Hydrazine (N2H4) is used as a rocket fuel since its reaction with oxygen is extremely exothermic : N2H4 (l) + O2(g) N2(g) + 2H2O(g) H = -534 kJ mol-1

Calculate the enthalpy of reaction when liquid water is produced instead of steam. N2H4 (l) + O2(g) N2(g) + 2H2O(l) [Given : H2O(l) H2O(g) H = + 40.7 kJ]

TUTORIAL 9 : THERMOCHEMISTRY

15.

Given : S(s) + O2(g) SO2(g) SO2(g) + O2(g) SO3(g) H = 297 kJ mol-1 H = kJ mol-1 99

Calculate Hf for the following reaction using energy cycle method: S(s) +

2 O2(g)

SO3(g)

16.

Given: 4HCl(g) + O2(g) 2H2O(l) + 2Cl2(g) H = 148.4 kJ HF(l) H2(g) + F2(g) H2(g) + O2(g) H2O(l) 2HCl(g) + F2(g) 2HF(l) + Cl2(g) H = + 600.0 kJ H = 285.8 kJ

Use the above data to calculate H for the reaction:

17.

When the plaster of Paris, CaSO4. H2O is mixed with water, it combines with water to produce gypsum, CaSO4.2H2O. The reaction is exothermic, which explains why a plaster cast on a broken leg or leg warms as it hardens. Given : H o f [CaSO4. H2O] = - 1573 kJ mol-1 H o f [CaSO4. 2 H2O] = - 2020 kJ mol-1 H o f [H2O] = - 293 kJ mol-1 Calculate H o ( in kJ) for the reaction: CaSO4. H2O(s) + 3/2 H2O(l) CaSO4.2H2O(s)

18.

Acetylene, C2H2 is a gas used in welding torches. It is produced by the action of water on calcium carbide CaC2. Calculate Hof for acetylene in kJ mol-1 by using the thermochemical equation given below. CaO(s) + H2O(l) Ca(OH)2 (s) CaO(s) + 3C(s,graphite) CaC2(s) + CO(g) CaC2(s) + 2H2O(l) Ca(OH)2(s) + C2H2(g) Ho = - 65.3 kJ Ho = + 462.3 kJ Ho = - 126.0 kJ

TUTORIAL 9 : THERMOCHEMISTRY C(s,graphite) + O2(g) CO(g) 2H2O(l) 2H2(g) + O2(g) 19. Ho = - 220.0 kJ Ho = + 572.0 kJ

The lattice energy of NaCl is -776 kJmol-1 and the enthalpy change when 1 mole of solid NaCl dissolved in water is + 4 kJmol-1. If the enthalpy of hydration of Na+ is -390 kJmol-1, calculate the enthalpy of hydration of Cl in the dissolution process of NaOH using the energy cycle.

20.

Lattice energy for potassium fluoride is -821 kJ mol-1 and its enthalpy of hydration is -819 kJ mol-1. Calculate enthalpy of solution for potassium fluoride.

21.

Construct a Born-Haber cycle diagram from the data below to determine the electron affinity of bromine atom. Reactions Br2(l) Br(g) Rb(s) Rb(g) Rb(g) Rb+(g) + e Rb+(g) + Br-(g) RbBr(s) Rb(s) + Br2(l) RbBr(s) H /kJ +112 +82 +400 -658 -389

22.

Use the data below to construct a Born-Haber cycle for copper(II)oxide and determine the lattice energy. Enthalpy of atomization of copper First ionization energy of copper Second ionization energy of copper Enthalpy of atomization of oxygen First electron affinity of oxygen Second electron affinity of oxygen Enthalpy of formation of copper (II) oxide : : : : : : : + 339 kJ mol-1 + 745 kJ mol-1 + 1960 kJ mol-1 + 248 kJ mol-1 141 kJ mol-1 + 791 kJ mol-1 155 kJ mol-1

TUTORIAL 9 : THERMOCHEMISTRY

23.

A Born-Haber cycle for the formation of calcium oxide is shown below. Ca2+(g) + O2-(g) H5 Ca2+(g) + O(g)

E N E R G Y

H4 Ca2+(g) + O2(g) H3 Ca+(g) + O2(g) H2 Ca(g) + O2(g) H1 Ca(s) + O2(g) H7 CaO(s) H1 = +193 kJmol-1 H2 = +590 kJmol-1 H3 = +1150 kJmol-1 H4 = +248 kJmol-1 H6 = -3513 kJmol-1 H7 = -635 kJmol-1 (a) What enthalpy change does H2, H6 and H7 represent? (b) Use the data given above to calculate H5. (c) By using the value of H5, calculate the first electron affinity if given the second electron affinity of oxygen is +844 kJmol-1. (d) Would the value of H2 be larger or smaller for magnesium than it is for calcium? Explain. H6