TOPIC 7 : THERMOCHEMISTRY

7.4 HESS’S LAW

1. When reactants are converted to products, the total enthalpy change, ΔH is the same whether the
reaction takes place in one step or in a series of steps.

2. Application of Hess’s Law

To calculate the enthalpy change of reactions that are too difficult to carry out directly in a
calorimeter. Using two method: Algebraic method, Energy cycle method.
EXAMPLE 1:
Given the following reactions and their enthalpy changes :
C2H2 (g) + 5/2O2 (g) → 2CO2 (g) + H2O (l) ΔH = -1299.6 kJ
C (s) + O2 (g) → CO2 (g) ΔH = -393.5 kJ
H2 (g) + 1/2O2 (g) → H2O (l) ΔH = -285.9 kJ
Calculate the enthalpy change for this reaction:
2C (s) + H2 (g) → C2H2 (g)

Algebraic method
 Energy cycle method

EXAMPLE 2:

The thermochemical equations are given as below:

C(s) + O2(g) → CO2(g) ΔH = - 393 kJ mol-1

H2(g) + 1/2O2 → H2O(g) ΔH = - 286 kJ mol-1

C2H6(g) + 7/2O2(g) → 2CO2(g)+ 3H2O(g) ΔH = - 1560 kJ mol-1

Calculate the enthalpy of formation for C2H6.

Algebraic method
 Energy cycle method 8.5 BORN-HABER

CYCLE

1. Electron Affinity

The heat change when ……………………………………………………. of electron to form …………………………………

ΔH for EA2 is always ....................because energy is ..................................... ..................to

overcome ......................................................................... between the approaching electron and the
negatively charge ion.
2. Lattice Energy

Symbol:
 The energy released when ................................................. compound is formed from .......................

3. Lattice Dissociation Energy

Symbol:

The energy required to completely ........................................... ionic compound into ......................

The magnitude of ΔHlattice remains but its sign changes.

Larger ∆Hlattice indicates ........................................................ and ........................................................ in

the ionic crystal.

The magnitude of lattice energy increases as :

۩ The ionic radii (r) ............................

☞ …………………………………….

۩ The ionic charges (Q) .........................

☞ .........................................................

Explain:

Why ΔHlattice for MgO is more negative than ΔHlattice for Na2O?
4.Born Haber cycle

1. A Born-Haber cycle summarizes the relationship between the various enthalpy changes
involved in the formation of an ionic crystal from the reaction of a metal (often a Group I
or Group II element) with a non-metal elements.
2. The Born-Haber cycle can be constructed using the energy cycle method.
3. The cycle connects enthalpy of formation with the lattice energy.
Given;
Enthalpy of formation NaCl = -411 kJmol -1
Enthalpy of sublimation of Na = +108 kJmol-1
First ionization energy of Na = +500 kJmol -1
Enthalpy of atomization of Cl = +121 kJmol -1
Electron affinity of Cl = -364 kJmol -1 Construct
the Born-Haber Cycle and determine the
lattice energy of NaCl.

Find the lattice energy from the following data:

−
K(s) → K(g) : +90 kJ mol 1 K(g) → K+(g) : +418 kJ
− −
mol 1 ½Cl2(s) → Cl(g) : +121 kJ mol 1 Cl(g) → Cl-(g)
−
: –364 kJ mol 1 K(s) + ½Cl2(g) → KCl(s) : –436 kJ
−
mol 1

TEST YOURSELF 2

1. Given the following enthalpies of reaction,

C(s) + 2F2(g) → CF4 (g) ΔH = -680 kJ

H2(g) + F2(g) → 2HF(g) ΔH = -537 kJ

C2H4(g) + 6F2(g) → 2CF4(g) + 4HF(g) ΔH = -2490 kJ

Calculate the enthalpy change for the reaction between carbon and hydrogen to form
 ethane, C2H4(g). Ans : ΔH = + 56kJ

2. The formation of carbon monoxide is shown by the equation as below :

C(s) + ½ O2(g) 🡪 CO(g)
Given :
C(s) + O2(g) 🡪 CO2(g) ΔH = -394 kJ mol-1

CO(s) + ½ O2(g) 🡪 CO2(g) ΔH = -283 kJ mol-1

Calculate the enthalpy of combustion of carbon to carbon monoxide. Ans: - 111 kJ mol-1

3. Use Hess’s law to determine ΔH for the reaction :

C3H4 (g) + 2H2 (g) → C3H8 (g)

Given that :
H2 (g) + 1/2O2 (g) → H2O (l) ΔH = -285.8 kJ

C3H4 (g) + 4O2 (g) → 3CO2 (g) + 2H2O (l) ΔH = -1937 kJ

C3H8 (g) + 5O2 (g) → 3CO2 (g) + 4H2O (l) ΔH = -2219.1 kJ Ans = -289.5 kJ 4. The

following data are given :

Ca(s) → Ca(g) = +178 kJ mol-1

½F2(s) → F(g) = +159 kJ mol-1
Ca(g) → Ca+(g) = +590 kJ mol-1
Ca+ (g) → Ca2+(g) = +1150 kJ mol-1
F(g) → F-(g) = -328 kJ mol
Ca(s) + F2(g) → CaF2(s) = -1220 kJ mol-1
. Ans =
Construct the Born-Haber cycle to calculate the lattice energy of CaF2 -2800 kJ/mol

5. Construct the Born-Haber cycle for the formation of magnesium fluoride and determine its
lattice energy.

−
Enthalpy of atomisation of magnesium : +148 kJ mol 1
−
First ionisation energy of magnesium : +738 kJ mol 1
−
Second ionisation energy of magnesium : +1450 kJ mol 1
−
Enthalpy of atomisation of fluorine : +159 kJ mol 1
−
Electron affinity of fluorine : –328 kJ mol 1
−
Enthalpy of formation of magnesium fluoride : –155 kJ mol 1 Ans: ΔHlattice = -2153 kJ/mol
6. 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 mol 1
−
First ionisation energy of copper : +745 kJ mol 1
−
Second ionisation energy of copper : +1960 kJ mol 1
−
Enthalpy of atomisation of oxygen : +248 kJ mol 1
−
First electron affinity of oxygen : –141 kJ mol 1
−
Second electron affinity of oxygen : +791 kJ mol 1
−
Enthalpy of formation of copper(II) oxide : –155 kJ mol 1 Ans: ΔHlattice = -4097 kJ/mol

7.State Hess’s law and explain why this law is useful in determining enthalpy values.

8. a) Define the term standard enthalpy of combustion.

b) Write equation for the standard enthalpy of formation of butane C4H10 c)
Calculate the standard enthalpy of formation of butane.
Standard enthalpies of combustion :
ΔHoc [C4H10 (g)] = -2877kJmol-1
ΔHoc [C (s)] = -394kJmol-1
ΔH c [H2 (g)] = -286kJmol-1 [129kJmol-1]
o

9. a) Define the term standard enthalpy of formation

b) Use the enthalpy of formation data to calculate the enthalpy change in the following
reaction :
2KHCO3(s) 🡪 K2CO3(s) + CO2(g) + H2O(l)
Standard enthalpies of formation ΔHof :
KHCO3(s) = -959kJmol-1
K2CO3(s) = -1146kJmol-1
CO2(g) = -394kJmol-1
H2O(l) = -286kJmol-1 [ +92kJmol-1 ]