Chapter 7 Chemical Energetics

Enthalpy of Reaction, ∆H Bomb Calorimeter In bomb calorimeter, combustion occurs.

m = mass of solution/water The heat released during the combustion
𝐻𝑒𝑎𝑡 𝑐ℎ𝑎𝑛𝑔𝑒 = 𝑚𝑐𝜃 𝐻𝑒𝑎𝑡 𝒂𝒃𝒔𝒐𝒓𝒃𝒆𝒅 = 𝑐∆𝑡 is absorbed by the calorimeter.
c = heat capacity of solution/water
c = heat capacity of calorimeter
3 marks question:
Enthalpy change of Heat released or absorbed in a chemical reaction. ▪ Formula [1]
reaction (∆Hr ) ∆Hr = ∑∆H°f (product) − ∑∆H°f (reactants) ▪ Substitution [1]
▪ Final answer [1]

Standard enthalpy change Heat change when 1 mole of the substance is formed from its elements under 3
Ca(s) + C(s) + O2 (g) → 𝐂𝐚𝐂𝐎𝟑 (𝐬)
of formation (∆H°f ) standard conditions. 2 ↑
1 mol
Product formed: Positive (not stable) | Negative (stable)

Standard enthalpy change Heat released when 1 mole of the substance is completely burnt in excess oxygen 𝐂𝟑 𝐇𝟖 (𝐠) + 5O2 (g) → 3CO2 (g) + 4H2O(g)
of combustion (∆H°c) under standard conditions. ↑
1 mol

Standard enthalpy change Heat released when 1 mole of gaseous ion is dissolves in water to form hydrated 𝐍𝐚+ (𝐠) → Na+ (aq)
↑
of hydration (∆H°hyd ) ions under standard conditions. 1 mol

(∆H°hyd(cation) + ∆H°hyd(anion) ) 𝐶ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝑖𝑜𝑛

∆H°hyd ∝ 𝐂𝐥− (𝐠) → Cl− (aq)
𝐼𝑜𝑛𝑖𝑐 𝑟𝑎𝑑𝑖𝑢𝑠 ↑
1 mol

Standard enthalpy change Heat change when 1 mole of the substance is dissolves in water to form solution at 𝐍𝐚𝐂𝐥(𝐬) + (aq) → Na+ (aq) + Cl− (aq)
of solution (∆H°soln ) infinite dilution under standard conditions. ↑
1 mol

Positive (less soluble) | Negative (more soluble)

Standard enthalpy change Heat released when 1 mole of hydrogen ion and 1 mole of hydroxide ion react to 𝐇𝐂𝐥(𝐚𝐪) + 𝐍𝐚𝐎𝐇(𝐚𝐪) → NaCl(aq) + 𝐇𝟐 𝐎(𝒍)
↑ ↑ ↑
of neutralisation form 1 mole of water under standard conditions. Strong acid Strong base 1 mol

(∆H°neutralisation ) ▪ Strong acid + strong base ∆H°neutralisation = −57.3kJ mol−1 (1 mol) (1 mol) ∆H = −57.3kJ mol−1
𝐂𝐇𝟑 𝐂𝐎𝐎𝐇(𝐚𝐪) + 𝐍𝐚𝐎𝐇(𝐚𝐪) → CH3 COONa(aq) + 𝐇𝟐 𝐎(𝒍)
▪ Weak acid + weak base ∆H°neutralisation < −57.3kJ mol−1 ↑ ↑
Weak acid Strong base
↑
(Weak acids and weak alkalis do not dissociate completely in aqueous. Some (1 mol) (1 mol)
1 mol
∆H = −55.2kJ mol−1
heat released is absorbed during dissociation of acid) 𝟏 1
𝐇 𝐒𝐎 (𝐚𝐪) + 𝐍𝐚𝐎𝐇(𝐚𝐪) → Na 2SO4 (aq) + 𝐇𝟐 𝐎(𝒍)
▪ Strong polyprotic acid + strong base ∆H°neutralisation > −57.3kJ mol−1 𝟐 𝟐 𝟒 2
↑ ↑ ↑
(the heal dilution of sulphuric acid is more exothermic) Strong
polyprotic acid
Strong base
(1 mol) 1 mol
(1 mol)
∆H = −66.4kJ mol−1
Standard enthalpy change ▪ Standard enthalpy change of atomisation of element 1
H (g) → 𝐇(𝐠)
of atomisation (∆H°atm ) Heat absorbed when 1 mole of the gaseous atom is formed from the element under 2 2 ↑
1 Applicable for standard conditions. 1 mol
∆H°atm = BE
2 diatomic gas
▪ Standard enthalpy change of atomisation of compound 𝐂𝐇𝟒 (𝐠) → C(g) + 4H(g)
atomisation Heat absorbed when 1 mole of the compound is converted to gaseous atom under ↑
A absorbed standard conditions.
1 mol

Average bond energy Average energy absorbed to break 1 mole of a covalent bond in a gaseous 𝐎𝟐 (𝐠) → 2O(g)
molecule under standard conditions. ↑
1 mol

∆H = ∑∆H(bond broken) − ∑∆H(bond formed)

Ionisation energy ▪ First ionisation energy Na(g) → Na+ (g) + 𝐞−

The minimum amount of energy required to remove 1 mole of electrons from 1 mole ↑
1 mol

of gaseous atoms to form unicharged gaseous ions under standard conditions.

▪ Second ionisation energy Na+ (g) → Na2+ (g) + 𝐞−

The minimum amount of energy required to remove 1 mole of electrons from 1 mole ↑
1 mol

of gaseous unicharged ions under standard conditions.

Electron affinity ▪ First electron affinity O(g) + 𝐞− → O− (g)

↑
Energy released when 1 mole of the gaseous atoms of the element gain 1 mole of 1 mol

electrons to form 1 mole of gaseous ions charged -1 under standard conditions.

o Energy is released when a force attraction is formed between the positive
nucleus and electron received

▪ Second electron affinity O− (g) + 𝐞− → O2− (g)

↑
Energy absorbed when 1 mole of the uninegative charged ions gain 1 mole of 1 mol

electrons to form 1 mole of gaseous ions charged -2 under standard conditions.

o Energy is absorbed to overcome the repulsive force between the electron
gained and negatively charged ion

Lattice energy Lattice energy is the heat released when 1 mole of ionic crystal is formed from its Na+ (g) + Cl− (g) → 𝐍𝐚𝐂𝐥(𝐬)
Strength of ionic bond ↑
gaseous ions under standard conditions. 1 mol
The more exothermic (negative),
the stronger the ionic bond
𝑃𝑟𝑜𝑑𝑢𝑐𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝑏𝑜𝑡ℎ 𝑖𝑜𝑛𝑠
𝐿𝑎𝑡𝑡𝑖𝑐𝑒 𝐸𝑛𝑒𝑟𝑔𝑦 ∝
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑖𝑜𝑛𝑠
Exothermic Reaction Endothermic Reaction
▪ The reaction that release heat energy to the surrounding. ▪ The reaction that absorb heat energy from the surrounding.

Reaction Coordination Reaction Coordination

Energy level diagram Energy level diagram ▪ ∆H = 𝐩𝐨𝐬𝐢𝐭𝐢𝐯𝐞

▪ ∆H = 𝐧𝐞𝐠𝐚𝐭𝐢𝐯𝐞 ▪ Heat / Energy absorbed
▪ Heat / Energy released ▪ Surrounding
▪ Surrounding temperature increases temperature decreases
∆H

Reaction Coordination

Energy profile diagram Energy profile diagram

Hess’ Law ∆Hr

A B+C
▪ Hess’ law states that the enthalpy changes of a reaction is
the same, regardless of the whether the reaction occurs in ∆H1 ∆H2
one step or few steps/independent of the route by which the ∆H3
reaction occurs, provided the initial and final conditions are
the same. D + E + F

∆Hr = −∆H1 + ∆H2 + ∆H3

Born-Haber Cycle
+
▪ Lattice energy is the measurement of the strength of the ionic bond in an ionic crystal.
▪ More heat released to form a stronger ionic bond
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝑏𝑜𝑡ℎ 𝑖𝑜𝑛𝑠
𝐿𝑎𝑡𝑡𝑖𝑐𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 ∝
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑖𝑜𝑛𝑠

▪ A Born-Haber cycle to determine the lattice energy of sodium chloride (NaCl) is shown below.
Energy / kJ

4
5
In general:

3
1. ∆H°f
2. ∆H°atm
3. IE
4. ∆H°atm
2 6 5. EA
6. LE

Solubility of Solids in Liquids

▪ ∆H°lat and ∆H°hyd are always negative. Hence, the enthalpy of solution depends on the values of lattice energy and hydration energy.
∆H°soln = −∆H°LE + ∆H°hyd

Gaseous Ions
Energy/ kJ

−∆H°LE
∆H°hyd(cation) + ∆H°hyd(anion)

Solute + Solvent
∆H°soln

Solution

Thermochemical Equation
▪ Example:

C3 H8 (g) + 5O2 (g) → 3CO2 (g) + 4H2 O(g) ∆H°c = −2202 kJ mol−1
Requirement:
1. Balanced equation
2. Physical state
3. Enthalpy change
Insist physical state Enthalpy change