Thermochemistry

Learning Outcomes
• The Concept
- Endothermic & Exothermic reactions
- Enthalpy Diagrams
• Standard Enthalpy Change of the reaction
- Determination of Enthalpy Change
- mc∆T
- Types of Standard Enthalpy Changes
• Hess law
- Bond dissociation enthalpy
Chemical Reaction
Chemical Reaction

Exothermic Reaction Endothermic Reaction

‐ Release Heat Energy ‐ Absorb Heat Energy
‐ Example: Combustion ‐ Example: Ba(OH)2 + NH4Cl
Enthalpy Change of Reaction

Enthalpy (H) = Heat content of the system (product/ reactant)

Enthalpy Change (∆H) = Heat energy released/ absorbed in a chemical reaction

• ∆H = Hproduct – Hreactant
• If reaction is Exothermic, ∆H < 0 (Hproduct < Hreactant)
• If reaction is Endothermic, ∆H > 0 (Hproduct > Hreactant)
Chemical Reaction
chemical reaction
A + B C + D
Hreactant Hproduct

Exothermic reaction, ∆H = negative (Hproduct < Hreactant) Endothermic reaction, ∆H = positive (Hproduct > Hreactant)
Enthalpy Change of Reaction
• Unit of ∆H = kJ mol-1
• The use of mol-1 does not imply per mole of any material formed or used up but
is per molar quantities

CH4 + 2O2 → CO2 + 2H2O ∆H = -890 kJ mol-1

2CH4 + 4O2 → 2CO2 + 4H2O ∆H = -1780 kJ mol-1 2 x 890 kJ mol-1

• Magnitude of ΔH is directly proportional to the amount of reactant consume

• ΔH for a reaction is equal in magnitude but opposite in sign to ΔH in reverse
reaction
CO2 + 2H2O → CH4 + 2O2 ∆H = 890 kJ mol-1
Question 1
The diagram represents the reaction pathway for the following reaction:

W(g) + X(g) → Y(g) + Z(g)

What statement can be made about the reverse reaction?

1. It will have a larger activation energy and a positive ΔH

2. It will have a larger activation energy and a negative ΔH
3. It will have a smaller activation energy and a positive ΔH
4. It will have a smaller activation energy and a negative ΔH
Determination of Enthalpy Change

Example:

CH4 + 2O2 → CO2 + 2H2O(g) ΔH = -890 kJ mol-1

• How to measure the enthalpy change of reaction, ∆H?

### Change in Temperature ###

Determination of Enthalpy Change

• ∆H = Enthalpy change of reaction (kJmol-1)

m = mass of H2O/solution(g)
mc∆T c = specific heat capacity of H2O (4.18 J g-1 °C-1 or 4.18 J g-1 K-1
∆H = ∆T = Temperature change (°C) or in Kelvin
1000n
n = no. of mol of sample

• Temperature increase, ∆H = Negative (Example: -10.0 kJ mol-1)

• Temperature decreases, ∆H = Positive (Example: 20.0 kJ mol-1)
Determination of Enthalpy Change
Instrument to measure enthalpy change of combustion
Question 1
Calorimeters are often calibrated by measuring the temperature change when a
compound of known heat of combustion was reacted. In a typical experiment
0.10 g of ethanol, was completely burnt in a calorimeter. The temperature of the
calorimeter changes from 25 °C to 29 °C.

C2H5OH(s) + 7/2O2 (g) → 2CO2 (g) + 3H2O (l) ΔH = -1000 kJ mol-1

i) How many moles of ethanol had reacted?

ii) How much heat energy was released during the reaction?
Question 2
The unsaturated hydrocarbon Z is obtained by cracking hexane and is important in
the chemical industry. The standard enthalpy change of combustion of Z is -2059 kJ
mol-1. When 0.47 g of Z were completely burnt in air, the heat produced raised the
temperature of 200 g of water by 27.5 ⁰C.

a) i. Calculate the amount of heat released in this experiment.

ii. Use the data above and your answer in i. to calculate the relative
molecular mass of Z.

b) Deduce the molecular formula of Z.

Question 3
The propane gas in the tank is used as a fuel in the factory. The equation for its
combustion is:

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) ∆H = –2220 kJ mol–1

Calculate the amount of heat energy, in kJ, produced during the combustion of 30.0
kg of propane gas and 1 kg of oxygen.
Types of Enthalpy Changes
Type of Enthalpy Concept Example

• Heat involved in production of 1 mole of product starting Formation of propane:

Formation, ΔHf from element. 3C(s) + 4H2(g) → C3H8(g) ΔH = -84.68 kJ mol
-1

• Heat involved in production of carbon dioxide and water

Combustion of methane:
by combination of organic compounds with oxygen.
Combustion, ΔHc • In most cases enthalpy-change is negative, and reaction
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
-1
ΔH = -890 kJ mol
is exothermic.

• Heat absorbed [always positive, endothermic] in the Bond-enthalpy of H-H:

Bond, ΔHD breaking of 1 mole of bonds. H2(g) → 2 H(g) ΔH = +436 kJ mol
-1

• Heat needed to produce 1 mole of gaseous atoms from Enthalpy of atomization of hydrogen:
Atomization, ΔHat the element in its standard state ½H2(g) → H(g) ΔH = +218 kJ mol
-1

• Heat needed to convert one mole of substance from Heat of vaporization of water:
Vaporization, ΔHvap liquid to gas [ΔH>0; endothermic] H2O(l) → H2O(g) ΔH = +41 kJ mol
-1

• Heat energy released when 1mole of water is formed in -1

Neutralisation, ΔHn the neutralisation between an acid and an alkali
NaOH + HCl → NaCl + H2O ∆H = -57 kJ mol

*Standard = 25 ᵒC and 1 atm/ 101 kPa

Hess Law
• The heat released/ absorbed in a chemical process/ reaction is the same whether
the process takes place in one or in several steps.

Start Finish

Stop

• Both lines accomplished the same result. Net result = Same.

Hess Law
• The enthalpy change depends only on the initial and final conditions of the
reactants and products.

A
Reactants Product

B C
Intermediate

• Mathematically: ΔHA = ΔHB + ΔHC

Hess Cycle/ Enthalpy Cycle
Steps in Hess Law

1. Show all chemical equations and identify types of enthalpy changes

2. Create the main and intermediate reactions
3. Construct Hess Cycle by placing the arrows (Reactant → Product)
Question 1
Given the following data:

ΔHf(CH4) = -74.8 kJ mol-1, ΔHf(CH3Cl) = -134.5 kJ mol-1, ΔHf(HCl) = -92.3 kJ mol-1

Calculate H for the reaction below:

CH4(g) + Cl2(g) → CH3Cl(g) + HCl(g)

Question 2
Which answer givers the correct enthalpy value for the reaction below?

2NaNO3 (s) → 2NaNO2(s) + O2(g)

ΔHf(NaNO2) = -359 kJ mol-1, ΔHf(NaNO3) = -468 kJ mol-1, ΔHf(O2) = 0 kJ mol-1

1. +109 kJ mol-1
2. -250 kJ mol-1
3. +218 kJ mol-1
4. +577 kJ mol-1
Question 3
Calculate the standard enthalpy change for the following reaction:
MgO(s) + 2HCl(g) → MgCl2(s) + H2O(l)

MgO(s) HCl(g) MgCl2(s) H2O(l)

ΔHf / kJ mol-1 -602 -92 -642 -286

1. -234 kJ mol–1
2. -142 kJ mol–1
3. +234 kJ mol–1
4. +142 kJ mol–1
Bond dissociation enthalpy/ Bond Energy

• Energy required to break 1 mole of covalent bond between 2 atoms.

A―B → A + B ∆H = + kJ mol-1

• Greater bond energy, stronger the bond.

Hess Law
• Endothermic: Energy must be absorbed to break any chemical bond
• Enxothermic: Energy must be released to form any chemical bond

Step 1:
Energy is put in to break bonds to form separate, gaseous atoms (∆H = +ve)

Step 2:
The gaseous atoms then combine to form bonds and energy is released. (∆H = -ve)
Hreaction = Hreactant (bond broken) – Hproduct(bond formed)
Question
NH3 + 3F2 → 3HF + NF3

What would be the value of enthalpy change for the reaction above?
(Average bond energies / kJ mol-1 : N-H = 390; F-F = 158; H-F = 562; N-F= 272)

*Bonds broken = endothermic reaction; Bonds formed = exothermic reaction

Thank You