Chemical Energetics

A Levels H2 Chemistry
Koh Wei Yi

Module 5:
1. Introduction and definitions
2. Energy profile diagrams
3. Calorimetry
4. Hess’ Law and enthalpy calculations
5. Entropy and Gibbs Free Energy
Energy profile diagram
 Enthalpy (H)
• Enthalpy is the measure of the energy content of a
substance
• When a reaction happens, the energy levels of the
reactants and products are different
• Enthalpy change of a reaction is the energy that is
absorbed or released when the reaction takes place
– Energy absorbed to break bonds
– Energy released from bond formation
 Enthalpy (H)
• Endothermic: Energy is absorbed – hence
energy level of reactants is lower than
products
 Enthalpy (H)
• Exothermic: Energy is released– hence energy
level of reactants is higher than products
 Definitions
Enthalpy change of reaction, ΔHfθ:
Enthalpy change when one mole of pure substance is
formed from its constituent elements (in standard states)
under standard conditions.
 Definitions
Enthalpy change of combustion, ΔHcθ:
Enthalpy change when one mole of pure substance is
burnt completely in excess oxygen under standard
conditions.
 Definitions
Bond energy:
Average energy required to break one mole of covalent
bonds in gaseous state to form gaseous ions

Bond dissociation energy:

Energy required to break one mole of a particular
covalent bond in a specific compound in the gaseous
state to form gaseous atoms
 Definitions
Enthalpy change of atomisation, ΔHatomθ:
(Elements) Energy required to produce one mole of
gaseous atoms from its elements in their standard states

(Compounds) energy required to convert one mole of

substance into its constituent gaseous atoms
 Definitions
1st ionization energy, IE:
Energy required to remove one mole of electrons from
one mole of gaseous atoms to form one mole of singly
charged gaseous cations.
 Definitions
1st electron affinity, EA:
Energy released when one mole of electrons are added to
one mole of gaseous atoms to form one mole of singly
charged gaseous atoms to form one mole of singly charged
anions.

2nd electron affinity:

Energy required to add one mole of electrons to one mole
of gaseous ions of -1 charge to form one mole og gaseous
ions of -2 charge.
 Definitions
Lattice energy:
Energy released when one mole of ionic solid is formed
from its constitutent gaseous ions.
 Definitions
Enthalpy change of hydration, ΔHhydθ:
Energy released when one mole of gaseous ions is
converted to one mole of aqueous ions under standard
conditions.
 Definitions
Enthalpy change of solution, ΔHsolnθ:
Enthalpy change when one mole of solute the
completely dissolved in a solvent to form an infinitely
dilute solution under standard conditions.
 Definitions
Enthalpy change of neutralisation, ΔHneutθ:
Energy released when one mole of water is formed
when an acid reacts completely with a base under
standard conditions.
 Definitions
Enthalpy change of vaporisation, ΔHvapθ:
Energy needed to convert one mole of substance from
the liquid state to the gaseous state.
 Enthalpy change
• State symbols are very important
 Energy profile diagram
Example 1:
Why does this reaction not occur spontaneously?
C (diamond)  C (graphite) ΔH = -1.83 kJ mol-1
 Calorimetry
• Measuring the enthalpy change of a reaction

Q = mcΔT
 Calorimetry
Calorimeter
 Calorimetry
Bomb calorimeter
 Calorimetry
Example 2:
An experiment was carried out to determine the enthalpy change of
combustion of methanol, CH3OH.
(a) Construct a balanced equation for the combustion of methanol,
including state symbols.
(b) You are asked to carry out the experiment. Write a plan for the
experiment to determine the enthalpy change of combustion of
methanol. Use a diagram to illustrate the set-up of the experiment.
(c) It was found that when a sample of methanol was burnt, the
temperature of 150g of water rose from 25°C to 40°C. Given that
the enthalpy change of combustion of methanol is -710 kJmol-1 and
that the process is 80% efficient, calculate the mass of methanol
burnt.
 Calorimetry
Example 2:
An experiment was carried out to determine the enthalpy change of
combustion of methanol, CH3OH.
(a) Construct a balanced equation for the combustion of methanol,
including state symbols.
 Calorimetry
Example 2:
An experiment was carried out to determine the enthalpy change of
combustion of methanol, CH3OH.
(b) You are asked to carry out the experiment. Write a plan for the
experiment to determine the enthalpy change of combustion of
methanol. Use a diagram to illustrate the set-up of the experiment.
 Calorimetry
Example 2:
An experiment was carried out to determine the enthalpy change of
combustion of methanol, CH3OH.
(c) It was found that when a sample of methanol was burnt, the
temperature of 150g of water rose from 25°C to 40°C. Given that
the enthalpy change of combustion of methanol is -710 kJmol-1 and
that the process is 80% efficient, calculate the mass of methanol
burnt.
 Hess Law
• The heat change of a reaction is determined by
the initial and final nature of the system and is
independent of the pathways taken.
 Hess Law
Example 3:
Calculate the enthalpy change of combustion of butanal,
CH3CH2CH2CHO, given the following standard enthalpy changes of
formation.
ΔHf (CH3CH2CH2CHO (l)) = -220 kJmol-1
ΔHf (CO2 (g)) = -394 kJmol-1
ΔHf (H2O (l)) = -286 kJmol-1
 Hess Law
Example 4:
The following reaction has an enthalpy change of -11.0 kJmol-1.
CH3OCH3 (l)  CH3CH2OH (l)
Using an energy level diagram, calculate the enthalpy change of
combustion of methoxymethane, given that the enthalpy change of
formation of ethanol is -277 kJmol-1, enthalpy change of formation of
water is -286kJmol-1 and the enthalpy change of combustion of graphite
is -394 kJmol-1.
 Enthalpy change of neutralisation
• Neutralisation between a strong acid and base
has a standard enthalpy change of -57 kJ mol -1
• However, reactions involving weak acids
and/or bases are not as exothermic
• Weak acids/bases are partially ionised
– Energy is expended during neutralisation to further
neutralise the acid/base
 Bond energy
Example 5:
Oxy-acetylene toches, which operate at temperatures as high as
3300°C, are fuelled by the combustion of acetylene, C2H2:
2C2H2 (g) + 5O2 (g)  4CO2 (g) + 2H2O (l)
(a) Estimate ΔHr for this reaction using bond enthalpies.
(b) Compare the result of this calculation with the value of ΔHθ from
the enthalpy change of formation.
(ΔHfθ /kJ mol-1: C2H2 (g) = 226.7; CO2 (g) = -395.5; H2O (l) = -241.8)
 Bond energy
Example 5:
Oxy-acetylene toches, which operate at temperatures as high as
3300°C, are fuelled by the combustion of acetylene, C2H2:
2C2H2 (g) + 5O2 (g)  4CO2 (g) + 2H2O (l)
(a) Estimate ΔHr for this reaction using bond enthalpies.
 Bond energy
Example 5:
Oxy-acetylene toches, which operate at temperatures as high as
3300°C, are fuelled by the combustion of acetylene, C2H2:
2C2H2 (g) + 5O2 (g)  4CO2 (g) + 2H2O (l)
(b) Compare the result of this calculation with the value of ΔHθ from
the enthalpy change of formation.
(ΔHfθ /kJ mol-1: C2H2 (g) = 226.7; CO2 (g) = -395.5; H2O (l) = -241.8)
 Born Haber Cycle
Example 6:
Construct a Born-Haber cycle for the formation of CaCl2(s) from its
elements. Use the cycle to calculate the lattice energy of CaCl2(s), using
the following data and relevant data from the Data Booklet.
ΔHatom (Ca) = -178 kJ mol-1
1st EA (Cl) = -364 kJ mol-1
ΔHf (CaCl2) = -816 kJ mol-1
 Born Haber Cycle
Example 7:
(a) 1.00 g of methane was burnt under a container of water which was
at 25°C. Given that the enthalpy change of combustion of methane
is -880 kJmol-1, and assuming that the burning process is 80%
efficient, find the maximum temperature reached.
(b) Calculate the bond energy of the C-H bond in methane. Represent
your answer on an energy level diagram.
Enthalpy change of combustion of C = -394 kJmol-1
Enthalpy change of combustion of H2 = -286 kJmol-1
Enthalpy change of atomisation of H = +218 kJmol-1
Enthalpy change of atomisation of C = +720 kJmol-1
 Born Haber Cycle
Example 7:
(a) 1.00 g of methane was burnt under a container of water which was
at 25°C. Given that the enthalpy change of combustion of methane
is -880 kJmol-1, and assuming that the burning process is 80%
efficient, find the maximum temperature reached.
 Born Haber Cycle
Example 7:
(b) Calculate the bond energy of the C-H bond in methane. Represent
your answer on an energy level diagram.
Enthalpy change of combustion of C = -394 kJmol-1
Enthalpy change of combustion of H2 = -286 kJmol-1
Enthalpy change of atomisation of H = +218 kJmol-1
Enthalpy change of atomisation of C = +720 kJmol-1
 Born Haber Cycle
Example 8:
Solid sucrose can be used as a fuel. The balanced equation for the combustion
of solid sucrose is given below:
C12H22O11(s) + 12 O2(g)  12 CO2 (g) + 11 H2O (l)
Given:
Enthalpy change of formation of C12H22O11(s) = -2220 kJmol-1
Enthalpy change of fusion of C12H22O11(l) = -10.0 kJmol-1
Enthalpy change of formation of H2O (l) = -286 kJmol-1
Enthalpy change of combustion of C (s) = -394 kJmol -1
Enthalpy change of vapourisation of H2O (l) = +44.0 kJmol-1
Liquid sucrose has a density of 1.55 gcm-3. By drawing an energy cycle,
calculate the heat evolved when 50 cm3 of liquid sucrose is completely burnt
in air to give CO2 (g) and H2O (g).
 Entropy (S)
• Measure of disorder in a system
• Measure of probability of a system
– Ways in which the energy can be distributed
• Like enthalpy, entropy change depends only on the
initial and final change
• Positive entropy change = system becomes more
disorderly
• Negative entropy change = system becomes more
ordered
 Entropy (S)
Factors affecting the entropy of a system
• Number of gas molecules
• Mixing of particles
– Mixing of gas particles
– Mixing of liquid particles
– Dissolution of an ionic solid
• Increase in temperature
• Change in phase
 Gibbs Free Energy (G)
• For a reaction to occur spontanously, the free
energy change must be negative
• Exergonic reactions have a negative ΔG
• Endergonic reactions have a positive ΔG

ΔG= ΔH – TΔS
 Gibbs Free Energy (G)
Exothermic reactions with increasing entropy
E.g. combustion of fuels
 Gibbs Free Energy (G)
Exothermic reactions with decreasing entropy
E.g. condensation and freezing, precipitation
 Gibbs Free Energy (G)
Endothermic reactions with increasing entropy
E.g. melting and boiling, dissolution of some ionic
compounds
 Gibbs Free Energy (G)
Endothermic reactions with decreasing entropy
E.g. photosynthesis
 Gibbs Free Energy (G)
Summary:
 Recap

Module 5:
1. Introduction and definitions
2. Energy profile diagrams
3. Calorimetry
4. Hess’ Law and enthalpy calculations
5. Entropy and Gibbs Free Energy

Next Module:
Module 6: Electrochemistry