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2022 JC1 H2 Chemistry (9729) Things

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Topic 5: Chemical Energetics (Part 1)
Thermochemistry (H) and Thermodynamics (S, G)
Assessment Objectives
Candidates should be able to:
(a) explain that most chemical reactions are accompanied by energy changes,
principally in the form of heat; usually associated with the breaking and forming of
chemical bonds, the reaction can be exothermic (H negative) or endothermic (H
positive)
(b) construct and interpret an energy profile diagram, in terms of the enthalpy change
of the reaction and of the activation energy
(c) explain and use the terms: Must memorise 10 defn! Write balanced eqn w/ s.s!
(i) enthalpy change of reaction and standard conditions, with particular
reference to: formation; combustion; hydration; solution; neutralisation;
atomisation
(ii) bond energy (H positive, i.e. bond breaking)
(iii) lattice energy (H negative, i.e. gaseous ions to solid lattice)
(d) calculate enthalpy changes from appropriate experimental results, including the
use of relationship: heat change = mcT Calc. Hr, Hn, Hc, Hsoln. (Practical)
(e) explain, in qualitative terms, the effect of ionic charge and of ionic radius on the
numerical magnitude of a lattice energy
(f) apply Hess’ Law to construct simple energy cycles, e.g. Born-Haber cycle, and
carry out calculations involving such cycles and relevant energy terms (including
ionisation energy and electron affinity), with particular reference to:
(i) (determining enthalpy changes that cannot be found by direct experiment,
e.g. an enthalpy change of formation from enthalpy changes of combustion
(ii) the formation of a simple ionic solid and of its aqueous solution
(iii) average bond energies

Section Content LOs Page

1 Introduction to Thermodynamics and Thermochemistry
1.1 Enthalpy and Enthalpy Changes (a) 2
1.2 Endothermic and Exothermic Reactions (includes
(a), (b) 23
Energy Profile diagram)
1.3 Standard Conditions (c)(i) 3
1.4 Experimental Determination of Enthalpy Change (d) 47
2 Standard Enthalpy Changes
2.1 Standard Enthalpy Change of Reaction (c)(i) 89
2.2 Standard Enthalpy Change of Neutralisation (c)(i) 1011
Lecture 1 2.3 Standard Enthalpy Change of Combustion (c)(i) 1213
3 Energy Cycle and Energy Level Diagram
3.1 Hess’ Law (f)(i) 1415
3.2 Standard Enthalpy Change of Formation (c)(i) 1617
3.3 Bond Energy (c)(ii), (f)(iii) 1819
Lecture 2 3.4 Standard Enthalpy Change of Atomisation (c)(i) 20
3.5 Born–Haber Cycle for Ionic Solids (Lattice Energy,
(c)(iii), (e), (f) 2125
Ionisation Energy, Electron Affinity
3.6 Standard Enthalpy Change of Solution (includes
Lecture 3 Hydration)
(c)(i), (f)(ii) 2628

Recommended Reference Text:

1) Chemistry for Advanced Level, P. Cann & P. Hughes
2) Chemistry in Context, Hill & Holman
3) Calculations in AS/A Level Chemistry, J. Clarks

2022 JPJC JC1 H2 Chemistry (9729) 1 Topic 5: Chemical Energetics (Part 1)

 1 INTRODUCTION TO THERMODYNAMICS AND THERMOCHEMISTRY

CHEMICAL THERMODYNAMICS
Study of heat (i.e. thermal energy) and how heat can be interconverted into
other energy forms (e.g. sound energy, light energy, potential energy etc)
G = H  TS Part 2

FIRST LAW OF THERMODYNAMICS

Energy cannot be created or destroyed; it can only be converted from one
form into another.

THERMOCHEMISTRY (H)
Measurement and interpretation of heat changes that occurs during chemical
reactions and phase changes.
Calorimetry, Nutrient Label
On a practical level, this study allows us to develop alternate fuel sources (e.g. fuel
cells or hybrid gas–electric engines) and to design plants that maximize yields or
improve safety. thermodynamic
On a molecular/fundamental level, this study allow us to investigate the feasibility
of reactions.

Lower the energy content,

1.1 ENTHALPY AND ENTHALPY CHANGES
always +ve higher the stability
The enthalpy of a substance, H, is the total energy content of a substance
at constant pressure. It reflects the thermodynamic stability of a substance.
Absolute enthalpy, H, cannot be measured.
https://tinyurl.com/
chemenerg1 However, we can measure the changes in enthalpy accompanying a process
Chemguide when the system moves from initial state (i.e. reactants) to final state
(products). The symbol for enthalpy change is H. can be +/-
In a reaction where the equation is reactants  products: Hpdt > Hrxt  H > 0 (+)
∆H =  H(products) – H(reactants). H
pdt < Hrxt  H < 0 (-)
final - initial
Example: Consider a hypothetical reaction, A + B  C + D
∆H = (HC + HD ) – (HA + HB)

1.2 ENDOTHERMIC AND EXOTHERMIC REACTIONS

To understand how to measure and interpret heat changes, we must first
establish the understanding of what a system and the surrounding means.
The system is defined as a part of the universe that is being studied. The
rest of the universe that is not part of the system is defined as the
surrounding.
Example: Consider the redox reaction
CuSO4(aq) + Zn(s)  ZnSO4(aq) + Cu(s)  to be investigated (i.e. system)
System:
Reactants (Cu2+, SO42, Zn) and products
(Zn2+, SO42, Cu)
Surrounding:
aqueous medium (water), reaction vessel
(beaker), surrounding air

2022 JPJC JC1 H2 Chemistry (9729) 2 Topic 5: Chemical Energetics (Part 1)

 Enthalpy change of a reaction/process H (units is kJ mol1) can be
 endothermic (i.e. H > 0, positive) or
 exothermic (i.e. H < 0, negative).
Table 1 below summarises the key differences between endothermic and
exothermic reaction.
Heat enters Heat exits syst.
syst.
Endothermic Reaction Exothermic Reaction
System absorbs heat from the System releases heat into the
surrounding during the process. surrounding during the process.
E.g. N2(g) + O2(g)  2NO(g) E.g. 2Mg(s) + O2(g)  2MgO(s)
H = +180 kJ mol1 H = 1204 kJ mol1

Direction of
heat transfer
SYSTEM SYSTEM
(reactants & (reactants &
products) products)
SURROUNDINGS SURROUNDINGS
aqueous medium aqueous medium

reaction vessel reaction vessel

air air

H = Hf - Hi Since heat is absorbed, the Since heat is released, the

products have higher energy products have lower energy
Sign of H content (i.e. Hfinal > Hinitial) content (i.e. Hfinal < Hinitial)
of the syst
 Positive (H > 0)  Negative (H < 0)
surrounding  Temperature surr. has less energy surr. has more energy
change (after Temperature of surrounding Temperature of surrounding
the reaction) decreases (i.e. colder) increases (i.e. hotter)
Lower the relative Since the products have higher Since the products have lower
energy content, Stability of energy content, the products energy content, the products
higher the rel. substance are energetically less stable are energetically more stable
than the reactants. than the reactants.
energetic
stability of the
substance

Energy Level
Diagram

incorporate Energy Energy

kinetic Energy
feasibility of Profile Ea
Diagram
the rxn (Activation energy,
Ea products reactants
(rate, EA) Ea, is the H > 0 H < 0
minimum energy
that the reactants
must possess for a reactants products
reaction to occur.)
progress of reaction / reaction coordinate progress of reaction / reaction coordinate

TABLE 1 A summary of the differences between endothermic reaction and exothermic reaction.

Note: For the energy profile diagram of a multi–steps reaction, refer to Topic 6
(Reaction Kinetics) for more details.
2022 JPJC JC1 H2 Chemistry (9729) 3 Topic 5: Chemical Energetics (Part 1)
 1.3 STANDARD CONDITIONS
Enthalpy changes have different values under different conditions such as
temperature, pressure, concentration and physical states.
For the purpose of valid comparison, enthalpy changes are usually quoted
for the same set of conditions. An enthalpy change measured under
standard conditions is known as standard enthalpy change, H .

The standard conditions, denoted by ‘’, are:

 temperature : 298 K (or 25 C)
Note:  pressure : 1 bar (or 105 Pa)
 concentration : 1 mol dm3 (for aqueous solution)
This is NOT  standard state : most stable physical state at 298 K and 1 bar
stp (0 C,1 bar)
e.g. Na(s), O2(g), Br2(l)
or Note: For elements that can exist as different allotropes under standard
rtp (20C, 1atm) conditions, the most stable allotrope is used as the standard and it
must be specified.

Example: Carbon exists in two allotropic form: graphite and diamond.

C(graphite) + O2(g)  CO2(g) H = 393 kJ mol–1
C(diamond) + O2(g)  CO2(g) H = 395 kJ mol–1
Energy / kJ mol–1
C(diamond)  C(graphite)
: exothermic C(diamond) + O2(g)
H = 2 kJ mol1
Length: rel. mag. −2
C(graphite) + O2(g) (exo)
−395
Graphite has a lower energy
−393 content than diamond.
 Graphite is energetically more
CO2(g) stable than diamond.

FIGURE 1 An energy level diagram showing the relative stabilities of graphite and diamond.

Since graphite is the more stable form of the two allotropes, C(s) in standard
state refers to graphite.
If diamond is used, it should be stated as C(diamond).

1.4 EXPERIMENTAL DETERMINATION OF ENTHALPY CHANGES

Heat is always transferred from a hot to a cold substance and this heat
change produces a change in temperature, T, which can be measured
using a thermometer.
Heat change, q, is a scalar quantity and hence, it is always positive. The
units of q is J or kJ. note the diff. in units

To determine the enthalpy change H (units: kJ mol1) of a reaction/process,

the reaction/process can be carried in a calorimeter and measure T that
results from the heat transfer. H can be positive (i.e. endothermic) or
T of surr.  negative (i.e. exothermic). T of surr. 
See Table 1 in Section 1.2 (Page 3).

2022 JPJC JC1 H2 Chemistry (9729) 4 Topic 5: Chemical Energetics (Part 1)

 1.4.1 The Calorimeter
To measure the heat absorbed/evolved from a physical/chemical
process, the following experimental setup can be used.
To minimise heat lost to or
gained from surrounding

https://tinyurl.com/
chemenerg2
Video on
Calorimetry

FIGURE 2
An aqueous solution in a
Styrofoam/polystyrene cup to
measure enthalpy heat of neutralization,
enthalpy change of solution and
enthalpy change of precipitation.
FIGURE 3
Water in metal can and substance to
be burnt in burner/spirit lamp to
measure enthalpy change of combustion.

1.4.2 Calculation of H from Experimental results

For a solution, where the thermometer is placed in

heat change, q (in J) = mcT
where m is the mass of the solution (in g) must tally
T/K = T/C + 273
c is the specific heat capcity of the solution (in J g1 K1)
T in K
T is the change in temperature of the solution (in C or K)
= T2/K – T1/K Note: T in C = T in K!
= (T2/C + 273) - (T1/C + 273) or
= T2/C - T1/C heat change, q = vcT
= T in C where v is the total volume of the solution (in cm3) must tally
c is the specific heat capcity of the solution (in J cm3 K1)
or
For a container/calorimeter,
heat change, q = CT
where C is the heat capcity of the container (in J K1)

For a system with 100 % efficiency,

heat evolved by reaction = heat gained by calorimeter & solution
(i.e. exothermic reaction  temperature of surrounding rises) H < 0 (-)

heat gained by reaction = heat lost by calorimeter & solution

(i.e. endothermic reaction  temperature of surrounding falls) H > 0 (+)

heat change, q = msolncsolnT + Ccalorimeter T in J or kJ

 heat change, q 
H =    in kJ mol1
 n 
where n is the amount of substance, defined by specific H (in mol)

2022 JPJC JC1 H2 Chemistry (9729) 5 Topic 5: Chemical Energetics (Part 1)

 Main reasons why exptal and theoretical H are different!
Assumptions made in the calculation (unless otherwise stated in Qn):
 heat capacity of calorimeter is zero, Ccalorimeter = 0
(i.e. the Styrofoam/polystyrene cup does not absorb any heat)
 system is perfectly 100 % efficient
(i.e. no heat lost to or gained from surrounding air)
 density of water/aqueous solution is 1.0 g cm3
in DB
 specific heat capacity of water/aqueous solution is 4.18 J g1 K1 or
4.18 J cm3 K1
(i.e. 4.18 J of heat energy is required to raise the temperature of 1 g
or 1 cm3 of water/aqueous solution by 1 C or 1 K)

1.4.3 Efficiency of the System

A simple experimental setup often involves significant experimental
errors (e.g. some heat is lost to or gained from surrounding air) and
hence, the system is not 100 % efficient (i.e. T measured is not the
true T). Less than 100 % of heat is transferred to/from the soln
To account for the efficiency, the formula for total heat change on
Page 5 is adjusted as follow:

% efficiency
× total heat change, q = msolncsolnT + CcalorimeterT
100
 total heat change, q 
H =   
 n 

Analysis & The efficiency of the calorimeter can be increased by:

minimise heat lost
Evaluation With reference to Figure 2 (page 5),
to/gained from surr
for Practical  stack two Styrofoam cups together,
 provide lagging around the calorimeter, and/or
 use a lid with two holes for thermometer and stirrer.

With reference to Figure 3 (page 5),

 place a draught shield around the setup,
 minimise the distance between the flame and base of metal can by
placing the spirit lamp on a wooden block
 ensure complete combustion by carrying out the reaction under an
oxygen–rich environment.

1.4.4 Measurement of Temperature Difference, T q = mcT or q = vcT

T, may be measured through two methods: How to measure m and v?
Linked to PC1: (a) Uncorrected T easy but less accurate
(Practical)
Thermochemistry Measure the initial temperature and final temperature
(highest/lowest) reached.
Take only the
T  (exo. rxn) T (in K or C) = | Tfinal – Tinitial | value for T
T  (endo. rxn) The disadvantage of this method is that it does not account for
the heat lost to or gained from the surrounding air.

2022 JPJC JC1 H2 Chemistry (9729) 6 Topic 5: Chemical Energetics (Part 1)

 has taken into a/c heat lost to/gained from air
Linked to PC1: (b) Corrected T (Heating/Cooling Correction curve)
(Practical)
Thermochemistry The temperature of the mixture is measured at specific time
interval before and after the point when the reaction starts.
Then, a graph of temperature against time is plotted.
The heating/cooling portion of the curve is extraplolated until the
time when the reaction starts. Then, the T is determined
graphically.
T  first then  due to cooling
Example: Cooling correction curve for exothermic reaction
temperature / C

cooling portion of
corrected Tmax curve due to heat
lost to surrounding
uncorrected Tmax

corrected
Tmax uncorrected
Tmax

Tinitial

time / min
reaction starts Do not measure T at the pt of mixing!
FIGURE 4 An example of cooling correction curve for an exothermic reaction.

Note: Correction for heat loss is commonly practised for

reactions which are slow or involve large T.

Exercise 1 (Heating correction curve for endothermic reaction)

In an experiment to determine the enthalpy change of solution of ammonium
nitrate (NH4NO3) in water, 8.00 g of solid ammonium nitrate (Mr = 80.0) was
added to 50 g of water and the temperature of the resultant solution
100 % efficient monitored at various time intervals. The following graph was obtained for the
& assume Ccal = 0 above experiment.

1 heat change, q
= mcT
= 50 × 4.18 × (20 – 10) Note:
= 2090 J = 2.09 kJ Do not include
the mass of
n(NH4NO3) dissolved
2 = 8.00  80.0 = 0.100 mol
corrected Tmin solid (NH4NO3)
= 10 C as it is the
water/solution
Since T falls, the reaction is
that absorbs
endothermic (i.e. H > 0). the heat from
q  2.09  (or loses heat
3 Hsoln = +   = +  
n  0.100  to) the reaction!
= +20.9 kJ mol1

What is the enthalpy change of solution, in kJ mol1, of NH4NO3, given that

the specific heat capacity of the resulting solution is 4.18 J g1 K1?
A +19.4 B +20.1 C +20.9 D +22.6

2022 JPJC JC1 H2 Chemistry (9729) 7 Topic 5: Chemical Energetics (Part 1)

 Queries about Lecture: www.tinyurl.com/j1chemlecture

2 STANDARD ENTHALPY CHANGES

After establishing the experimental method and calculations, some standard
enthalpy changes can be determined experimentally: reaction, neutralisation,
combustion and solution (dissolving of solid).
For standard enthalpy change of solution of a solid substance, see Section 3.6 on
Page 26.

2.1 STANDARD ENTHALPY CHANGE OF REACTION, H r

Definition: H can be +/-
It is the heat change when molar quantities of reactants, as specified
in the chemical equation, react completely to form products under
the standard conditions of 298 K and 1 bar.

Experimentally determined:
 heat change, q 
Hr =  
 nlimiting reagent 
× stoichiometric coefficient of limiting reagent
 

To understand the purpose of ’stoichiometric coefficient’ in the calculation of

Hr, we need to establish the guidelines for writing and interpreting
thermochemical equation.
A thermochemical equation is a balanced chemical equation which shows
the number of moles of reactants and its associated enthalpy change.

Guidelines for writing and interpreting thermochemical equation:

 State symbols must be included in a thermochemical equation as H
varies with the physical state of the substance.
 When both sides of the thermochemical equation is multiplied by a
factor, H must be multiplied by the same factor.
 H for the reverse reaction has same magnitude but opposite in sign.

Example: Consider the thermochemical equation of the reaction of hydrogen

gas with oxygen gas.
2H2(g) + O2(g)  2H2O(l) Hr = 572 kJ mol1
This means 572 kJ of heat is released when 2 moles of H2 gas reacts with
1 mole of O2 gas to form 2 moles of liquid water at 298 K and 1 bar.
2 mole of eqn
×2 Note: The term ‘per mole’ in the units refers to ‘per molar amounts as shown
in the equation’ (i.e. ‘per mole of equation’).

Hence, for the following equation:

4H2(g) + 2O2(g)  4H2O(l) Hr = 2(572) = 1144 kJ mol1

Exercise 2: Given the following,

4NH3(g) + 3O2(g)  2N2(g) + 6H2O(l) Hr = 1260 kJ mol1
×¼ ×¼
3 1 3
(a) NH3(g) + O2(g)  N2(g) + H2O(l) Hr = 315 kJ mol1
4 2 2
×(2) ×(2)
(b) 4N2(g) + 12H2O(l)  8NH3(g) + 6O2(g) Hr = +2520 kJ mol1

2022 JPJC JC1 H2 Chemistry (9729) 8 Topic 5: Chemical Energetics (Part 1)

 Exercise 3: Consider the following reactions.
H2(g) + ½O2(g)  H2O(l) Hr = 286 kJ mol1
H2(g) + ½O2(g)  H2O(g) Hr = 242 kJ mol1 less heat evolved
Account for the difference in the standard enthalpy changes for the above
reactions.
The second reaction is less exothermic as some heat is absorbed to
convert liquid water to steam. Energy req’d to
H2O(l)  H2O(g) H = +44 kJ mol overcome HB betw.
 1

H2O molecules
H2(g) + ½O2(g) 286 H2O(l) Hvap H2O(g)

242

Alternative:
H2(g) + ½O2(g)  H2O(g) (242)
H2O(l)  H2(g) + ½O2(g) (286)
H2O(l)  H2O(g) +44

Exercise 4 convert to g
1.00 g of magnesium powder was added to 80.0 cm3 of 1.0 mol dm–3
hydrochloric acid solution at 22.0 C. The temperature of the mixture rose to
34.5 C.  exo (H < 0)
Given that the specific heat capacity of the resulting solution is 4.18 J g–1 K–1 q = mcT
and that the density of the resulting solution is 1.00 g cm–3, calculate the
enthalpy change of the following reaction. Hr  find nLR
Mg(s) + 2HCl(aq)  MgCl2(aq) + H2(g) Hr

Assuming the heat transfer is 100 % effficient and Ccalorimeter = 0,

1 heat change, q = mcT
Note: density =
mass
= (80.0 × 1.0) × 4.18 × (34.5 – 22.0) volume
= 4180 J = 4.18 kJ  mass = density × volume
Note:
2 n(Mg) used = 1.00  24.3 = 0.04115 mol Do not include the mass
of solid as it is the solution
80.0 that absorbs the heat from
n(HCl) used = 1.0 × = 0.0800 mol
1000 the reaction!

Since 1Mg  2HCl, HCl is the limiting reagent.

Since the temperature rises, the reaction is exothermic (i.e. H < 0).
 heat change, q 
3 Hr =  
 nlimiting reagent 
× stoichiometric coefficient of limiting reagent
 
 4.18 
=   ×2
 0.0800 
= 104.5 = 105 kJ mol1 Level 2: Qn 15

2022 JPJC JC1 H2 Chemistry (9729) 9 Topic 5: Chemical Energetics (Part 1)

 2.2 STANDARD ENTHALPY CHANGE OF NEUTRALISATION, H n
Definition: HO bond is formed.
It is the heat evolved when 1 mole of water is formed from the
reaction of an acid and an alkali under the standard conditions of
298 K and 1 bar. (i.e. Hn is always negative.)
H+(aq) + OH(aq)  H2O(l) Hn = 57.3 kJ mol1
Note: This value of Hn is only true for the reaction between strong acid
and strong base.
 heat change, q 
Experimentally determined: Hn =   
 nwater formed 

Examples:
NaOH(aq) + HCl(aq)  NaCl (aq) + H2O(l) Hn = 57.3 kJ mol1
NaOH(aq) + ½H2SO4(aq)  ½Na2SO4(aq) + H2O(l) Hn = 57.3 kJ mol1
2NaOH(aq) + H2SO4(aq)  Na2SO4(aq) + 2H2O(l) H n = 2(-57.3)
Acid Alkali Hn Acid Alkali Hn
HCl NaOH 57.3 CH3COOH NaOH 55.2 less exo
HNO3 KOH 57.3 HCN NaOH 11.6
H2SO4 KOH 57.3 HCl NH3 52.2 less exo
HNO3 Ba(OH)2 57.3 CH3COOH NH3 51.5
TABLE 2 Some values of enthalpy change of neutralisation.

Linked to Topic 15: 2.2.1 Strong acid–Strong base neutralisation

Acids & Bases
Equilibria Table 2 shows that Hn for the reaction between strong acid and
strong base are the same and equal 57.3 kJ mol1.
This is because strong acid/base ionises/dissociates completely in
water prior to neutralisation.
Examples: HCl(aq)  H+(aq) + Cl(aq)
NaOH(aq)  OH(aq) + Na+(aq)

2.2.2 Strong acid–Weak base (or Weak acidStrong base) neutralisation

Table 2 shows that Hn for the reactions involving weak acid/base
are less exothermic than 57.3 kJ mol1 (i.e. less heat is evolved for
the same amount of water formed).
This is because weak acid/base ionises/dissociates partially in
water prior to neutralisation.
Examples: CH3COOH(aq)  H+(aq) + CH3COO(aq)
NH3(aq) + H2O(l)  OH(aq) + NH4+(aq)

The ionisation of weak acid/base (bond breaking) is endothermic.

Hence, some heat evolved from the neutralisation is absorbed
to fully ionised the remaining unionised weak acid/base.
Overall, less heat is evolved and H n will be less exothermic.

2022 JPJC JC1 H2 Chemistry (9729) 10 Topic 5: Chemical Energetics (Part 1)

 Exercise 5: total vol?
250 cm3 of 0.400 mol dm–3 aqueous sodium hydroxide was added to 250 cm3
of 0.800 mol dm–3 aqueous sulfuric acid in a polystyrene cup. The initial
average temperature of the two solutions was 26.0 C. After the reaction, the
temperature rose to a maximum of 28.4 C.  exo (H < 0)
If 4.3 J are required to raise the temperature of 1 cm 3 of solution by 1 C,q = vcT
calculate the enthalpy change of neutralisation for the reaction.Hn  find nwater
NaOH(aq) + ½H2SO4(aq)  ½Na2SO4(aq) + H2O(l) Hn

Assuming the heat transfer is 100 % effficient and Ccalorimeter = 0,

1 heat change, q = vcT
= (250 + 250) × 4.3 × (28.4 – 26.0)
= 5160 J = 5.16 kJ

250
2 n(NaOH) used = 0.400 × = 0.100 mol
1000
250
n(H2SO4) used = 0.800 × = 0.200 mol
1000
Since 1NaOH  ½H2SO4, NaOH is the limiting reagent.
n(H2O) formed = 0.100 mol

Since the temperature rises, the reaction is exothermic (i.e. H < 0).
 heat change, q   5.16 
3 Hn =    =   Why is the Hn is less
 n water   0.100  exothermic than 57.3 even
though strong acid and
= 51.6 kJ mol1 strong base are used?
Some heat lost to cup
Exercise 6: & surrounding air.
The standard enthalpy change of neutralisation of hydrochloric acid and
sodium hydroxide is –57.3 kJ mol–1. The standard enthalpy change of
neutralisation of ethanoic acid and sodium hydroxide is –55.2 kJ mol–1.
(a) Account for the difference in values.
NaOH is a strong base and HCl is a strong acid. Both ionises
completely in water prior to neutralisation. Hence, when mixed, Hn is
57.3 kJ mol1.
However, CH3COOH is a weak acid which ionises partially in water
prior to neutralisation. Hence, during neutralisation, some heat
evolved from the neutralisation is absorbed to fully ionise the
remaining unionised CH3COOH.
Overall, less heat is evolved and Hn is less exothermic.

(a) Calculate the enthalpy change for the ionisation of CH 3COOH.

CH3COOH(aq)  H+(aq) + CH3COO(aq)
ionisation neutralisation
H H+(aq)

+ OH (aq) H2O(l)
CH3COOH(aq) 
+ CH3COO (aq) 57.3 + CH3COO(aq)

+ OH 55.2
H + (57.3) = 55.2 Level 1: Qn 2, 12
H = +2.1 kJ mol1 Level 2: Qn 17, 18

2022 JPJC JC1 H2 Chemistry (9729) 11 Topic 5: Chemical Energetics (Part 1)

 Queries about Lecture: www.tinyurl.com/j1chemlecture
2.3 STANDARD ENTHALPY CHANGE OF COMBUSTION, H c
Definition:
It is the heat evolved when 1 mole of a substance is completely burnt
in excess oxygen under the standard conditions of 298 K and 1 bar.
(i.e. Hc is always negative.)
 heat change, q 
Experimentally determined: Hc =   
 nsubstance burnt 
Note: Substance which does not undergo combustion (e.g. H2O, O2, CO2
and most oxides), have Hc = 0 kJ mol1.

Hc Hc
Substance Substance
/ kJ mol1 / kJ mol1
hydrogen, H2(g) 286 propane, CH3CH2CH3(g) 2202
C(diamond) 395 butane, CH3CH2CH2CH3(g) 2877
C(graphite) 393 methanol, CH3OH(l) 715
magnesium, Mg(s) 602 ethanol, CH3CH2OH(l) 1367
carbon monoxide, CO(g) 283 propan-1-ol, CH3CH2CH2OH(l) 2017
methane, CH4(g) 882 glucose, C6H12O6(s) 2816
ethane, CH3CH3(g) 1542 sucrose, C12H22O11(s) 5644
TABLE 3 Some values of enthalpy change of combustion.

The Hc values allow us to compare the

energy values of fuel.
The more exothermic the H c,
the higher the energy value of the fuel.
https://tinyurl.com/
chemenerg3 Other than the simple experimental setup
Video on Bomb
Calorimeter
shown in Figure 3 on Page 5, a bomb
calorimeter (Figure 5) can be used to
accurately determine the energy
change of combustion of a substance.
Not enthalpy change since the
pressure is not kept constant. FIGURE 5
An illustration of a bomb calorimeter.

Exercise 7:
A student carried out an experiment to
determine the enthalpy change of thermometer
combustion of ethanol (Mr = 46.0) using
the setup on the right.
stirrer
The following measurements are taken:
metal can
convert to g  Volume of water = 300 cm3 with water

Initial temperature of water = 25.0 C spirit lamp

exo (H < 0)  Final temperature of water = 35.0 C containing
ethanol
Mass of ethanol burnt = 0.750 g wooden block
Density of water = 1.0 g cm‒3
70 % efficient  30 % lost
Assuming only 70% of the heat produced is used to heat the water, calculate
the standard enthalpy change of combustion of ethanol. Hc  find nsubst burnt
[Specific heat capacity of water is 4.18 J g1 K1] q = mcT
mass = density × volume

2022 JPJC JC1 H2 Chemistry (9729) 12 Topic 5: Chemical Energetics (Part 1)

 Alternative:
Exercise 7: (continued) 70
× q = [(300 × 1.0) × 4.18 × (35.0 – 25.0)] + 0
Assuming Ccalorimeter = 0, 100
1 heat absorbed by water = mcT
= (300 × 1.0) × 4.18 × (35.0 – 25.0)
= 12540 J = 12.54 kJ (i.e. 70 % of heat change)
100 need to find 100 %
total heat change, q = 12.54 × = 17.91 kJ
70

2 n(CH3CH2OH) burnt = 0.750  46.0 = 0.0163 mol

Since temperature rises, the reaction is exothermic (i.e. H < 0).

 heat change, q 
3 H
c of CH3CH2OH =   
 nsubstance burnt 
 17.91 
 = 1100 kJ mol
1
= 
 0.0163 

Note: The above setup does not give an accurate determination of  Hc.
Some of the errors are:
 Heat lost to the surroundings due to air convection.
 Incomplete combustion of the fuel as spirit lamp does not receive
pure oxygen supply like in the case of a bomb calorimeter.
 Evaporation of fuel from the spirit lamp. Hence, the mass of fuel
burnt cannot be determined accurately.

Exercise 8 convert to g (from DB: c of water = 4.18 J g1 K1

1.80 g of propan1ol, C3H8O, was used to heat a metal calorimeter
containing 250 cm3 of water. The temperature of the water rose from 25.0 C
to 66.5 C.  exo (H < 0) Ccalorimeter q = mcT + CcalT
Assume the heat capacity of the metal calorimeter to be 25.0 J K –1, and only
75 % efficient 75 % of heat is transferred to the metal calorimeter and water, calculate the
enthalpy change of combustion of propan1ol. Hc  find nsubst burnt
Alternative:
75
T = 66.5 – 25.0 = 41.5 C 100 × q = [(250 × 1.0) × 4.18 × 41.5] + [25.0 × 41.5]
1 heat absorbed by water = msolcsolT + CcalorimeterT
= [(250 × 1.0) × 4.18 × 41.5] + [25.0 × 41.5]
= 44405 J = 44.405 kJ (i.e. 75 % of heat change)
100
total heat change, q = 44.405 × = 59.21 kJ
75

2 n(C3H8O) burnt = 1.80  60.0 = 0.0300 mol

Since temperature rises, the reaction is exothermic (i.e. H < 0).

 heat change, q 
3 H c of C3H8O =  


 nsubstance burnt 
 59.21 
 = 1970 kJ mol
1
= 
 0.0300  Level 1: Qn 5
Level 2: Qn 16
2022 JPJC JC1 H2 Chemistry (9729) 13 Topic 5: Chemical Energetics (Part 1)
3 ENERGY CYCLE AND ENERGY LEVEL DIAGRAMS
Some enthalpy changes cannot be experimentally determined. However, they
can be indirectly calculated from other H of known values by applying the Hess’
Law. This indirect method requires the drawing of energy cycle or energy level
diagrams.

3.1 HESS’ LAW

Definition:
Hess’ Law states that the enthalpy change, ∆H, accompanying a
chemical reaction is the same regardless of the route by which the
chemical change occurs, provided that the initial and final states are
the same.

Consider the energy cycle below:

H1
start A B end
route 1 By Hess’ Law,
H(route 1) = H(route 2)
H2 H4
H1 = H2 + H3 + H4
route 2
C D
H3

Consider another energy cycle below:

H1
start V + W Z end
route 1 By Hess’ Law,
H2 H3 H4 H(route 1) = H(route 2)
route 2
H1 = H2 + H3  H4
X + Y Z  X + Y H4
X + Y  Z H4
Note: Hess’ Law is simply an application of the Law of Conservation of
Energy. It may not be the true representation of the actual processes.

Exercise 9: Given the following energy cycle, calculate H.

Hr CaO(s) + CO2(g) end
start CaCO3(s)

1207 635 393

3
Ca(s) + C(s) + O2(g)
2
By Hess’ Law,
Hr = (1207) + (635) + (393) = +179 kJ mol1

2022 JPJC JC1 H2 Chemistry (9729) 14 Topic 5: Chemical Energetics (Part 1)

 General steps to construct an energy cycle and calculate H:
1) Write the balanced equation (with state symbols) for the H to be
determined.
2) Complete the cycle by adding in equations that correspond to the
data given, ensuring all equations are balanced with state symbols.
3) Write the corresponding H values/symbols next to the arrow, with
appropriate multiplier.
4) Apply Hess’ Law to calculate the required H.

Exercise 10: Given the following data,

K2CO3(s) + 2HCl(aq)  2KCl(aq) + CO2(g) + H2O(l) H = 32.8 kJ mol1
KHCO3(s) + HCl(aq)  KCl(aq) + CO2(g) + H2O(l) H = +23.3 kJ mol1 ×2
Construct an energy cycle and use it to calculate the enthalpy change, Hr,
of the following reaction.
2KHCO3(s)  K2CO3(s) + CO2(g) + H2O(l) Hr
Hr
Check LHS = RHS! 2KHCO3(s) K2CO3(s) + CO2(g) + H2O(l)

+ 2HCl(aq) + 2HCl(aq)
2(+23.3) 32.8 0 0

2KCl(aq) + 2CO2(g) + 2H2O(l)

By Hess’ Law,
Hr = 2(+23.3)  (32.8) = +79.4 kJ mol1

Exercise 11: Given the following enthalpy changes of combustion,

Hc of C(graphite) = 393 kJ mol1 C(graphite) + O2(g)  CO2(g) x3
Hc of H2(g) = 286 kJ mol1 H2(g) + ½O2(g)  H2O(l) x4
1
H c of C3H8(g)

= 2220 kJ mol C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
Construct an energy cycle to calculate Hr for the reaction:
3C(graphite) + 4H2(g)  C3H8(g)

Hr
Check LHS = RHS! 3C(graphite) + 4H2(g) C3H8(g)

+ 3O2(g) + 2O2(g) + 5O2(g)

3(393) 4(286) 2220
3CO2(g) + 4H2O(l)
By Hess’ Law,
Hr = [3(393) + 4(286)]  (2220) = 103 kJ mol1

mHc(reactants) nHc(products)
In general,
Hr
reactants products

mHc(reactants) nHc(products)

combustion products
This leads to the universally applicable formula when given H c data:
If Qn doesn’t
require you to H r = mH c(reactants)  nH c(products)
where m & n are the stoichiometric coefficient in the thermochemical equation
draw energy cycle
2022 JPJC JC1 H2 Chemistry (9729) 15 Topic 5: Chemical Energetics (Part 1)
 Queries about Lecture: www.tinyurl.com/j1chemlecture
Exercise 12:
Given that the standard enthalpy change of combustion of C6H12O6(s) and
CH3CH2OH(l) are 2816 kJ mol1 and 1367 kJ mol1 respectively, calculate
the standard enthalpy change, Hr, for the following reaction:
C6H12O6(s)  2CH3CH2OH(l) + 2CO2(g)
(2816) 2(1367) 2(0)
Hr = mHc(reactants)  nHc(products)
= (2816)  [2(1367) + 2(0)] = 82 kJ mol1

Level 1: Qn 6, 8, 13
Level 2: Qn 17
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3.2 STANDARD ENTHALPY CHANGE OF FORMATION, Hf

Definition: H can be +/-
It is the heat change when 1 mole of substance is formed from its
constituent elements in their standard states under the standard
conditions of 298 K and 1 bar.

Note: Hf of an element = 0 since it is being ‘formed’ from itself.

e.g. Na(s)  Na(s) Hf of Na(s) = 0
Hf(C(graphite)) = Hf(Na(s)) = Hf(Br2(l)) = Hf(O2(g)) = 0

For elements that can exist as different allotropes under standard

conditions, the most stable allotrope is used as the standard and it must
be specified.
Example: Since graphite is the more stable form of the two allotropes, C(s)
in standard state refers to graphite (see Page 4).

Also, the same reaction may be represented by more than one definition.
Examples: C(s) + O2(g)  CO2(g) Hc(C(s)) = Hf(CO2(g))
H2(g) + ½O2(g)  H2O(l) Hc(H2(g)) = Hf(H2O(l))
They share the same balanced eqn with same s.s!
Hf value gives us an idea of the energetically stability of the compound
formed compared to its elements. In general, a compound with a more
negative H f is energetically more stable.
Example:
 Hf(A) > 0  A has higher energy content,
enthalpy A is energetically less stable than the
A
elements.
 Hf(B) < 0  B has lower energy content,
Hf(A)
elements B is energetically more stable than the
0
elements.
Hf(B)
Hf(C)  Hf(C) is more negative than Hf(B)
B
 C has lower energy content than B
C
 C is energetically more stable than B

 Stability of A < B < C.

2022 JPJC JC1 H2 Chemistry (9729) 16 Topic 5: Chemical Energetics (Part 1)

 must have state symbols!
Exercise 13: Write an equation each to represent the standard enthalpy
change of formation for the following substances.
(a) bromochloromethane, CH2BrCl(l):
C(s) + H2(g) + ½ Br2(l) + ½Cl2(g)  CH2BrCl(l)
Not 2C(s) + 2H2(g) + Br2(l) + Cl2(g)  2CH2BrCl(l)
(b) nitrobenzene, C6H5NO2(l):
5 1
6C  s   H2  g   N2  g   O2  g   C6H5NO2  l 
2 2
Not 12C(s) + 5H2(g) + N2(g) + 2O2(g)  2C6H5NO2(l)
C(s) + 2H2(g) C(s) + 2Cl2(g) ½H2(g) + ½Cl2(g)
Exercise 14:
substance CH4(g) CCl4(l) HCl(g)
H 
f
1
/ kJ mol 74.8 139 92.3 x4

Given the above data, construct an energy cycle and use it to calculate the
standard enthalpy change, Hr of the following reaction:
CH4(g) + 4Cl2(g)  CCl4(l) + 4HCl(g) Hr
Check LHS = RHS!
Hr
CH4(g) + 4Cl2(g) CCl4(l) + 4HCl(g)

74.8 4(0) 139 4(92.3)

C(s) + 4Cl2(g) + 2H2(g)

By Hess’ Law,
Hr = [(74.8)  4(0)] + [(139) + 4(92.3)] = 433 kJ mol1

mHf(reactants)  nHf(products)

In general,
Hr
reactants products

mHf(reactants) nHf(products)

elements (standard state)

This leads to the universally applicable formula when given H f data:
If Qn doesn’t
H r = mH f(products)  nH f(reactants)
require you to where m & n are the stoichiometric coefficient in the thermochemical equation
draw energy cycle

Exercise 15:
Given that the standard enthalpy change of formation of CHCl3(l) and HCl(g)
are 134 kJ mol1 and 92 kJ mol1 respectively, calculate the standard
enthalpy change of formation of COCl2(g).
2CHCl3(l) + O2(g)  2COCl2(g) + 2HCl(g) Hr = 356 kJ mol1
2(134) (0) 2Hf 2(92)
H 
r = mH f(products)  nHf(reactants)


356 = [2H f(COCl2(g)) + 2(92)]  [2(134) + (0)]

H f(COCl2(g)) = 220 kJ mol1
Level 1: Qn 7,10,11

2022 JPJC JC1 H2 Chemistry (9729) 17 Topic 5: Chemical Energetics (Part 1)

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 Queries about Lecture: www.tinyurl.com/j1chemlecture

3.3 BOND ENERGY, E(XY)

Definition:
It is the heat absorbed when 1 mole of a covalent bond between 2
atoms in the gaseous state is broken. (i.e. E(XY) is always positive.)
Note: Bond energies are defined under gaseous condition. The reactant
molecules and resulting atoms are all in gaseous state.

The bond energy value indicates the strength of covalent bond between
two atoms present in the gaseous state. The same amount of energy is
released when one mole of the same bond in the gaseous state is formed
Linked to Topic 2: (i.e. reverse process of breaking bond).
Chemical Bonding
Topic 9: Coz no other molecules has these bonds!
The Periodic Table
Also, bond energies in diatomic molecules are accurate/exact values.
Examples: HH(g)  2H(g) E(HH) = +436 kJ mol1
O=O(g)  2O(g) E(O=O) = +496 kJ mol1
CO(g)  C(g) +O(g) E(CO) = +1077 kJ mol1

Exercise 16:
Using the bond energy values from the Data Booklet, draw an energy cycle
and calculate the standard enthalpy change, Hr, of the following reaction.
C2H4(g) + H2(g)  C2H6(g)
Advice: Good to draw
displayed structure Hr
(g) + HH(g) (g)
to identify all the
bonds involved!
Note: (+610) (+436) (+350)
C=C  2 CC + 4(+410) + 6(+410)
(+) (2) 2C(g) + 6H(g)
By Hess’ Law,
E(bonds in rxtants)  E(bonds in pdts)
Hr = [(+610) + 4(+410) + (+436)]  [(+350) + 6(+410)]
= 124 kJ mol1

In general,
Hr
gaseous reactants gaseous products
E(all bonds in reactants) E(all bonds in products)
gaseous atoms
This leads to the universally applicable formula when given bond energies:
If Qn doesn’t
H r = E(all bonds in reactants)  E(all bonds in products)
require you to
draw energy cycle

2022 JPJC JC1 H2 Chemistry (9729) 18 Topic 5: Chemical Energetics (Part 1)

 When calculating H using bond energies, the calculated value and actual
values may have discrepancies and this is due to:
 the bond energies in Data Booklet are average values derived from a
full range of molecules containing that particular bond, except for diatomic
molecules.
 the reactants and/or products are not in gaseous state and hence,
Hvap and/or Hfus is not accounted for in the calculation.
 the ring strain in 3 or 4membered ring causes angle strain and
weaken the bond.
 the reaction may not take place under standard conditions.

Exercise 17:
Pentane, CH3CH2CH2CH2CH3, is often used as solvents in the laboratory.
(a) Write an equation to represent the standard enthalpy change of
combustion of pentane.
CH3CH2CH2CH2CH3(l) + 8 O2(g)  5 CO2(g) + 6 H2O(l)

(b) Use relevant data from the Data Booklet to estimate a value of the
standard enthalpy change of combustion, ∆Hc, of pentane.

Hr
(g) + 8O=O(g) 5O=C=O(g) + 6HOH(g)

Bonds Energy Bonds Energy

broken required formed evolved
4 CC 4(+350) 10 C=O 10(+805)
12 CH 12(+410) 12 OH 12(+460)
8 O=O 8(+496)
Total +10288 Total +13570
Hr = E(all bonds in reactants)  E(all bonds in products)
= (+10288) – (+13570) = 3282 kJ mol1

(c) The actual value of ∆Hc of pentane is –3509 kJ mol1. Suggest an

explanation for the discrepancy in this value and that obtained in (b).
Quoted from DB
Pentane and water are liquid, not in gaseous state. Hence, their
standard enthalpy changes of vaporisation have not been taken
into account in the calculation.
Also, the bond energies quoted from the Data Booklet are average
values.

2022 JPJC JC1 H2 Chemistry (9729) 19 Topic 5: Chemical Energetics (Part 1)

 3.4 STANDARD ENTHALPY CHANGE OF ATOMISATION, H a
Definition:
It is the heat absorbed when 1 mole of gaseous atoms is formed from
its element in its standard state under standard conditions of 298 K
and 1 bar. (i.e. Ha is always positive.)

Exercise 18: For each of the following, write an equation to represent its
standard enthalpy change of atomisation.
(a) Ha(Mg) : Mg(s)  Mg(g)
(b) Ha(O) : ½O2(g)  O(g)
(c) Ha(Br) : ½Br2(l)  Br(g)
(d) Ha(I) : ½I2(s)  I(g)

Relationship between Ha and Bond Energy:

(a) Consider diatomic gaseous molecules:
O2(g)  2O(g) 2Ha(O) = E(O=O) For diatomic gaseous molecule,
Cl2(g)  2Cl(g) 2Ha(Cl) = E(ClCl) 2Ha(X) = E(XX)

(b) Consider diatomic molecules which are not in gaseous state:

2Ha(Br) 2Br(g)
Br2(l)
By Hess’ Law,
H 
vap(Br2) E(BrBr) 2Ha(Br) = Hvap(Br2) + E(BrBr)
Br2(g)

2Ha(I)
I2(s) 2I(g)
By Hess’ Law,
Hsublim(I2) E(II) 2Ha(I) = Hsublim(I2) + E(II)
I2(g)

Exercise 19:
Using the following enthalpy changes and other data from the Data Booklet,
Hf(CH4(g)) = –76 kJ mol–1 C(s) + 2H2(g)  CH4(g)
Ha(C(s)) = +720 kJ mol–1 C(s)  C(g)
construct an energy cycle and use it to calculate the average bond energy of
the C–H bond in CH4(g). ¼CH4(g)  ¼C(g) + H(g)

Alternative:
4E(CH) C(g) + 4H(g)
CH4(g) 76
C(s) + 2H2(g) CH4(g)

76 +720 2(+436)

2E(H-H) +720 2(+436) 4E(CH)
C(s) + 2H2(g)
By Hess’ Law, C(g) + 4H(g)

4E(CH) = (76) + [(+720) + 2(+436)] Level 1: Qn 3,

E(CH) = +417 kJ mol1 Level 2: Qn 19, 20
(deviates from that in Data Booklet, why?)
2022 JPJC JC1 H2 Chemistry (9729) 20 Topic 5: Chemical Energetics (Part 1)
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3.5 BORN–HABER CYCLE FOR IONIC SOLIDS

BornHaber cycle is an application of Hess’ Law to calculate the lattice
energy of an ionic compound which cannot be experimentally determined.
BornHaber cycle is a specific name given when drawing an energy cycle
involving Hf of an ionic solid from the reaction between a metal and a
nonmetal. elements  ionic solid
To establish the Born–Haber cycle, we need to understand a few other
enthalpies change: lattice energy, electron affinity and ionisation energy.

3.5.1 Lattice Energy of an Ionic solid, LE anion(g) + cation(g)  ionic solid

Definition:
It is the heat evolved when 1 mole of ionic solid is formed
from its gaseous ions under standard conditions of 298 K
and 1 bar. (i.e. LE is always negative.)

Exercise 20: For each of the following, write an equation to represent

its lattice energy.
(a) LE of Na2O : 2Na+(g) + O2(g)  Na2O(s)
(b) LE of Mg(NO3)2 : Mg2+(g) + 2NO3(g)  Mg(NO3)2(s)
form IB (exo, LE)
anion(g) + cation(g)  ionic solid
+ lattice energy
break IB (endo, LE)

Linked to Topic 2: The lattice value provides a measure of the strength of the ionic
Chemical Bonding bonds between the oppositely charged ions. The same amount of
energy is required when one mole of the same ionic solid is broken
(i.e. reverse process of forming bond).
The more exothermic the LE, the stronger the ionic bond.
or the larger the magnitude of LE, stronger the IB
(a) Factors affect LE of an ionic compound

q  q
| lattice energy | 
r  r q q

Note: The effect of (q+ × q) on LE is greater

r r
than that of (r+ + r) on LE.
where q+ and q are the ionic charges on cation and anion respectively
r+ and r are the ionic radius on cation and anion respectively
(r+ + r) are the inter–ionic distance

From the above relationship,

 The larger the ionic charges, the larger the magnitude of the
lattice energy (i.e. LE becomes more exothermic).
 The larger the ionic radii, the smaller the magnitude of the
lattice energy (i.e. LE becomes less exothermic).

2022 JPJC JC1 H2 Chemistry (9729) 21 Topic 5: Chemical Energetics (Part 1)

 Exercise 21: State and explain the magnitude of lattice energy of CaCl2
as compared to that of CaBr2. Difference is anion
Cl and Br have the same ionic charge but Cl has smaller ionic
radius than Br.
q  q
Since lattice energy  , the magnitude of lattice energy of
r  r
CaCl2 is larger than that of CaBr2 (or the lattice energy of CaCl2 is
more exothermic).

Exercise 22:
Compare and arrange the magnitude of lattice energy of the following
compounds in ascending order. Explain your answer.
BaCl2 LiF CaO
all ionic charges & radius are different!
q  q
Since lattice energy  , the effect of (q+ × q) on LE is
r  r
greater than that of (r+ + r) on LE.

BaCl2 LiF CaO

q+  q (2+)  (1) (1+)  (1) (2+)  (2)

Hence, the magnitude of LE of LiF < BaCl2 < CaO.

(b) Discrepancies between experimental and theoretical LE values

Lattice energies determined from Born–Haber cycle (see
Section 3.5.4 on Page 24) are experimental values since they
are calculated using enthalpies which are experimentally
determined enthalpies.
Theoretical LE values assume a 100 % purely ionic model.

Hence, when the theoretical and experimental LE values differ,

it implies that the ionic compound shows covalent character.
See Chem Bonding for The larger the difference between the experimental and
Extent of Polarisation theoretical LE values, the greater the covalent character
in the ionic compound.
Example:
Compound Theoretical LE Experimental LE
NaCl 766 771
NaBr 731 742
AgF 953 967
AgI 808 889
 For NaCl, NaBr and AgF, there is close agreement between
the theoretical and experimental values (i.e. the bonding in
these halides is largely ionic).
Linked to Topic 2:
 For AgI, there is significant difference between the
Chemical Bonding theoretical and experimental values (i.e. AgI has ionic bonds
with some degree of covalent character).
electron cloud of large I is polarized to larger extent

2022 JPJC JC1 H2 Chemistry (9729) 22 Topic 5: Chemical Energetics (Part 1)

 anion(g) + cation(g)  ionic solid

3.5.2 Ionisation Energies, IE atom(g)  cation(g) + e

Linked to Topic 1: Definition:
Atomic Structure
1st IE is the heat absorbed when 1 mole of electrons is
removed from 1 mole of gaseous atom to form 1 mole of
singly charged gaseous cation. (i.e. IE is always positive.)

2ndt IE is the heat absorbed when 1 mole of electrons is

removed from 1 mole of singly charged gaseous cation to
form 1 mole of doubly charged gaseous cation.

Exercise 21: For each of the following, write an equation to represent

the stated ionisation energy.
(a) 1st IE of Na : Na(g)  Na+(g) + e
(b) 2nd IE of Mg : Mg+(g)  Mg2+(g) + e
1st: Ca(g)  Ca+(g) + e
2nd: Ca+(g)  Ca2+(g) + e (c) 1st + 2nd IE of Ca : Ca(g)  Ca2+(g) + 2e
not 2 × 1st IE (i.e 2Ca(g)  2Ca+(g) + 2e

3.5.3 Electron Affinity, EA atom(g) + e  anion(g)

Definition: e 

1st EA is the heat evolved when 1 mole of electrons is added

to 1 mole of gaseous atom to form 1 mole of singly charged
gaseous anion. (i.e. 1st EA is always negative.)

2ndt EA is the heat absorbed when 1 mole of electrons is

added 1 mole of singly charged gaseous anion to form 1
mole of doubly charged gaseous anion. (i.e. Subsequent EA is
always positive.)

Exercise 22: For each of the following, write an equation to represent

the stated electron affinity.
(a) 1st EA of Cl : Cl(g) + e  Cl(g)
(b) 2nd EA of O : O(g) + e  O2(g)
1st: S(g) + e  S(g) (c) 1st + 2nd EA of S : S(g) + 2e  S2(g)
2nd: S(g) + e  S2(g)
not 2 × 1st EA (i.e 2S(g) + 2e  2S(g)
e

Exercise 23:
Given: O(g) + e  O(g) 1st EA of O = –141 kJ mol–1
O(g) + e  O2(g) 2nd EA of O = +790 kJ mol–1
Explain why the second electron affinity for oxygen is endothermic.

For the 2nd EA, an electron is added to an anion.

Energy is needed to overcome the electrostatic repulsion between the
negatively charged anion and the negatively charged electron to
be added.
Hence, the process is endothermic.

2022 JPJC JC1 H2 Chemistry (9729) 23 Topic 5: Chemical Energetics (Part 1)

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3.5.4 Constructing Born–Haber Cycle
A BornHaber cycle an be drawn either as an energy cycle or an
energy level diagram (a subset of energy cycle).
https://tinyurl.com/
Developed by German scientist, Max Born and Fritz Haber, this
chemenerg4 energy cycle breaks down the formation of an ionic compound into a
Video on series of simpler steps.
Born–Haber Cycle elements  ionic solid cation(g) + anion(g)  ionic solid

elements  atoms(g) atom(g)  cation(g) + anion(g)

FIGURE 6 A simplified illustration of processes in Born–Haber cycle.
[modified from Elementix, Alamy stock photo].

By Hess’ Law, Hf = (Ha and BE) + (IE) + (EA) + LE

An energy cycle can be used to represent the illustration in Figure 6.

Exercise 24: Given the following enthalpy changes:

Ha of sodium = +107 kJ mol–1 Na(s)  Na(g)
H a of chlorine

= +122 kJ mol –1 ½Cl2(g)  Cl(g)
first electron affinity of chlorine = –360 kJ mol–1
Cl(g) + e  Cl(g)
Hf of solid sodium chloride = – 411 kJ mol–1Na(s) + ½Cl2(g)  NaCl(s)
Using the above data and appropriate data from the Data Booklet,
construct a BornHaber cycle and use it to calculate the lattice energy
of sodium chloride. Na+(g) + Cl(g)  NaCl(s)
Checklist for Energy Cycle: Hf = 411 NaCl(s)
For each process, the
Na(s) + ½Cl2(g)
following must be fulfilled: Ha(Na) Ha(Cl)
 balanced equations = +107 = (+122)
 correct state symbols
 correct arrow directions not ½(+122)!!
 correct H values/symbols Na(g) + Cl(g)
 appropriate multipliers LE(NaCl)
 “+” required for LE equation
1st IE 1st EA
= +494 = 360

Na+(g) + Cl(g)
By Hess’ Law,
(411) = (+107) + (+122) + (+494) + (360) + LE(NaCl)
LE(NaCl) = 774 kJ mol1
2022 JPJC JC1 H2 Chemistry (9729) 24 Topic 5: Chemical Energetics (Part 1)
 Exercise 25:
Using the following data and appropriate data from the Data Booklet,
Ha of sodium = +107 kJ mol–1 Na(s)  Na(g)
first electron affinity of oxygen = –147 kJ mol –1 O(g) + e  O(g)
second electron affinity of oxygen = +753 kJ mol–1 O(g) + e  O2(g)
lattice energy of Na2O = –2488 kJ mol–1 2Na+(g) + O2(g)  Na2O(s)
construct an energy level diagram, using the grid given below, to
calculate the enthalpy change of formation of sodium oxide.
2Na(s) + ½O2(g)  Na2O(s)
enthalpy or energy / kJ mol1

Same type of enthalpies 2Na+(g) + O2(g)

for the same element 1st + 2nd EA
= (147) + (+753)
can be grouped together
= +606
2Na+(g) + 2e + O(g)

2(1st IE)
= 2(+494)
LE
= (2488)
2Na(g) + O(g)
½E(O=O)
2Na(g) + ½O2(g) = ½(+496)

2Ha
If the level contains only 0 2Na(s) + ½O2(g) = 2(+107)
elmts in std state, the Hf
reference (not absolute) Na2O(s)
energy level is “0”!

By Hess’ Law,
Hf of Na2O = 2(+107) + ½(+496) + 2(+494) + (+606) + (2488)
= –432 kJ mol–1

Checklist for Energy Level:

For each process, the following must be fulfilled:
 balanced equations with correct state symbols
 correct arrow directions( for endothermic and  for exothermic)
 (endothermic) : energy level of product is higher than reactant
 (exothermic) : energy level of product is lower than reactant
 correct H values/symbols
 appropriate multipliers
 “0” for energy level of element in standard states (where applicable)
 Includes electrons in equations for IE and EA (IE first then EA)

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Level 1: Qn 9, 14
Level 2: Qn 21

2022 JPJC JC1 H2 Chemistry (9729) 25 Topic 5: Chemical Energetics (Part 1)

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3.6 STANDARD ENTHALPY CHANGE OF SOLUTION, H soln
Definition: H can be +/-
It is the heat change when 1 mole of a substance is completely
dissolved in enough water under the standard conditions of 298 K
and 1 bar so that there is no further heat change upon adding more
water. implies completely dissolved
1) q = mcT
 heat change, q 
Experimentally determined: Hsoln =    2) Find nsubst dissolved
 nsubstance dissolved  3) Calc. H

Examples: NaCl(s) + aq  Na+(aq) + Cl(aq) Hsoln = +3.9 kJ mol1

CuSO4(s) + aq  Cu (aq) + SO4 (aq) Hsoln = 73.2 kJ mol1
2+ 2

3.6.1 Standard Enthalpy Change of Hydration, H hyd

Definition:
It is the heat evolved when 1 mole of gaseous ions is hydrated
under the standard conditions of 298 K and 1 bar.
(i.e. Hhyd is always negative.)

Examples: Cl(g) + aq  Cl(aq) Hhyd of Cl

Ca2+(g) + aq  Ca2+(aq) Hhyd of Ca2+

Linked to Topic 2: Hhyd is exothermic since ion–dipole interaction is formed between

Chemical Bonding the gaseous ions and water molecules to give aqueous ions.

FIGURE 7 Formation of ion–dipole interactions between ions and water molecules.

Hence, the magnitude of H hyd of an ion depends on the charge

density of the ion.
charge of ion not the same
| Hhyd of an ion | 
radius of ion q+  q
as
r+  r
From the above relationship,
 The larger the ionic charge, the larger the magnitude of Hhyd
(i.e. Hhyd becomes more exothermic).
 The larger the ionic radii, the smaller the magnitude of Hhyd
(i.e. Hhyd becomes less exothermic).

Ion H hyd / kJ mol1 Ion H hyd / kJ mol1

Na+ 406 F 504
Mg2+ 1926 Cl 384
Al3+ 4680 Br 328
I 287

2022 JPJC JC1 H2 Chemistry (9729) 26 Topic 5: Chemical Energetics (Part 1)

 Exercise 26: Explain why the enthalpy change of hydration of halide ions
become less exothermic down Group 17.

Down Group 17, the ionic charge of X is the same while the ionic radius
increases and hence, the charge density of X decreases.

charge of ion
Since Hhyd  , the strength of iondipole interactions
radius of ion
between X and water molecules decreases. Hence, the magnitude of
Hhyd of X decreases (or Hhyd of X becomes less exothermic).

3.6.2 Relationship between H soln, H hyd and LE

The dissolution of MX(s) can be divided into two processes:

 Breaking the ionic lattice of the solid to form its constituent
gaseous ions (i.e. energy absorbed  H is positive).
 Hydrating gaseous ions through forming ion–dipole interactions
with water molecules (i.e. energy released  H is negative).

FIGURE 8 A simplified illustration of processes during the dissolution of an ionic solid.

By Hess’ Law, Hsoln = LE + Hhyd(ions)

Linked to Topic 2: From the relationship, +ve -ve
Chemical Bonding
 Hsoln >> 0  substance is generally less soluble or sparingly
soluble in water.
Energy released from the formation of ion–dipole interaction
between ions and water molecules is insufficient to compensate
the energy required to break the strong ionic bonds between
oppositely charged ions and hydrogen bonds between water
molecules (i.e. | LE | > | Hhyd(ions) | ). Eg. (+545) + (345)

 Hsoln < 0  substance is generally more soluble in water.

Energy released from the formation of ion–dipole interaction
between ions and water molecules is more than sufficient to
compensate the energy required to break the strong ionic bonds
between oppositely charged ions and hydrogen bonds between
water molecules (i.e. | LE | < | Hhyd(ions) | ). Eg. (+345) + (545)
2022 JPJC JC1 H2 Chemistry (9729) 27 Topic 5: Chemical Energetics (Part 1)
 Exercise 27: Given the following enthalpy changes,
Hsoln of potassium bromide = +20 kJ mol–1 KBr(s)  K+(aq) + Br(aq)
Hhyd of potassium ion = –322 kJ mol–1 K+(g)  K+(aq)
H hyd of bromide ion

= –336 kJ mol–1 Br(g)  Br(aq)
Construct an energy level diagram and use it to calculate the lattice energy of
potassium bromide. +
K (g) + Br (g)  KBr(s)


enthalpy or energy / kJ mol1 Checklist for Energy Level:

For each process, the
K+(g) + Br(g) following must be fulfilled:
 balanced equations
Hhyd(Br)  correct state symbols
= (336)  correct arrow directions
( for endo and  for exo)
K+(g) + Br(aq)  (endo) energy level of
product is higher than
LE(KBr) Hhyd(K+) reactant
= (322)  (exo) energy level of
K+(aq) + Br(aq) product is lower than
reactant
 correct H values/symbols
Hsoln = +20  appropriate multipliers
KBr(s)
Note:
This energy level does not
By Hess’ Law, have a zero reference level
since there are no elements
LE of KBr = (336) + (322)  (+20) in their standard states.
= 678 kJ mol1

If the question did not ask for ‘energy level’ and/or did not provide grid for
energy level, the following energy cycle can be drawn:

Hsoln = (+20)
KBr(s) K+(aq) + Br(aq) Checklist for Energy Cycle:
(+aq) For each process, the
following must be fulfilled:
Hhyd(K+) Hhyd(Br)  balanced eqn
LE(KBr)
= (322) = (336)  correct state symbols
 correct arrow directions
K+(g) + Br(g)  correct H values/symbols
 appropriate multipliers
By Hess’ Law,
(+20) = LE(KBr) + [(322) + (336)] Level 1: Qn 4
LE(KBr) = 678 kJ mol1 Level 2: Qn 22

2022 JPJC JC1 H2 Chemistry (9729) 28 Topic 5: Chemical Energetics (Part 1)

 SUMMARY (LIST OF DEFINITIONS & FORMULAE)

1 Hess’ Law states that the enthalpy change accompanying a chemical reaction is
the same regardless of the route by which the chemical change occurs, provided
that the initial and final states are the same.

2 Experimental Determination of H:

Assuming 100 % efficiency,
heat change, q = msolcsolT + CcalorimeterT (or q = vsolcsolT + CcalorimeterT)
where msol = mass of solution (in g)
vsol = total volume of solution (in cm3)
csol = specific heat capacity of solution (in J g1 K1 or J cm3 K1)
Ccalorimeter = heat capacity of calorimeter (in J K1)

% efficiency
Otherwise, × total heat change, q = msolcsolT + CcalorimeterT
100
 heat change, q 
Then H =   
 n 
where n = amount of substance, defined by specific H (in mol)

3 Standard enthalpy change of reaction, H r

It is the heat change when molar quantities of reactants, as specified in the
chemical equation, react completely to form products under the standard
conditions of 298 K and 1 bar.

Experimentally determined:
 heat change, q 
Hr =  
 nlimiting reagent 
× stoichiometric coefficient of limiting reagent
 
From Hess’ Law:
If Hc given : Hr = mHc(reactants)  nHc(products)
If Hf given : Hr = mHf(products)  nHf(reactants)
where m & n are the stoichiometric coefficient in the thermochemical equation
If use BE data : Hr = E(all bonds in reactants)  E(all bonds in products)

4 Standard enthalpy change of neutralisation, H n

It is the heat evolved when 1 mole of water is formed from the reaction of an
acid and an alkali under the standard conditions of 298 K and 1 bar. (i.e. Hn is
always negative.)
e.g. NaOH(aq) + ½H2SO4(aq)  ½Na2SO4(aq) + H2O(l) Hn = 57.3 kJ mol1
 heat change, q 
Experimentally determined: Hn =   
 nwater formed 

5 Standard enthalpy change of combustion, Hc

It is the heat evolved when 1 mole of a substance is completely burnt in
excess oxygen under the standard conditions of 298 K and 1 bar. (i.e. Hc is
always negative.)
e.g. CH3CH2OH(l) + 3O2(g)  2CO2(g) + 3H2O(l) Hc of ethanol
 heat change, q 
Experimentally determined: Hc =   
 nsubstance burnt 

2022 JPJC JC1 H2 Chemistry (9729) 29 Topic 5: Chemical Energetics (Part 1)

6 Standard enthalpy change of formation, H f
It is the heat change when 1 mole of substance is formed from its constituent
elements in their standard states under the standard conditions of 298 K and 1
bar.
5 1
e.g. 6C(s) + H2(g) + N2(g) + O2(g)  C6H5NO2(l) Hc of C6H5NO2(l)
2 2

7 Bond energy, E(XY)

It is the heat absorbed when 1 mole of a covalent bond between 2 atoms in
the gaseous state is broken. (i.e. E(XY) is always positive.)
e.g. ¼CH4(g)  ¼C(g) + H(g) E(C–H)

8 Standard enthalpy change of atomisation, Ha

It is the heat absorbed when 1 mole of gaseous atoms is formed from its
element in its standard state under standard conditions of 298 K and 1 bar.
(i.e. Ha is always positive.)
e.g. ½I2(s)  I(g) Ha of I

9 Ionisation energy, IE
It is the heat absorbed when 1 mole of electrons is removed from 1 mole of
gaseous atom to form 1 mole of singly charged gaseous cation. (i.e. IE is always
positive.)
e.g. Mg(g)  Mg+(g) + e 1st IE of Mg

2ndt IE is the heat absorbed when 1 mole of electrons is removed from 1 mole
of singly charged gaseous cation to form 1 mole of doubly charged gaseous
cation.
e.g. Mg+(g)  Mg2+(g) + e 2nd IE of Mg

9 Electron affinity, EA
It is the heat evolved when 1 mole of electrons is added to 1 mole of gaseous
atom to form 1 mole of singly charged gaseous anion. (i.e. 1st EA is always
negative.)
e.g. O(g) + e  O(g) 1st EA of O

2ndt EA is the heat absorbed when 1 mole of electrons is added 1 mole of

singly charged gaseous anion to form 1 mole of doubly charged gaseous anion.
(i.e. Subsequent EA is always positive.)
e.g. O(g) + e  O2(g) 2nd EA of O

10 Lattice energy, LE
It is the heat evolved when 1 mole of ionic solid is formed from its gaseous
ions under standard conditions of 298 K and 1 bar. (i.e. LE is always negative.)
e.g. Ca2+(g) + 2Br(g)  CaBr2(s) LE of CaBr2

q  q Note: The effect of (q+ × q) on LE is greater than

| lattice energy | 
r  r that of (r+ + r) on LE.

2022 JPJC JC1 H2 Chemistry (9729) 30 Topic 5: Chemical Energetics (Part 1)

11 Standard enthalpy change of hydration, Hhyd
It is the heat evolved when 1 mole of gaseous ions is hydrated under the
standard conditions of 298 K and 1 bar. (i.e. Hhyd is always negative.)
e.g. Ca2+(g)  Ca2+(aq) Hhyd of Ca2+
charge of ion
| Hhyd of an ion | 
radius of ion

12 Standard enthalpy change of solution, H soln

It is the heat change when 1 mole of a substance is completely dissolved in
enough water under the standard conditions of 298 K and 1 bar so that there is no
further heat change upon adding more water.
 heat change, q 
Experimentally determined: Hsoln =   
 nsubstance dissolved 
From Hess’ Law: Hsoln = LE + Hhyd(ions)

Extension Exercise (Summary)

Complete the following table by placing a tick () in the appropriate column for each
enthalpy process.
Always Always Can be Remarks
Enthalpy
exothermic endothermic exothermic or
Process
(H < 0) (H > 0) endothermic
Formation of compound (in any states)
Hf  from its constituent elements in their
standard states.
Complete burning of compound in
Hc  excess O2 to form products with much
stronger bonds (e.g. C=O bonds in CO2)
Hn  Formation of H2O from H+(aq) & OH(aq)
Formation of gaseous atoms from its
Ha 
element in its standard state.
Bond Breaking of covalent bonds in the gas

Energy phase to form gaseous atoms.
Formation of gaseous cations, M+(g) by
st
1 IE  removing electrons from gaseous
atoms, M(g).
Formation of gaseous anions, X(g) by
st
1 EA  adding electrons to gaseous atoms,
X(g).
Formation of ionic compound from its
LE 
gaseous ions.
Formation of aqueous ions from its
Hhyd 
gaseous ions via iondipole interactions.
Complete dissolving of ionic compound
Hsoln 
in water to give aqueous ions.
Hvap  Converting a liquid to a gas.
Hfus  Converting a solid to a liquid.
Hsublime  Converting a solid to a gas directly.

2022 JPJC JC1 H2 Chemistry (9729) 31 Topic 5: Chemical Energetics (Part 1)