Energetics

6.1 What is Energetics?

6.2 Enthalpy Changes Related to Breaking and
Forming of Bonds
6.3 Standard Enthalpy Changes
6.4 Experimental Determination of Enthalpy
Changes by Calorimetry
6.5 Hess’s Law
6.6 Calculations involving Standard Enthalpy
Changes of Reactions
1 New Way Chemistry for Hong Kong A-Level Book 1
6.1 What is energetics? (SB p.136)

What is energetics?
Energetics is
Energetics is the
the study
study of
of energy
energy changes
changes
associated with
associated with chemical
chemical reactions.
reactions.

Thermochemistry is
Thermochemistry is the
the study
study of
of heat
heat changes
changes
associated with
associated with chemical
chemical reactions.
reactions.
Some terms
Enthalpy(H) = heat content in a substance
Enthalpy change(H)
= heat content of products - heat content of
reactants
= Hp - H r
2 New Way Chemistry for Hong Kong A-Level Book 1
6.1 What is energetics? (SB p.136)

Law of conservation of energy

The law
The law of
of conservation
conservation of
of energy
energy states
states that
that
energy can
energy can neither
neither be
be created
created nor
nor destroyed.
destroyed.

3 New Way Chemistry for Hong Kong A-Level Book 1

6.1 What is energetics? (SB p.137)

Internal energy and enthalpy

e.g. Zn(s) + 2HCl(aq)  ZnCl2(aq) + H2(g)

4 New Way Chemistry for Hong Kong A-Level Book 1

6.1 What is energetics? (SB p.138)

Internal energy and enthalpy

Heat change at Change in Work done

constant = internal + on the
pressure energy surroundings
Enthalpy (Heat change at
change constant volume)

5 New Way Chemistry for Hong Kong A-Level Book 1

6.1 What is energetics? (SB p.138)

Exothermic and endothermic

reactions

An exothermic
An exothermic reaction
reaction is
is aa reaction
reaction that
that
releases heat
releases heat energy
energy to
to the
the surroundings.
surroundings.
(H == -ve)
(H -ve)
6 New Way Chemistry for Hong Kong A-Level Book 1
6.1 What is energetics? (SB p.139)
Check Point 6-1
Exothermic and endothermic
reactions

An endothermic
An endothermic reaction
reaction is
is aa reaction
reaction that
that
absorbs heat
absorbs heat energy
energy from
from the
the surroundings.
surroundings.
(H == +ve)
(H +ve)
7 New Way Chemistry for Hong Kong A-Level Book 1
 6.
2
Energy Changes
Related to
Breaking and
Forming of Bonds
8 New Way Chemistry for Hong Kong A-Level Book 1
6.2 Enthalpy changes related to breaking and forming of bonds (SB p.140)

Enthalpy changes related to breaking

and forming of bonds
e.g. CH4 + 2O2 CO2 + 2H2O

9 New Way Chemistry for Hong Kong A-Level Book 1

6.2 Enthalpy changes related to breaking and forming of bonds (SB p.140)

Enthalpy changes related to breaking

and forming of bonds

In an
In an exothermic
exothermic reaction,
reaction, thethe energy
energy required
required in in
breaking the
breaking the bonds
bonds in
in the
the reactants
reactants is
is less
less than
than
the energy
the energy released
released in
in forming
forming the
the bonds
bonds in in the
the
products (products
products (products contain
contain stronger
stronger bonds).
bonds).

10 New Way Chemistry for Hong Kong A-Level Book 1

6.2 Enthalpy changes related to breaking and forming of bonds (SB p.140)

Enthalpy changes related to breaking

and forming of bonds

11 New Way Chemistry for Hong Kong A-Level Book 1

6.2 Enthalpy changes related to breaking and forming of bonds (SB p.140)

Enthalpy changes related to breaking

and forming of bonds

In an
In an endothermic
endothermic reaction,
reaction, the
the energy
energy required
required
in breaking
in breaking the
the bonds
bonds in
in the
the reactants
reactants is
is more
more
than the
than the energy
energy released
released inin forming
forming the
the bonds
bonds
in the
in the products
products (reactants
(reactants contain
contain stronger
stronger
bonds).
bonds).

Check Point 6-2

12 New Way Chemistry for Hong Kong A-Level Book 1
 6.
3 Standard
Enthalpy
Changes
13 New Way Chemistry for Hong Kong A-Level Book 1
6.3 Standard enthalpy changes (SB p.141)

Standard enthalpy changes

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g)

H = -802 kJ mol-1

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

H = -890 kJ mol-1

14 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.141)

Standard enthalpy changes

As enthalpy changes depend on temperature
and pressure, it is necessary to define standard
states and conditions:
1. elements
1. elements oror compounds
compounds in in their
their normal
normal
physical states;
physical states;
2.
2. a pressure of 1 atm (101325 Nm );); and
a pressure of 1 atm (101325 Nm -2
-2 and
3.
3. a temperature of 25ooC (298 K)
a temperature of 25 C (298 K)

Enthalpy change under standard conditions denoted

by symbol: H
ø

15 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.142)

Standard enthalpy changes of

neutralization
Standard enthalpy
Standard enthalpy change
change ofof neutralization
neutralization
(Hneut
neut)) is
is the
the enthalpy
enthalpy change
change whenwhen one
one mole
mole
ø

(H
of water
of water is is formed
formed from
from the
the neutralization
neutralization of
of an
an
acid by
acid by an an alkali
alkali under
under standard
standard conditions.
conditions.

e.g. H+(aq) + OH-(aq)  H2O(l)

ø
Hneut = -57.3 kJ mol-1

16 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.142)

Standard enthalpy changes of

neutralization
Acid Alkali Hneu

ø
HCl NaOH -57.1
HCl KOH -57.2
HCl NH3 -52.2
HF NaOH -68.6

H+(aq) + OH-(aq)  H2O(l)

17 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.142)

Standard enthalpy changes of

neutralization

Enthalpy level diagram for the neutralization of

a strong acid and a strong alkali
18 New Way Chemistry for Hong Kong A-Level Book 1
6.3 Standard enthalpy changes (SB p.142)

Standard enthalpy change of

solution
Standard enthalpy
Standard enthalpy change
change of of solution
solution (H
(Hsoln
soln)) is
is

ø
the enthalpy
the enthalpy change
change when
when one one mole
mole of of aa
solute is
solute is completely
completely dissolved
dissolved in in aa sufficiently
sufficiently
large volume
large volume ofof solvent
solvent to
to form
form an
an infinitely
infinitely
dilute solution
dilute solution under
under standard
standard conditions.
conditions.

19 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.143)
Standard enthalpy change of
solution
e.g. NaCl(s) + water  Na+(aq)+Cl-(aq)
Hsoln= +3.9 kJ mol-1

ø
Enthalpy level
diagram for the
dissolution of NaCl
20 New Way Chemistry for Hong Kong A-Level Book 1
6.3 Standard enthalpy changes (SB p.143)
Standard enthalpy change of
solution
e.g. LiCl(s) + water  Li+(aq) + Cl-(aq)
Hsoln= -37.2 kJ mol-1

ø Enthalpy level
diagram for the
dissolution of LiCl in
21 New Way Chemistry for Hong Kong A-Level Book 1 water
6.3 Standard enthalpy changes (SB p.143)
Standard enthalpy change of
solution
Salt Hsoln(kJ mol-1)

ø
NaOH -44.7
NaCl +3.9
KOH -57.8
KBr +20.0

22 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.144)

Standard enthalpy change of

formation

Standard enthalpy
Standard enthalpy change
change of of formation
formation (H
(Hf f ))

ø
is the
is the enthalpy
enthalpy change
change of of the
the reaction
reaction when
when
one mole
one mole of of the
the compound
compound in in its
its standard
standard
state is
state is formed
formed from
from its
its constituent
constituent elements
elements
under standard
under standard conditions.
conditions.

23 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.144)
Standard enthalpy change of
formation
e.g. 2Na(s) + Cl2(g)  2NaCl(s)
H = -822 kJ mol-1

ø
Na(s) + ½Cl2(g)  NaCl(s)

ø
Hf = -411 kJ mol-1

Standard enthalpy change of

formation of NaCl is -411 kJ mol-1.
24 New Way Chemistry for Hong Kong A-Level Book 1
6.3 Standard enthalpy changes (SB p.144)
Standard enthalpy change of
formation
What is Hf [N2(g)] ?
ø
N2(g)  N2(g)

Hf [N2(g)] = 0
ø

The enthalpy
The enthalpy change
change of
of formation
formation of
of an
an
element is
element is always
always zero.
zero.

25 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.146)
Standard enthalpy change of
combustion
e.g. C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
H1 = -2220 kJ
2C3H8(g) + 10O2(g) 6CO2(g) + 8H2O(l)
H2 = ?
H2 = -4440 kJ
 It is more convenient to report enthalpy
changes per mole of the main reactant
reacted/product formed.
26 New Way Chemistry for Hong Kong A-Level Book 1
6.3 Standard enthalpy changes (SB p.146)
Standard enthalpy change of
combustion
Standard enthalpy
Standard enthalpy change
change of
of combustion
combustion (H
(Hcc ))

ø
of aa substance
of substance is is the
the enthalpy
enthalpy change
change when
when one
one
mole of
mole of the
the substance
substance burns
burns completely
completely under
under
standard conditions.
standard conditions.

e.g. C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)

1 mole
Hc = -2220 kJ mol-1
ø

27 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.147)
Standard enthalpy change of
combustion
Substance Hc (kJ mol-1)

ø
H2(g) -285.8
C (diamond) -395.4
C (graphite) -393.5
CO(g) -283.0
CH4(g) -890.4

Check Point 6-3

28 New Way Chemistry for Hong Kong A-Level Book 1
 6.
4 Experimental
Determination
of Enthalpy
Changes by
29
Calorimetry
New Way Chemistry for Hong Kong A-Level Book 1
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.148)

Experimental determination of enthalpy

changes by calorimetry

Calorimeter = a container used for measuring

the temperature change of solution

30 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.149)
Determination of enthalpy change of
neutralization

31 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.149)

Heat evolved = (m1c1 + m2c2) ΔT

where m1 is the mass of the solution,
m2 is the mass of calorimeter,
c1 is the specific heat capacity of the
solution,
c2 is the specific heat capacity of
calorimeter,
ΔT is the temperature change of
the reaction
Example 6-4A
32 New Way Chemistry for Hong Kong A-Level Book 1
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.150)
Determination of enthalpy change
of combustion

The Philip Harris

calorimeter used for
determining the
enthalpy change of
combustion of a liquid
fuel
33 New Way Chemistry for Hong Kong A-Level Book 1
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.151)
Determination of enthalpy change
of combustion

A simple apparatus used to determine the

enthalpy change of combustion of ethanol
34 New Way Chemistry for Hong Kong A-Level Book 1
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.151)

Heat evolved = (m1c1 + m2c2) ΔT

Where m1 is the mass of water in the calorimeter,
m2 is the mass of the calorimeter,
c1 is the specific heat capacity of the water,
c2 is the specific heat capacity of
calorimeter,
ΔT is the temperature change of the
reaction
Example 6-4B
35 New Way Chemistry for Hong Kong A-Level Book 1
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.152)
Determination of enthalpy change
of solution

• By measuring the temperature change when

a known mass of solute is added to a known
volume of solvent in a calorimeter
• Heat change = (m1c1 + m2c2) T

Example 6-4C

36 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)
Determination of enthalpy change
of formation

• The enthalpy change of formation of a

substance can be quite high
• Found out by applying Hess’s law of
constant heat summation

Check Point 6-4

37 New Way Chemistry for Hong Kong A-Level Book 1

 6.
5 Hess’s Law

38 New Way Chemistry for Hong Kong A-Level Book 1

6.5 Hess’s law (SB p.153)
Hess’s
Law
Route 1
A+B C+D
H1

H2 H3
E
H11== H
H H22 ++ H
H33
Route 2

Hess’s law
Hess’s law ofof constant
constant heat
heat summation
summation states
states
that the
that the total
total enthalpy
enthalpy change
change accompanying
accompanying aa
chemical reaction
chemical reaction is
is independent
independent ofof the
the route
route by
by
which the
which the chemical
chemical reaction
reaction takes
takes place.
place.
39 New Way Chemistry for Hong Kong A-Level Book 1
6.5 Hess’s law (SB p.154)
Enthalpy level
diagram
• Relate substances together in terms of
enthalpy changes of reactions

Enthalpy level
diagram for the
oxidation of
C(graphite) to
40 New Way Chemistry for Hong Kong A-Level Book 1
CO2(g)
6.5 Hess’s law (SB p.155)

Enthalpy cycle (Born-Haber cycle)

• Relate the various equations involved in a
reaction

Enthalpy cycle for the

oxidation of
C(graphite) to CO2(g)
41 New Way Chemistry for Hong Kong A-Level Book 1
6.5 Hess’s law (SB p.155)

Importance of Hess’s law

The enthalpy change of some chemical reactions
cannot be determined directly because:

• the reactions cannot be performed in the

laboratory
• the reaction rates are too slow
• the reactions may involve the formation of side
products
But the enthalpy change of such reactions
can be determined indirectly by applying
Hess’s Law.
42 New Way Chemistry for Hong Kong A-Level Book 1
6.5 Hess’s law (SB p.153)
Enthalpy change of formation of CO(g)
Given: Hf [CO2(g)] = -393.5 kJ mol-1;

ø
Hc [CO(g)] = -283.0 kJ mol-1

ø
Hf [CO(g)]

ø
C(graphite) + ½O2(g) CO(g)

+ +
½O2(g) H1 H2 ½O2(g)
CO2(g)
Hf f[CO(g)]
H H22 == H
[CO(g)] ++ H H11
ø

Hf [CO(g)] = H1 - H2

ø

= -393.5 - (-283.0 )
= -110.5 kJ mol-1
43 New Way Chemistry for Hong Kong A-Level Book 1
 Enthalpy change of formation of
6.5 Hess’s law (SB p.153)

CaCO3(s)
Hf [CaCO3(s)]

ø
Ca(s) + C(graphite) + 3 O2 CaCO3(s)
2

H1 H2
CaO(s) +
CO2(g)
Høf [CaCO3(s)] = H1 + H2
= -1028.5 kJ mol-1 + (-178.0) kJ mol-1
= -1206.5 kJ mol-1

44 New Way Chemistry for Hong Kong A-Level Book 1

 Enthalpy change of hydration of
6.5 Hess’s law (SB p.153)

MgSO4(s)
ΔH

ø
MgSO4(s) + 7H2O(l) MgSO4·7H2O(s)
aq aq
ΔH1 ΔH2

Mg2+(aq) + SO42-(aq) + 7H2O(l)

ΔH = enthalpy of hydration of MgSO4(s)

ø

ΔH1 = molar enthalpy change of solution of anhydrous

magnesium sulphate(VI)
ΔH2 = molar enthalpy change of solution of magnesium
sulphate(VI)-7-water
Check Point 6-5
ΔH = ΔH - ΔH
ø

45 1 Kong A-Level
New Way Chemistry for Hong 2 Book 1
 6.
6Calculations
involving
Standard Enthalpy
Changes of
46 Reactions
New Way Chemistry for Hong Kong A-Level Book 1
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.159)
Calculation of standard enthalpy
change of reaction from standard
enthalpy changes of formation

Hreaction
H =  H
reaction = Hf f [products]
[products] --  H
Hf f [reactants]
[reactants]
ø

47 New Way Chemistry for Hong Kong A-Level Book 1 ø

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.159)

Example 6-6A Example 6-6B

Example 6-6C Example 6-6D

48 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.162)
Calculation of standard enthalpy
change of formation from standard
enthalpy changes of combustion

Hf f ==  H
H Hcc [products]
[products] --  H
Hcc [reactants]
[reactants] ø
ø
ø

49 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.162)

Example 6-6E Example 6-6F

Check Point 6-6

50 New Way Chemistry for Hong Kong A-Level Book 1

6.7 Entropy change (SB
p.164)

6.
7 Entropy
Change

51 New Way Chemistry for Hong Kong A-Level Book 1

6.7 Entropy change (SB
p.164)
Entropy
A process is said to be spontaneous
• If no external forces are required to keep the
process going
• The process may be physical change or a
chemical change
• Example of spontaneous physical change:
cooling of hot water
• Example of spontaneous chemcial change:
burning of wood once the fire is started
52 New Way Chemistry for Hong Kong A-Level Book 1
6.7 Entropy change (SB
p.164)

Entropy
• Exothermicity is the reason for the spontaneity
of a process
• Some spontaneous changes are endothermic
• Examples: Melting of ice, dissolution of
ammonium nitrate in water

53 New Way Chemistry for Hong Kong A-Level Book 1

6.7 Entropy change (SB
p.164)

Melting of ice

Dissolution of
ammonium nitrate in
54 New Way Chemistry for Hong Kong A-Level Book 1
water
6.7 Entropy change (SB
p.165)
Entropy
• Entropy is a measure of the randomness or
the degree of disorder of a system

Solid Liquid Gas

Entropy increases
55 New Way Chemistry for Hong Kong A-Level Book 1
6.7 Entropy change (SB
p.166)
Entropy
change
• Entropy change means the change in the
degree of disorder of a system
S = Sfinal - Sinitial

56 New Way Chemistry for Hong Kong A-Level Book 1

6.7 Entropy change (SB
Positive
p.166)

entropy
• Increase in entropy
• Final state has a larger entropy that the initial
state
• Example:
Ice (less entropy)  Water (more entropy)
S = Swater – Sice = +ve

57 New Way Chemistry for Hong Kong A-Level Book 1

6.7 Entropy change (SB
Negative
p.166)

entropy
• Decrease in entropy
• Initial state has a larger entropy that the final
state
• Example:
Water (more entropy)  Ice (less entropy)
S = Sice – Swater = -ve
Check Point 6-7
58 New Way Chemistry for Hong Kong A-Level Book 1
 6.
8 Free
Energy
Change

59 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.168)
Free energy
change
• Entropy is temperature dependent
• At a higher temp, the entropy of the system is
higher
• At a lower temp, the entropy of the system is
lower

60 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.168)
Free
energy
• Another driving force for a process
• Called free energy (G)
G = H – TS
where H is the enthalpy
T is Kelvin temperature
S is the entropy

61 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.168)

Free energy change

G = H – TS
• At a given temp, there are two driving forces
for a process to occur
• Overall enthalpy of the system tends to be low
• Overall entropy of the system tends to be high

62 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.168)

Significance of the equation

• Process favoured by:

H = -ve; S = +ve
• Process not favoured by:
H = +ve; S = -ve

63 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.168)

Significance of the equation

• A process is spontaneous or favourable

when G is negative
• A process is not spontaneous or favourable
as indicated when G is positive, but is
spontaneous in the opposite direction

64 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.169)

How H and S affect the

spontaneity of a process
H S G = H - TS Result
-ve +ve -ve Process is spontansous
at all temepratures
+ve -ve +ve Process is not
spontaneous at any
temperature (reverse
process is spontaneous
at all temperatures)
65 New Way Chemistry for Hong Kong A-Level Book 1
6.8 Free energy change (SB p.170)
Effects of relative magnitudes of H and
S on the spontaneity of a process
H S Condition G = H - Result
TS
+ve +ve At high temp, G = -ve Process is
TS > H spontaneous at
high temp
+ve +ve At low temp, G = +ve Process is not
H > TS spontaneous
-ve -ve At high temp, G = +ve Process is not
TS > H spontaneous
-ve -ve At low temp, G = -ve Process is
H > TS spontaneous at
66 New Way Chemistry for Hong Kong A-Level Book 1 low temp
6.8 Free energy change (SB p.170)

Check Point 6-8

67 New Way Chemistry for Hong Kong A-Level Book 1

 The END

68 New Way Chemistry for Hong Kong A-Level Book 1

6.1 What is energetics? (SB p.140)
Back

State whether the following processes are

exothermic or endothermic.
(a) Melting of ice.(a) Endothermic
(b) Endothermic
(b) Dissolution of table salt.
(c) Exothermic
(c) Condensation of steam.
Answer

69 New Way Chemistry for Hong Kong A-Level Book 1

6.2 Enthalpy changes related to breaking and forming of bonds (SB p.141)

(a)State the difference between exothermic and

endothermic reactions with respect to
(i) the sign of H;
(ii) Answer
the heat change with the surroundings;
(iii) the total enthalpy of reactants and
products.
(a) (i) Exothermic reactions: H = -ve; endothermic reactions: H =
+ve
(ii) Heat is given out to the surroundings in exothermic
reactions whereas heat is taken in from the surroundings in
endothermic reactions.
(iii) In exothermic reactions, the total enthalpy of products is
less than that of the reactants. In endothermic reactions, the
70
total enthalpy is greater than that of the reactants.
New Way Chemistry for Hong Kong A-Level Book 1
6.2 Enthalpy changes related to breaking and forming of bonds (SB p.141)

(b)Draw an enthalpy level diagram for a reaction

which is
(i) endothermic, having a large activation
energy.
Answer
(ii) exothermic, having a small activation
energy.

71 New Way Chemistry for Hong Kong A-Level Book 1

6.2 Enthalpy changes related to breaking and forming of bonds (SB p.141)

(b) (i)

72 New Way Chemistry for Hong Kong A-Level Book 1

6.2 Enthalpy changes related to breaking and forming of bonds (SB p.141)

Back

(ii)

73 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.147)

(a)Why must the condition “burnt completely in

oxygen” be emphasized in the definition of
standard enthalpy change of combustion?
Answer
(a) If the substance is not completely burnt
in excess oxygen, other products such as
C(s) and CO(g) may be formed. The
enthalpy change of combustion
measured will not be accurate.

74 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.147)

(b) The enthalpy change of the following

reaction under standard conditions is –566.0
kJ.
2CO(g) + O2(g)  2CO2(g)
What is the standard enthalpy changeAnswer of
combustion
(b) of carbon
Standard enthalpy monoxide?
change of combustion of CO
1
=  (-566.0) kJ
2
= -283.0 kJ

75 New Way Chemistry for Hong Kong A-Level Book 1

6.3 Standard enthalpy changes (SB p.147)

(c)What terms may be given for the enthalpy

change of the following reaction?
1
N (g) + O2(g)  NO2(g)
2 2
(c) Enthalpy change of combustion of nitrogen or
enthalpy change of formation of nitrogen Answer
dioxide.

Back

76 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.149)

Determine the enthalpy change of neutralization

of 25 cm3 of 1.25 M hydrochloric acid and 25 cm3
of 1.25 M sodium hydroxide solution using the
following data:
Mass of calorimeter = 100 g
Initial temperature of acid = 15.5 oC (288.5
K)
Initial temperature of alkali = 15.5 oC
(288.5 K)
Final temperature of the reaction mixture
= 21.6 oC (294.6 K)
Answer
The specific heat capacities of water and
77 New Way Chemistry for Hong Kong A-Level Book 1
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.149)

Assume that the density of the reaction mixture is the same as that of
water, i.e. 1 g cm-3.
Mass of the reaction mixture = (25 + 25) cm3  1 g cm-3 = 50 g = 0.05 kg
Heat given out = (m1c1 + m2c2) T
= (0.05 kg  4200 J kg-1 K-1 + 0.1 kg  800 J kg-1 K-1) 
(294.6 – 288.5) K
= 1769 J
H+(aq) + OH-(aq)  H2O(l)
Number of moles of HCl = 1.25 mol dm-3  25  10-3 dm3 = 0.03125 mol
Number of moles of NaOH = 1.25 mol dm-3  25  10-3 dm3 = 0.03125 mol
Number of moles of H2O formed = 0.03125 mol

78 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.149)

Heat given out per mole of H2O formed

1769 J
=
0.03125 mol
= 56608 J mol-1
The enthalpy change of neutralization is –56.6 kJ mol -1.

Back

79 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.151)

Determine the enthalpy change of combustion of

ethanol using the following data:
Mass of spirit lamp before experiment =
45.24 g
Mass of spirit lamp after experiment =
44.46 g
Mass of water in copper calorimeter = 50 g
Mass of copper calorimeter without water =
380 g
Initial temperature of water = 18.5 oC
(291.5 K)

80
Final temperature of water =
New Way Chemistry for Hong Kong A-Level Book 1
39.4 Answer
o
C (312.4
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.151)

Heat evolved by the combustion of ethanol

= Heat absorbed by the copper calorimeter
= (m1c1 + m2c2) T
= (0.05 kg  4200 J kg-1 K-1 + 0.38 kg  2100 J kg-1 K-1) 
(312.4 – 291.5)K
= 21067 J
C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)
Mass of ethanol burnt = (45.24 – 44.46) g = 0.78 g
0.78 g
Number of moles of ethanol burnt = 46.0 g mol  1 = 0.017 mol

81 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.151)

Back
Heat given out per mole of ethanol
21067 J
=
0.017 mol
= 1239235 J mol-1
= 1239 kJ mol-1
The enthalpy change of combustion of ethanol is –1239 kJ mol -1.
There was heat loss by the system to the surroundings, and incomplete
combustion of ethanol might occur. Also, the experiment was not carried
out under standard conditions. Therefore, the experimentally determined
value (-1239 kJ mol-1) is less than the theoretical value of the standard
enthalpy change of combustion of ethanol (-1371 kJ mol -1).

82 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.152)

0.02 mol of anhydrous ammonium chloride was

added to
45 g of water in a polystyrene cup to determine
the enthalpy change of solution of anhydrous
ammonium chloride. It is found that there was a
temperature drop from 24.5 oC to
23.0 oC in the solution.
Given that the specific heat capacity of water is
4200 J kg-1 K-1 and
NH4Cl(s) + aq  NH4Cl(aq)
Calculate the enthalpy change of solution of
anhydrous ammonium chloride.
Answer
(Neglect
83 the
Newspecific
Way Chemistry forheat
Hong Kongcapacity
A-Level Book 1 of the
6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.152)

Heat absorbed = m1c1T ( c2  0)

= 0.045 kg  4200 J kg-1 K-1  (297.5 – 296) K
= 283.5 J (0.284 kJ)
0.284 g
Heat absorbed per mole of ammonium chloride = 0.02 mol
= 14.2 kJ mol-1
The enthalpy change of solution of anhydrous ammonium chloride is
+14.2 kJ mol-1.
Back

84 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)

(a) A student tried to determine the enthalpy

change of neutralization by putting 25.0 cm3
of 1.0 M HNO3 in a polystyrene cup and adding
25.0 cm3 of 1.0 M NH3 into it. The temperature
rise recorded was 3.11 oC. Given that the mass
of the polystyrene cup is 250 g, the specific
heat capacities of water and the polystyrene
cup are
4200 J kg-1 K-1 and 800 J kg-1 K-1 respectively.
Determine the enthalpy change of Answer
neutralization of nitric acid and aqueous
ammonia. (Density of water = 1 g cm-3)

85 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)

(a) Heat evolved = m1c1T + m2c2 T

= 0.050 kg  4200 J kg-1 K-1  3.11 K + 0.25 kg 
800 J kg-1 K-1  3.11 K
= (653.1 + 622) J
= 1275.1 J
No. of moles of HNO3 used = 1.0 M  25  10-3 m3
= 0.025 mol

86 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)

(a) No. of moles of NH3 used = 1.0 M  25  10-3 dm3

= 0.025 mol
No. of moles of H2O formed = 0.025 mol
Heat evolved per mole of H2O formed
1275.1 J
= 0.025 mol
= 51.004 kJ mol-1
The enthalpy change of neutralization of nitric acid and aqueous
ammonia is –51.004 kJ mol-1.

87 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)

(b)When 0.05 mol of silver nitrate was added to

50 g of water in a polystyrene cup, a
temperature drop of 5.2 oC was recorded.
Assuming that there was no heat absorption
by the polystyrene cup, calculate the enthalpy
change of solution of silver nitrate.
(Specific heat capacity of water = 4200 J kg-1
K )
-1 Answer

88 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)

(b) Energy absorbed = mcT

= 0.05 kg  4200 J kg-1 K-1  5.2 K
= 1092 J
No. of moles of AgNO3 used = 0.05 mol
1092 J
Energy absorbed per mole of AgNO3 used = 0.05 mol
= 21.84 kJ mol-1
The enthalpy change of solution of silver nitrate is +21.84 kJ mol -1.

89 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)

(c) A student used a calorimeter as shown in Fig.

6-15 to determine the enthalpy change of
combustion of methanol. In the experiment,
1.60 g of methanol was used and 50 g of water
was heated up, raising the temperature by 33.2
o
C. Given that the specific heat capacities of
water and copper calorimeter are 4200 J kg-1 K-1
and
2100 J kg-1 K-1 respectively and the mass of the
Answer
calorimeter is 400 g, calculate the enthalpy
change of combustion of methanol.

90 New Way Chemistry for Hong Kong A-Level Book 1

6.4 Experimental determination of enthalpy changes by calorimetry (SB
p.153)

Back

(c) Heat evolved = m1c1T + m2c2 T

= 0.05 kg  4200 J kg-1 K-1  33.2 K + 0.4 kg 
2100 J kg-1 K-1  33.2 K
= (6972 + 27888) J
= 34860 J
1.60 g
No. of moles of methanol used = 32.0 g mol -1
= 0.05 mol
34860 J
Heat evolved per mole of methanol used = 0.05 mol
= 697.2 kJ mol-1
The enthalpy change of combustion of methanol is –697.2 kJ mol -1.

91 New Way Chemistry for Hong Kong A-Level Book 1

6.5 Hess’s law (SB p.158)

(a)Given the following thermochemical equation:

2H2(g) + O2(g)  2H2O(l)
(i) Is the reaction endothermic or
exothermic?
(ii) What is the enthalpy change for the
following reactions?
(1) 2H12O(l)  2H2(g) + O2(g)
2
(2) H2(g) + O2(g)  H2O(l)
(iii) If the enthalpy change for the reaction
H2O(l)  H2O(g) is +41.1 kJ mol-1, calculate Answer
92 the H forNew2H (g) +for HongOKong
Way2Chemistry 2(g) 
A-Level Book2H
1 2O(g).
6.5 Hess’s law (SB p.158)

(a) (i) Exothermic

(ii) (1) +571.6 kJ mol-1
(2) –285.8 kJ mol-1
(iii)

H = [-571.6 + 2  (+41.1)] kJ mol-1 = -489.4 kJ mol-1

93 New Way Chemistry for Hong Kong A-Level Book 1

6.5 Hess’s law (SB p.158)

(b)Given the following information about the

enthalpy change of combustion of allotropes
of øcarbon:
Hcø [C(graphite)] = -393.5 kJ mol-1
Hc [C(diamond)] = -395.4 kJ mol-1
(i) Which allotrope of carbon is more stable?
(ii) What is the enthalpy change for the
following process? Answer
C(graphite)  C(diamond)

94 New Way Chemistry for Hong Kong A-Level Book 1

6.5 Hess’s law (SB p.158)

(b) (i) Graphite

(ii)

H = [-393.5 – (-395.4)] kJ mol-1 = +1.9 kJ mol-1

95 New Way Chemistry for Hong Kong A-Level Book 1

6.5 Hess’s law (SB p.158)

(c)The formation of ethyne (C2H2(g) can be

represented by the following equation:
2C(graphite) + H2(g)  C2H2(g)
(i) Draw an enthalpy level diagram relating
the above equation to carbon dioxide
and water.
(ii) Calculate the standard enthalpy change of
formation ofø ethyne.

(Given:
ø Hc [C(graphite)] = -393.5 kJ mol-
1
; ø
Answer
Hc [H2(g)] = -285.8 kJ mol -1
;
96 New Way Chemistry for Hong Kong A-Level Book 1
-1
6.5 Hess’s law (SB p.158)

Back

(c) (i)

Hf [C2H2(g)] = Hc [C(graphite)]  2 + Hc [H2(g)] – Hc

ø
(ii)
ø
ø

ø
[C2H2(g)]
= [(-393.5)  2 + (-285.8) – (-1299)] kJ mol-1
97 = +226.2
New Way kJHong
Chemistry for molKong A-Level Book 1
-1
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.159)

Given the following information, find the

standard enthalpy change of the reaction:
C2H4(g) + H2(g)  C2H6(g)
Hf [C2H4(g)] = +52.3 kJ mol-1
ø
ø

Hf [C2H6(g)] = -84.6 kJ mol-1

Answer

98 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.159)
Back

ø ø ø
Note: H1 = [Hf (reactants)] = Hf [C2H4(g)] + Hf [H2(g)]
ø ø
H2 = [Hf (products)] = Hf [C2H6(g)]
Applying Hess’s law,
ø

ø
H1 + H = H2
H =ø H2 - H1 ø ø

= Hf [C2H6(g)] – (Hf [C2H4(g)] + Hf [H2(g)])

= [-84.6 – (+52.3 + 0)] kJ mol-1 =-136.9 kJ mol-1
99 New Way Chemistry for Hong Kong A-Level Book 1
-1
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.160)

Given the following information, find the

standard enthalpy change of the reaction:
6PbO(s) + O2(g)  2Pb3O4(s)
Hf [PbO(g)] = -220.0 kJ mol-1
ø
ø

Hf [Pb3O4(g)] = -737.5 kJ mol-1

Answer

100 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.160)
Back

ø ø ø
Note: H1 = [Hf (reactants)] = 6  Hf [PbO(s)] + Hf [O2(g)]
ø ø

H2 = [Hf (products)] = 2  Hf [Pb3O4(s)]

Applying Hess’s law,
ø

ø H1 + H = H2
H = Hø2 - H1 ø ø

= 2  Hf [Pb3O4(s)] – (6  Hf [PbO(s)] + Hf [O2(g)])

= [2  (-737.5) – 6  (-222.0) – 0] kJ mol-1 =-155.0 kJ mol-1
101 New Way Chemistry for Hong Kong A-Level Book 1
The standard enthalpy change of the reaction is –155.0 kJ mol -1.
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.160)

Given the following information, find the

standard enthalpy change of the reaction:
Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g)
Hf [Fe2O3(s)] = -822.0 kJ mol-1
ø
ø

Hf [CO(g)] = -110.5 kJ mol-1

ø

Hf [CO2(g)] = -393.5 kJ mol-1 Answer

102 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.160)
Back

ø ø ø
Note: H1 = [Hf (reactants)] = Hf [Fe2O3(s)] + 2  Hf [CO(g)]
ø ø ø
H2 = [Hf (products)] = 2  Hf [Fe(s)] + 3  Hf [CO2(g)]
Applying Hess’s law,
ø

ø
H1 + H = H2
H = Hø 2 - H1 ø ø
ø
= 2  Hf [Fe(s)] + 3  Hf [CO2(g)] - Hf [Fe2O3(s)] - 3 
Hf [CO(g)]
= [2  (0) + 3  (-393.5) –(-822.0) – 3  (-110.5)] kJ mol-1
103 =-27.0
New WaykJ mol-1 for Hong Kong A-Level Book 1
Chemistry
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.161)

Given the following information, find the

standard enthalpy change of the reaction:
4CH3 · NH · NH2(l) + 5N2O4(l)
 4CO2(g) + 12H2O(l) +
9N2(g)
ø

Hf [CH3 · NH · NH2(l)] = +53 kJ mol-1

ø

Hf [N2O4(l)] = -20 kJ mol-1

ø
ø

Hf [CO2(g)] = -393.5 kJ mol-1 Answer

Hf [H2O(l)] = -285.8 kJ mol-1
104 New Way Chemistry for Hong Kong A-Level Book 1
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.161)
Back

ø
Note:H1 = [Hf (reactants)] = 4  Hf [CH3·NH ·NH2(l)] + 5  Hf [N2O4(l)]
ø
H2 = [Hf (products)] = 4  Hf [CO2(g)] + 12  Hf [H2O(l)] + 9  Hf [N2(g)]
Applying Hess’s law,
ø

ø
H1 + H = H2
H = Hø2 - H1 ø ø
ø
= (4  Hf [CO2(g)] + 12  H
ø
f [H2O(l)] + 9  Hf [N2(g)] – (3 
Hf [CH3·NH ·NH2(l)] + 5 Hf [N2O4(l)]
= [4  (-393.5) + 12  (-285.8) + 9  (0) – 4  (+53) – 5  (-20)] kJ
105 mol
-1
New Way Chemistry for Hong Kong A-Level Book 1
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.162)

Given the following information, find the standard

enthalpy change of formation of methane gas.
C(graphite) + O2(g)  CO2(g)
Hc [C(graphite)] = -393.5 kJ mol-1

ø
1
H2(g) +2 O2(g)  H2O(l) Hc [H2(g)] = -

ø
285.8 kJ mol-1
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)

ø Answer
Hc [CH4(g)] = -20 kJ mol-1

106 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.162)

Direct measurement of ΔHf [CH4(g)] is impossible because carbon(graphite)

ø
and hydrogen do not combine directly, and methane does not decompose
directly to form carbon(graphite) and hydrogen. Since methane contain
carbon and hydrogen only, they can be related to carbon dioxide and water
by the combustion of methane and its constituent elements as shown in the
diagram below.

107 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.163)
Back

Note: H1 = Hc [C(graphite)]

ø
H2 = 2  Hc [H2(g)]
ø

H3 = Hc [CH4(g)]

Applying Hess’s law,
ø

Hf [CH4(g)] + H3 = H1 + H2

ø

Hf [CH4(g)] = H1 + H2 - H3

ø
ø

ø
= Hc [C(graphite)] + 2  Hc [H2(g)] - Hc [CH4(g)]
= [-393.5 + 2  (-285.8) –(-890.4)] kJ mol-1
= -74.7 kJ mol-1
The standard enthalpy change of formation of methane gas is –74.7 kJ mol -1.

108 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.163)

Given the following information, find the standard

enthalpy change of formation of methanol.
C(graphite) + O2(g)  CO2(g)
Hc [C(graphite)] = -393.5 kJ mol-1

ø
1
H2(g) +2 O2(g)  H2O(l) Hc [H2(g)] = -

ø
285.8 kJ mol-1
C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l)
ø

Answer
Hc [C2H5OH(l)] = -1371 kJ mol-1

109 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.163)

110 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.163)
Back

Note: H1 = 2  Hc [C(graphite)]

ø
H2 = 3  Hc [H2(g)]
ø

H3 = Hc [C2H5OH(l)]

Applying Hess’s law,
ø

Hf [C2H5OH(l)] + H3 = H1 + H2

ø

Hf [C2H5OH(l)] = H1 + H2 - H3

ø
ø

= 2  Hc [C(graphite)] + 3  Hc [H2(g)] - Hc [C2H5OH(l)]

= [2  (-393.5) + 3  (-285.8) –(-1371)] kJ mol-1
= -273.4 kJ mol-1
The standard enthalpy change of formation of ethanol is –273.4 kJ mol -1.

111 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.164)

(a) Find the standard enthalpy change of

formation of butane gas (C4H10(g)).
ø
Given: Hc [C(graphite)] = -393.5 kJ mol-1
ø
Hc [H2(g)] = -285.8 kJ mol-1
ø
Hc [C4H10(g)] = -2877 kJ mol-1
Answer

112 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.164)
ø

Hf [C4H10(g)]
ø
ø

= Hc [C(graphite)]  4 + Hc [H2(g)]  5 - Hc [C4H10(g)]

= [(-393.5)  4 + (-285.8)  5 – (-2877)] kJ mol-1
113 New Way Chemistry for Hong Kong A-Level Book 1
= -126 kJ mol -1
6.6 Calculations involving standard enthalpy changes of reactions (SB
p.164)

(b) Find the standard enthalpy change of the

reaction:
Br2(l) + Cø2H4(g)  C2H4Br2(l)
Given: H
ø f [C2H4(g)] = +52.3 kJ mol-1

Answer
Hf [C2H4Br2(l)] = -80.7 kJ mol -1

114 New Way Chemistry for Hong Kong A-Level Book 1

6.6 Calculations involving standard enthalpy changes of reactions (SB
p.164)
Back

H
ø

= [Hf (products)] - [Hf (reactants)]

ø

ø
= [-80.7 – (+52.3) – 0)] kJ mol-1
= -133 kJ mol-1

115 New Way Chemistry for Hong Kong A-Level Book 1

6.7 Entropy change (SB
p.167) Back

Predict whether the following changes or

reactions involve an increase or a decrease in
entropy. (a) Increase
• Dissolving salt in water to form salt
(b) solution
Decrease
• Condensation of steam on a cold mirror
(c) Increase
• Complete combustion of carbon (d) Decrease
• Complete combustion of carbon monoxide
• Oxidation
(e) Decrease of sulphur dioxide to sulphur trioxide
Answer

116 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.170)

Back

In the process of changing of ice to water, at what

temperature do you think G equals 0?

G equals 0 means that neither the forward nor

Answer
the reverse process is spontaneous. The
system is therefore in equilibrium. Melting point
of ice is 0 oC (273 K) at which the process of
changing ice to water and the process of water
turning to ice are at equilibrium. At 0 oC, G of
the processes equals 0.

117 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.170)

(a)At what temperatures is the following process

spontaneous at 1 atmosphere?
Water  Steam (a) 100 oC

(b)What are the two driving forces that determine

(b) Enthalpy and entropy
the spontaneity of a process?
Answer

118 New Way Chemistry for Hong Kong A-Level Book 1

6.8 Free energy change (SB p.170)
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(c)State whether each of the following cases is

spontaneous at all temperatures, not
spontaneous at any temperature, spontaneous
at high temperatures or spontaneous at low
temperatures.
(i) positive S and positive H
(ii) positive S and negative H
(iii) negative S and positive H
(iv)
(i) negative and
Shigh
Spontaneous at negative H
temperatures
(ii) Spontaneous at all temperatures
(iii) Not spontaneous at any temperature
Answer
(iv) Spontaneous at low temperatures
119 New Way Chemistry for Hong Kong A-Level Book 1