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9.

0 THERMOCHEMISTRY
( 4 HOURS)
9.1
9.2
9.3
9.4

Concept of enthalpy
Calorimetry
Hesss law
Born- Haber cycle

AHH

9.1 Concept of enthalpy

Learning outcomes
a) Explain endothermic and exothermic reactions using
the energy profile diagrams.
b) State standard conditions of reaction and define the
following term s;
i. Enthalpy
ii. Standard enthalpy
c) Define enthalpy of formation, combustion,
atomisation, neutralisation, hydration, and solution
(dissolution).
d) Write the thermochemical equation for each
enthalpy.
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What is
thermochemistry

Thermochemistry
A study of heat change in chemical reactions.
Almost all chemical reactions absorb or
released energy (in the form of heat)
Two types of chemical reactions:

Exothermic
Endothermic

9.1.0

Enthalpy, H

The Concept of Enthalpy


(refers to the total value of energy of a system)

Is a measure of the heat content of a substance at


constant pressure.
Cannot be determined experimentally.

Enthalpy change, H

The heat exchange with surroundings when reaction occurs


at constant pressure.
Can be determined experimentally

Hreaction = H product H reactant

Example :
A+B

C+D

H = (H C + H D ) - (H A + H B )
PRODUCT

REACTANT

Standard Enthalpy, H

An enthalpy change under standard conditions,


(25C and 1 atm)
The symbol is H298 or simply H.
All substances involved in the reaction are in
their normal physical state, [ Na (s), H2O(l) and
CO2(g) ].
Elements in their normal states (elements already exist)
have been attributed zero enthalpy.
Example: H [H2 (g) ] = 0

Exothermic reactions

Enthalpy of products < Enthalpy of reactants


H is negative.
Energy is released from the system to its
surroundings.

Consider the following reaction:


A (g) + B (g) C (g)
(reactants)
(product)

H = ve

reactants
enthalpy
H = -ve
products
reaction pathway

Energy profile diagram for exothermic reaction


10

Endothermic Reactions

Enthalpy of products > enthalpy of reactants


H is positive
Energy is absorbed by the system from its
surrounding

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Consider the following reaction


A (g) + B (g) C(g)
H = + ve
(reactants)
(product)

Energy profile of diagram endothermic reactions


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Thermochemical Equation

The thermochemical equation shows the enthalpy changes.


Example : H2O(s) H2O(l)

H = +6.01 kJ

1 mole of H2O(l) is formed from 1 mole of H2O(s) at 0C,


H = +6.01 kJ

However, when 1 mole of H2O(s) is formed from 1 mole of


H2O(l), the magnitude of H remains the same but its sign
changes.
H2O(l) H2O(s)
H = 6.01 kJ
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If both sides of a thermochemical equation are multiplied by a


factor n, then H must also be multiplied by the same factor

Example:
2H2O(l) 2H2O(s)

H = 12.02 kJ

The physical states of all reactants and products must be specified


because they help determine the actual enthalpy changes.

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Types of Enthalpies

There are many kind of enthalpies such as:


Enthalpy of formation

Enthalpy of combustion
Enthalpy of atomisation
Enthalpy neutralisation
Enthalpy hydration
Enthalpy solution

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Enthalpy of Formation, Hf

The heat change when 1 mole of a compound


is formed from its elements in their most
*stable state at stated condition.
H2 (g) + O2(g) H2O (g)

Hf = 241.8 kJ mol1

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The standard enthalpy of formation of any


element in its most stable state form is ZERO.
(because no heat changes is involved when an element is formed from itself)

O2 (g) O2 (g)

Hf (O2 ) = 0

Cl2 (g) Cl2 (g)

Hf (Cl2) = 0

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Standard Enthalpy of Formation,


H0f
The heat change when 1 mole of a compound
is formed from its elements in their most
stable state under standard conditions (250C
and 1 atm
H2 (g) + O2(g) H2O (l)

Hf = 285.8 kJ mol1

KMP-SK027-2008/2009

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Enthalpy of Combustion, Hc

The heat released when 1 mole of substance is


burned completely in excess oxygen
C(s) + O2(g) CO2(g)
Hc = 393 kJ mol1
The standard enthalpy of combustionThe heat released when 1 mole of substance is
burned completely in excess oxygen under standard
conditions
C3H8 (g) + 5O2(g) CO2(g) + 4H2O(l) Hc = 2220 kJmol1

(H value is always ve because combustion is an exothermic)

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Enthalpy of Atomisation, Ha

The heat absorbed (energy required) when 1 mole of gaseous


atoms is formed from its element
Ha is always positive because it involves only breaking of
bonds
Na(s) Na(g)
Ha = +109 kJ mol-1
Cl2(g)

Cl(g)

Ha = +123 kJ mol-1

The standard enthalpy of atomisationThe heat absorbed (energy required) when 1 mole of gaseous atoms is
formed from its element under standard conditions
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Enthalpy of Neutralization,
Hn

The heat released when 1 mole of water, H2O is formed from


the neutralization of acid and base
HCl(aq)+ NaOH(aq) NaCl(aq) +H2O(l) Hn = 57.3 kJ mol1
Standard enthalpy of neutralization
The heat released when 1 mole of water, H2O is formed from
the neutralization of acid and base under standard

conditions
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Enthalpy of Hydration, Hhyd

The heat change when 1 mole of gaseous ions is


hydrated in water.
Na+(g) Na+(aq) Hhyd = 406 kJ mol-1
Cl-(g) Cl-(aq)
Hhyd = 363 kJ mol-1

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Enthalpy of Solution, Hsoln

The heat change when 1 mole of a substance is


dissolves in excess water to form a very dilute
solution
KCl(s) K+(aq) + Cl(aq) Hsoln = +690 kJ mol-1

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Exercises
1. 2C(s) + H2(g) C2H2(g)
H= +226.6kJmol-1
(a)How much heat is absorbed when 1 gram
of ethyne gas is formed according to the
above equation?
(b)How much heat would be absorbed when 1
mole of carbon reacts according to the
above equation?
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2.

2H2 (g) + O2 (g) 2H2O(l)

H= -575 kJ

(a)How much heat is released when 1 mole


of hydrogen gas reacts according to the
thermochemical equation?
(b)How many gram of liquid water is formed
when 159.7 kJ of heat was released?

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9.2 Calorimetry

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Learning outcomes

a) Define
i) heat capacity, C
ii) specific heat capacity, c

b) Calculate heat change in a;


i) Constant-pressure calorimetry (simple
calorimeter)
ii) Constant-volume calorimetry (bomb
calorimeter)
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Calorimetry is the
experimental technique to
determine enthalpy of
reactions.
It will depend on
understanding of specific
heat and heat capacity.

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What are the specific heat and heat


capacity???

The specific heat (c)


of a substance is the
amount of heat
required to raise the
temperature of one
gram of the substance
by one degree Celcius.

The unit is J/g C

The heat capacity (C)


of a substance is the
amount of heat
required to raise the
temperature of a given
quantity of the
substance by one
degree Celcius.
The unit is J/C
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The set of apparatus used is


known as a calorimeter

A simple calorimeter

A bomb calorimeter

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A bomb calorimeter

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Basic Principle in Calorimeter


Heat released
by a reaction

Heat absorbed
by surroundings

Surroundings may refer to


the:
i. Calorimeter itself or;
ii. The water and calorimeter
qreaction= mcT or CT

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Heat released by
substance

Heat absorbed
by calorimeter

q = mcT
q = heat released by substance
m= mass of substance
c = specific heat capacity
T = temperature change

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The equation for calculating the


heat change (q) is given by :-

q = mcT
Where:
q @ H
m
T
c
C

q = CT

= enthalpy change (kJ mol-1)


= the mass of the sample (g)
= the temperature change (C )
( Tfinal T initial)
= the specific heat (J/g.C)
= the heat capacity (J/C)
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By using a bomb calorimeter, heat is absorbed by both


the water and the metal parts of the calorimeter.

Heat released by fuel = heat absorbed by water + heat


absorbed by calorimeter

q = mwcwT + mcccT
where

mc

= mass of calorimeter
mw = mass of water
cw
= specific heat of water
cc
= specific heat of calorimeter
T = temperature change
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Example 1:

A 466 g sample of water is heated from


8.50 C to 74.60 C. Calculate the amount
of heat absorbed by the water.

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Solution
By using the equation:
q = mcT
=(466 g)(4.184 J/g.C)(74.60C8.50C)
= 1.29 x 105 J
= 129 kJ
Therefore the amount of heat absorbed by
the water is 129 kJ.
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Example 2
1.
Calculate the amount of heat released in a
reaction in an aluminum calorimeter with a
mass of 3087.0 g and contains 1700.0 mL of
water. The initial temperature of the calorimeter
is 25.0C and it increased to 27.8C.
Given:
Specific heat capacity of aluminum = 0.553Jg-1 C-1
Specific heat capacity of water = 4.18 Jg-1 C-1
Water density = 1.0 g mL-1

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Solution
T = (27.8 -25.0 )C = 2.8C
Heat released

Heat absorbed by
water

Heat absorbed by
aluminium
calorimeter

q = mwcwT + mcccT
= (1700.0 g)(4.18 Jg-1 C-1)(2.8 C) +
(3087.0 g)(0.553 Jg-1 C-1)(2.8C)
= 24676.71 J
= 24.7 kJ

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Example 3

A sample of magnesium metal weighing 0.14 g


is combusted in a bomb calorimeter containing
3.0 x 102 g water at an initial temperature of
25.0C. The maximum temperature recorded
was 26.0C. If the heat capacity of the
calorimeter 1769 J/C and the specific heat
of water is 4.184 J/g.C
Calculate the enthalpy of combustion of magnesium.
Write the thermochemical equation for the
combustion of magnesium.
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Solution

Enthalpy of combustion
= mwcwT + mcccT
= 3.0 x 102 g x 4.184 Jg-1C-1 x 1.0C) + (1769 JC-1 x 1.0C)
= 3.0 x 103 J
Mol of Mg = 0.14 g
24.31 gmol-1
= 5.76 x 10-3 mol Mg
5.76 x 10-3 mol Mg released 3.0 x 103 J
1.0 mol Mg released :
3.0 x 103J
5.76 x 10-3 mol
= 5.2 x 105 J/mol
Thus, enthalpy of combustion is - 5.2 x 102 kJmol-1
Thermochemical equation is :
Mg(s) + O2(g)
MgO(s)

H = - 5.2 x 102 kJ
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9.3 Hesss
Law
42

Learning outcomes
1. Define Hess Law
2. Apply Hesss law to calculate enthalpy
changes using the algebraic method and the
energy cycle.

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Hesss Law

Hesss Law states that,


The overall enthalpy change for a
reaction is equal to the sum of the
enthalpy changes for the individual steps
in the reaction.
The enthalpy change depends only on the
nature of the reactants and products
and is independent of the route taken.
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How To Solve Problem Using


Hesss Law
The enthalpy changes , H can be calculated by :

Algebraic
Method
Energy Cycle
Method
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Example 1

Find the standard enthalpy of formation


of ethane C2H6(g). Given the following
data:
Hc C(graphite) = -393 kJmol-1
Hc H2(g)
= -286 kJmol-1
Hc C2H6(g)

= -1560 kJmol-1

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Using Algebraic Method

There are 3 steps to calculate an unknown H:


1.

Identify the target equation, the step whose H is


unknown, and note the number of moles of reactants
and products.

2.

Manipulate the equations for which H is known so


that the target numbers of moles of reactants and
products are on the correct sides. Remember to:
1.
2.

3.

Change the sign of H when you reverse an equation.


Multiply number of moles and H by the same factor.

Add the manipulated equations to obtain the target


equation. All substances except those in the target
equation must cancel. Add their H values to obtain
the unknown H.
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Example
Write the chemical equations for the given
enthalpy change.
a.

C (s) + O2 (g) CO2 (g)

H= -393kJ

b.

H2 (g) + O2 (g) H2O(l)

c.

C2H6 (g) + 7/2 O2 2CO2 (g) + 3H2O (l)


H = -1560 kJ

H= -286 kJ

48

Chemical equation for the formation of ethane from its element:


2C (s) + 3H2 (g) C2H6 (g)
=?
Since we want to obtain one equation containing C and H2 as reactants
and C2H6 as product, O2 , CO2 and H2O are need to be eliminated
from equations given.
Reverse the equation c (as well as the sign of H), then multiply a by
2 and b by 3 (so as the H). Next, total up all the enthalpies.
2CO2(g) + 3H2O(l) C2H6(g) + 7/2 O2(g)

H = +1560 kJ

2C(s)

H = 2(-393) kJ

2O2(g)

2CO2(g)

3H2(g) + 3/2 O2(g) 3H2O(l)


2C (s) + 3H2 (g) C2H6 (g)

H = 3(-286) kJ
= +1560-786-858
= -84 kJ

Standard enthalpy of formation of ethane is -84 kJ/ mol.


49

Using Energy Cycle Method

Write the chemical equation for required


enthalpy change.
Look at the data given, if values are given,
complete the cycle by writing the
combustion equation . If the values are
given , elements must make up the cycle.
Draw the cycle and add the values
(multiplying by a factor where necessary)
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Energy Cycle
H Of
2 C (s )

3 H 2 (g )
H

H O1

2 O 2 (g )

O
2

C 2 H 6 (g )
= 3 (-2 8 6 )

3 /2 O 2 ( g )

= 2 (-3 9 3 )

7 /2 O 2 ( g )
H O3 = - ( - 1 5 6 0 )

2 C O 2 (g ) + 3 H 2O (l )

Hf = 2( H1 ) + 3( H2 ) + H
3
2(-393) 3(-286) 1560
- 84 kJ
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Example 2
Let us consider the formation of tin(IV) chloride,

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Algebraic Method

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Energy Cycle Method

KMP-SK027-2008/2009

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9.4 Born- Haber cycle

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Learning outcomes
a. Define lattice energy and electron affinity.
b. Explain the following effects on the magnitude
of lattice energy.
i. ionic charges
ii. Ionic radii
c. Explain the dissolution process of ionic solids.
d. Construct Born-Haber cycle for simple ionic
solids using energy cycle diagram.
e. Calculate the enthalpy changes using BornHaber cycles.
56

Lattice Energy, Hlattice

is the energy required to completely separate one


mole of a solid (ionic compound) into gaseous
ions
NaCl(s)

Na+(g) + Cl-(g) Hlattice = +771 kJ mol-1


(lattice dissociation)
Lattice Energy also means the heat/energy released
when 1 mole of solid(ionic compound) formed from
gaseous ions.

Na+(g) + Cl-(g)

NaCl(s) Hlattice = -771 kJ mol-1


(lattice formation)
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The magnitude of lattice energy increases as


the ionic charges increase
the ionic radii decrease

There is a strong attraction between small ions and


highly charged ions so the H is more negative.

H for MgO is more negative than H for Na2O


because Mg2+ is smaller in size and has bigger
charge than Na+, therefore
Hlattice (MgO) > Hlattice (Na2O)
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Example: Ionic Radii

Increasing ionic radii


Increasing Lattice Energy
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Example: Ionic Charges

Increasing Ionic Charges


Increasing Lattice Energy
60

Lattice energy is a measure of the


stability of ionic compounds.
The higher the lattice energy:
the more stabile the compounds.
the more strongly the ions are held
together in the crystal lattice.
The melting point increase.

61

Example: Sodium halide

62

Exercises
1.

The ionic radii of sodium, calcium,


fluoride and oxide are of comparable
size. Their radii are shown below:-

a) Considering NaF and CaO,


indicate which has the large lattice
63
KMP-SK027-2008/2009
energy???

b) Considering NaF
and CaO, which has
the lower melting
point???

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Answer: 1 (a)

65

Answer: 1 (b)

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2. What do you think the lattice


energy and the melting point of
CaF2 should be compared to
CaO???

67

Answer: 2

68

Ionisation Energy, IE
energy required to remove 1 mole of electron
from 1 mole of atom in gaseous state.
Mg (g) Mg+ (g) + e
IE1 = +740 kJmol1
(First ionization energy of Mg)
Mg+ (g) Mg2+ (g) + e

IE2 = +1400 kJmol1

(Second ionization energy of Mg)

Electron Affinity, EA
the heat change when 1 mole of gaseous atoms
gains 1 mole of electrons to form 1 mole of gaseous
ions.
O (g) + e O (g)
EA1 = 142 kJmol1
(First electron affinity of O)
O (g) + e O2( (g)
EA2 = +844 kJ mol-1
(Second electron affinity of O)

Hydration Process of Ionic Solid

Na+ and Cl- ions in the solid crystal are separated from
each other and converted to the gaseous state (Hlattice)

The electrostatic forces between gaseous ions and polar


water molecules cause the ions to be surrounded by water
molecules (Hhydr)

Hsoln = Hlattice + Hhdyr

72

Na+ and Cl- ion in


the gaseous state

ic
t
t
La

r
e
n
E
e

He
at
of
Hy
d ra
tio

gy

Heat of Solution
Na+ and Cl- ion in
the solid state

Hydrated Na+ and Cl- ion

73

Born-Haber Cycle
Born-Haber Cycle is an energy cycle for ionic
compound. It connects enthalpy of formation,
which can be determined experimentally.
It is often used to calculate the lattice energy
of an ionic compound which cannot be
determined experimentally.
The Born-Haber Cycle contains enthalpy of
sublimation, enthalpy of atomisation, IE, EA
and lattice energy.

74

Example 1: Enthalpy changes in


the formation of sodium chloride

Note: This is cycle method, not energy cycle method!


75

Solution

76

Example 2 :

i.
ii.
iii.
iv.
v.
vi.

Given;
Enthalpy of formation NaCl =
Enthalpy of sublimation of Na =
First ionization energy of Na =
Enthalpy of atomization of Cl =
Electron affinity of Cl
=
Lattice energy of NaCl
=

-411 kJmol-1
+108 kJmol-1
+500 kJmol-1
+122 kJmol-1
-364 kJmol-1
?

77

Example: A Born-Haber cycle for NaCl


energy
Na+(g) + e + Cl(g)

NOTE!
In this Born-Haber cycle
*energy diagram:
positive (+ve)values are
denoted as going
upwards(),
negative(-ve) values as
Lattice energy going downwards().

Ionisation
Electron Affinity of
Energy of
Cl
Na
Na+
+ Cl- (g)
Na(g) + Cl(g)
(g)

HaCl
+ve

Na(g) + Cl2(g)

HaNa

From Hesss Law:

Na(s) +
E=0 Cl2(g)
-ve

Hf

Hf NaCl
NaCl(s)

NaCl

= HaNa + HaCl +IENa +


EACl + Lattice Energy

Solution :
H0f HS IE Ha(Cl) EA Hlattice
Hlattice H0f HS IE Ha(Cl) EA
Hlattice 411
kJ 108kJ 500kJ 122kJ 364kJ
Hlattice 777kJ

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Exercise 1: Calculate the value of Ha

80

Answer: Exercise 1

KMP-SK027-2008/2009

81

Exercise 2

Construct the Born-Haber cycle for KF


and using appropriate data, calculate the
electron affinity of fluorine.

82

Answer: Exercise 2

83

84

Exercise 3:

i.
ii.
iii.
iv.
v.
vi.

Construct a Born-Haber cycle to explain why


ionic compound NaCl2 cannot form under
standard conditions. Use the data below:
Enthalpy of sublimation of sodium =+108 kJmol -1
First ionization energy of sodium
=+500 kJmol-1
Second ionization energy of sodium=+4562 kJmol -1
Enthalpy of atomization of chlorine=+121kJmol -1
Electron affinity of chlorine =
-364 kJmol-1
Lattice energy of NaCl2
=
-2489 kJmol-1

Answer: +2195 kJmol-1


The standard enthalpy of formation of NaCl2 is highly
endothermic thus this compound is unstable with respect to its
elements and cannot exists under standard conditions
85