You are on page 1of 176

1

Introduction

Every chemical change is accompanied by


energy/ entalphy changes, principally in
the form of

HEAT ENERGY.

To understand why such, lets take a look


at how a reaction takes place.

GENERALLY (For stable


compounds)
Bond breaking is an
endothermic process.
Reactants
Bond
making/ formation
is an exothermic process.
Products

However,

Different chemical reactions involves


different heat change/ entalphy change,
i.e:
The evolution or the absorption of heat
The amount of energy evolved / absorbed

Directionality of Heat Transfer

Heat always transfer from hotter object


to cooler one.

EXOthermic: heat transfers from


SYSTEM to SURROUNDINGS.

T(surrounding) goes up

Directionality of Heat Transfer

ENDOthermic: heat transfers from


SURROUNDINGS to SYSTEM.

T (surr) goes down

SUMMARY OF EXOTHERMIC RXN &


ENDOTHERMIC
RXN
EXOTHERMIC RXN
ENDOTHERMIC RXN
Heat is released to the
surroundings

Heat is absorbed from


surroundings

The temperature of rxn


mixture rises

The temperature of rxn


mixture drops

The entalphy change, H is


negative

The entalphy change, H is


positive

The entalphy of products is


lower than that of reactants
Energy
Reactants

The entalphy of products is


higher than that of reactants
Energy

-H

Products
+H

Products
Weaker bonds are broken,

Reactants
Stronger bonds are broken,

DEFINITIONS:

Enthalpy change of reaction,


Enthalpy change of formation,
Enthalpy change of combustion,
Enthalpy change of hydration,
Enthalpy change of solution,
Enthalpy change of neutralisation,
Enthalpy change of atomisation
Bond energy,
Ionisation energy, and
Electron affinity.
8

Enthalpy Changes

Entalphy = Total energy content of


reacting materials. Symbol: H

We CANNOT measure entalphy, we


can only measure the entalphy
CHANGE.
10

DEFINITION:
Enthalpy change for a reaction, H
= The total heat energy absorbed or
liberated in a chemical reaction
= The energy exchange with the
surroundings where a reaction takes
place

Enthalpy change is measured in kJ mol1


11

THERMOCHEMICAL
EQUATION:
E.g.:

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)


H = -890 kJ mol1
Standard
conditions:
25 C/ 298 K
1 atm
17

The entalphy of reaction depends on:


(a)The number of moles of products and
reactants
(b)The direction of the reaction
18

E.g:

H2(g) + 0.5 O2(g) H2O(l)


H = -285.8 kJ

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


H = -571.6 kJ
21

E.g.:

HgO(s) Hg(l) + O2(g)

H =+90.7 kJ

Hg(l) + O2(g) HgO(s)

H =-90.7 kJ
23

Example 1:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
H = -890 kJ mol1
(a)

Is the rxn endothermic or


exothermic?

(b)

Is the total entalphy for the


reactants larger or smaller than the
total entalphy for the products?
24

Example 1:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
H = -890 kJ mol1
(c)

What is the value of H for the


reaction:
i.

2CH4(g) + 4O2(g) 2CO2(g) + 4H2O(l)

ii. CH4(g) + O2(g) CO2(g) + H2O(l)


iii. CO2(g) + 2H2O(l) CH4(g) + 2O2(g)
iv. 3CO2(g) + 6H2O(l) 3CH4(g) + 6O2(g)
25

Five factors that affect the


value of the entalphy change:
1.

temp. of the experiment being carried


out

2.

Physical states of the reactants

3.

Allotropic forms of the reactants

4.

Pressure of the gaseous reactants

5.

Concentration of the reactants


26

The Standard Conditions


For Calculating Enthalpy
Changes
-

T = 25C or 298 K

P = 101 kPa or 1 atm

[Reactant] = 1.0 mol dm-3

For Allotropic reactants, the most stable


allotrope at 298 K and 1 atm is used
27

Entalphy change measured


under standard conditions
is described as Standard
Entalphy change of
reaction, H.

28

CALCULATION 2:
When solutions are involved,

Q @ H = mc
Where
H = entalphy change
m = mass of solution
c = specific heat capacity of water
= 4.2 J g1 C1
= change in temperature
Assumptions when using the formula:
Density of solution = 1 g cm3
Ignore mass of solid added
When 1 g of solution absorbs 4.2 J energy,
temperature increases by 1C
29

Example 2:
Cu2+(aq) + Zn(s) Zn2+(aq) + Cu(s)H=-218 kJmol1
Calculate the amount of heat evolved when excess zinc
is added to 100 cm3 of 0.20 mol dm3 copper(II)
nitrate.

SOLUTION:
Number of moles of Cu2+ = 0.20 x 100 /
1000 = 0.020
Quantity of heat evolved = 0.020 x 218 =
4.36 kJ
30

QUICK CHECK 7.1 (p.4)

31

7.1b Standard Entalphy


change of

Formation,
H
Definition: the HEAT RELEASED
f when

(+&-)

one mole of pure compound is formed


from its elements under standard
conditions.
H2(g) + O2(g) H2O(l)
Hf = -241 kJ mol-1
2H2(g) + O2(g) 2H2O(l)
H = 2 x -241 kJ

X
32

Thermochemical equations
for formation of some
compounds:
The formation of Carbon dioxide:
C(s) + O2(g) CO2(g)

Hf= -394 kJ mol1

The formation of Urea:


C(s) + 2H2(g) + N2(g) + O2(g) CO(NH2) 2 (s)

Hf= -333.5 kJ mol1


The formation of Potassium nitrate:
K(s) + 1 N2(g) + 3O2(g) KNO3(s)

Hf= -x kJ mol1
33

Hf of elements = 0
Eg:

- H2 (g) H2 (g)
- Na (s) Na (s)
- Ne (g) Ne (g)
- He (g) He (g)

34

Which of the following are


correct equations for Hf?
1.

NaOH (aq) + HCl (aq) NaCl (aq)

2.

Na (s) + Cl2 (g) NaCl (s)

3.

Na (s) + Cl2 (g) NaCl (aq)

4.

2C(s) + 2H2(g) + O2(g) CH3COOH (l)

5.

C2H5OH(l) + 2[O] CH3COOH (l) + H2O(l)

6.

C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)

7.

2Fe (s) +

3
O (g) Fe2O3(s)
2 2

35

Some typical Standard Entalphy


change of formation, Hf (kJ mol 1)
Substance/ Compound

Hf (kJ mol1)
K

C (s), Graphite
C (s), Diamond
CH4 (g), methane

0
+1.90
74.81

C3H6 (g), propene

+ 20.42

CO (g), carbon monoxide


CO2 (g), carbon dioxide

110.92
395.01

HCOOH (l), methanoic acid 424.72


CH3COOH (l), ethanoic
484.5
acid

* 298

36

Most compounds have negative standard


enthalpies of formation

They are called exothermic compounds


VERY EXOTHERMIC compounds are stable
Formation is spontaneous

The more negative the Hf, the more


stable is the product.

37

Few compounds have positive standard


enthalpies of formation

They are called endothermic


compounds
VERY ENDOTHERMIC Compounds are

unstable

38

H and Stability
of a compound

39

+
Sodium
Metal

Na (s)

Chlorine
gas

Table
salt

Cl2 (g) NaCl (s)


Hf = - 414 kJ mol1

40

Sketch an energy diagram for the


formation of NaCl.

Indicate on your energy diagram, which


substance is stable, and which is not.

Infer on the relationship of the value of


Hf with the energetical stability of the
reactants and products.

41

Hf and Stability of a
compound

Example 1 (At standard conditions):


C (diamond) C (graphite)

Hf = -2 kJ mol 1

The ve Hf shows that graphite is more stable


than diamond. I.e. graphite is more stable
energetically.

Diamond tends to change to graphite.

But this reaction (diamond graphite) is very


slow. Hence, diamond is energetically unstable,
but kinetically stable.
42

Example 2 (At room conditions):


H2 (g) + O2 (g) H2O2 (l)
1.

Hf = -188 kJ mol1

Is H2O2 (l) stable energetically?

2. Does the above reaction occur


spontaneously?
3. Given:
H2(g) + O2(g) H2O(l) Hf = 286 kJ mol1
a) Which substance is more stable energetically,

H2O2 (l) or H2O (l)? Explain.


b) Find the value of the H of:

H2O2 (l) H2O (l) + O2 (g)


43

Example 3: Hf and the energetic


stability of hydrogen halides:
Hydrogen
halides
Hf (kJ mol1)

Cl

HF(g HCl(g HBr(g HI(g


)
)
)
)
+26.
-271 -92
-36
5

Br

HF is a very exothermic
compound. It is energetically
The
The
The
strength
size
bond
ofItlength
halogen
of HX
ofbonds
atoms
HX
increases
decreases
increases
stable.
does
not
decompose

44

QUICK CHECK 7.2 (p.6)

45

Using H to
calculate

H reaction

46

Calculate H
of reaction?

In general, when ALL


enthalpies of formation are
known:

oo
oo
Hoorxn
=
H
(products)
H
ff
ff (reactants)
rxn

Remember that always = final initial


47

Example:
Given,

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

H 394kJmol

1
H 2 ( g ) O2 ( g ) H 2O(l ) H 2 286kJmol
2
5
C2 H 2 ( g ) O2 ( g ) 2CO2 ( g ) H 2O(l )
2

1
H 3 1300kJmol
Calculate H for the following reaction:

2C ( s ) H 2 ( g ) C2 H 2 ( g )
52

Answer :
H = +226kJ

53

SOLUTION:
Given,
Let:

Hf (CO2) = 394 kJ mol1


Hf (H2O) = 286 kJ mol1
Hf (C2H2) = x kJ mol1

Thermochemical
equation:
5

C2H2(g) + 2O2(g) 2CO2(g) + H2O (l) H = 1300 kJ mol1


Solution:
5
C2H2(g) + 2O2(g) 2CO2(g) + H2O (l)

Hf(kJ mol1):

2(394)

(286)

H = Hf(products) Hf(reactants)

[2(394) + (286)] [x + 0] = 1300


x = +266 kJ mol1

54

Example:

The standard entalphy of formation of Ag +


(g), Cl-1(g), and AgCl(s) are +105 kJ mol-1,
-167 kJ mol-1, and -127 kJ mol-1 respectively.
(a)Write

a thermochemical equation to
represent each of the three Hf
(b)Calculate

the entalphy change for the


following reaction:
AgCl(s) Ag+(g) + Cl-1(g)
55

+65 kJ

56

QUICK CHECK 7.3 (p.7)

57

7.1c Standard Molar


Enthalpy Change of
Combustion, Hc

Definition: The heat/ energy evolved when one


mole of substance is completely burned in excess
oxygen under standard conditions

E.g. 1:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
Hc = -890 kJmol-1
When one mole of methane, CH4 (g) is completely

burnt in excess oxygen under standard conditions, 890


kJ of heat energy is released.
58

E.g. 2: Combustion of carbon:

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

Hc = -394 kJmol-1

When one mole of carbon, C (s) is completely burnt in

excess oxygen under standard conditions, 394 kJ of


heat energy is released.

E.g. 3: Combustion of carbon:


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

Hc = -242 kJmol-1

When one mole of hydrogen gas, H2 (g) is completely

burnt in excess oxygen under standard conditions, 242


kJ of heat energy is released.

Sometimes, Hc = Hf
59

Correct thermochemical equations


for Hc?
1.

CH4 (g) + 2O2(g) CO2(g) + 2H2O(l)

2.

CH4 (g) + 2O2(g) CO2(g) + 2H2O(g)

3.

3CH4 (g) + 6O2(g) 3CO2(g) + 6H2O(l)

4.

Mg (s) + O2 (g) MgO (s)

5.

C2H5OH (l) + 2[O] CH3COOH (l) + H2O(l)

6.

C2H5OH (l) + 3O2(g) 2CO2(g) + 3H2O(l)


60

7.

2Fe (s) + 3 O2(g) Fe2O3(s)


2

8.

Fe (s) + O2(g) Fe2O3(s)

9.

2H2 (g) + O2 (g)

2H2O (l)

10.

H2 (g) + O2 (g)

H2O (g)

11.

H2 (g) + O2 (g)

H2O (l)

12.

N2 (g) + O2 (g)

NO2 (g)

13.

N2 (g) + 2O2 (g)

2NO2 (g)

Which TE indicates a formation?

61

62

Hc

is always exothermic

Hc

can be determined by using a

bomb calorimeter

63

Hc and molecular
structure

Chemical reactions occurs in two steps:


1. Energy is absorbed to break

bonds

between atoms in reactants.


2. Energy is liberated when the atoms form
new bonds to form the products.

The magnitude of Hc depends on the


type/ strength of bonds.
64

E.g.: For the combustion of methane


CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
Hc = -890 kJmol-1

H
H

C
H

Heat is

O
C + 4H +
4O

Energ
y
CH4 +

65

E.g.: For the combustion of methane


CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
Hc = -890 kJmol-1

H
H

C
C
H
H

H
H

H
H
Energ
y

Heat is released

O
O

O
O

O
O

O
O
C + 4H +
4O
CO2 +

66

C + 4H +
4O
Energ
y

CH4 + 2O2

CO2 + 2H2O

Hence, Hreaction @ Hcombustion


= Amount of heat change
= +(Heat absorbed) (Heat released)
67

Hc and bond strength:


SAME or DIFFERENT?

Butane VS methyl propane

1-butene VS cyclobutane

Alkanes

69

Standard entalphies of combustion of the first


ten (straight chain) alkanes

Hc
(kJmol-1)

Alkan Hc (kJmol-1) Difference in


Hc
e
CH2
CH4
890
670
CH2
1560
C2H6
660
2220
CH2
C3H8
657

2877
CH
4

C 3H 8
CH4

1
9

C 2H 6

2
10

10

C5H12
C4H10

C7H16
C6H14

C9H20
C8H18

C10H2
2

8
70

Each alkane is different from the next alkane by


the addition of a CH2 group.

The difference in the Hc between each


successive member of the series is about 650
kJ mol1.
This 650 kJ mol1 corresponds to the breaking
and forming of bonds when one mole of CH2
group undergoes combustion to form CO2 and
H2O.

CH2 +

32
O
2

650 kJ mol CO
1

(g) + H2O(l)
71

E.g. 1: Hc of butane & methyl


Butane, C4H10
Methylpropane, C4H10
Hydrocarbon
propane
Structural
formula

Hc /kJmol-1

H C
H
H

2877

H
H

H
H

H
H

H
2870

# of bonds
fused

Three CC bonds Three CC bonds


and ten CH bonds & ten CH bonds

# of bonds
formed

Eight C=O bonds


Eight C=O bonds
and ten OH
and ten OH bonds
bonds
72

Both butane and methylpropane contain


the same number of atoms and the
same type of chemical bonds.

Their Hc are similar.

This suggests that when each type of


bond is broken or formed, a fixed value
of energy is absorbed/ liberated.

73

e.g. 2: Hc of 1-butene &


Cyclobutane,
Hydrocarb
cyclobutane
1-butene, C H
4

on

Structural
formula

Hc
(kJmol-1)
# of bonds

H C
H
H

H
H

C4H8

H C
H

H
H

2717

2800

Two CC bonds,
one C=C bond &

Four CC bonds
& eight CH
74

The Hc for 1-butene and cyclobutane are


different.

This is because different type of bonds in


reactants (1-butene and cyclobutane) are
broken to form 4 moles of CO2 and 4 moles
of H2O.

75

C=C bond in but-1-ene is shorter and


stronger than CC bond in cyclobutane.

More heat is absorbed to break/ dissociate


a C=C bond.

Hence, the combustion of but-1-ene


releases less heat than cyclobutane.

76

Hc of 1-butene &
cyclobutane Energy
Energy

4C + 8H + 12O
4C + 8H + 12O

1-butene
+ 6O2

cyclobutan
e + 6O2

H1
4CO2 +
4H2O

H2
4CO2 +
4H2O

77

Your turn

Which bond is stronger, the CC bond or


C=C bond?

The breaking of a stronger bond also


requires more energy. Hence, the
dissociation of a C=C bond is more
endothermic than a
bond.
CC

The formation of a stronger bond releases


more energy. Hence, the formation of
C=C bond is more exothermic.
78

Summary Hc

Definition: The heat/ energy evolved when one


mole of substance is completely burned in
excess oxygen under standard conditions
Hc is always exothermic.

Isomers have similar Hc.

Molecule with more bonds has a more negative


Hc.

Molecule with stronger bonds has a more


negative Hc.

79

DETERMINATION OF Hc
USING A BOMB
CALORIMETER

80

CALORIMETRY

Measuring Heats of Reaction

Some heat from reaction warms


water
qwater = (sp. ht.)(water mass)
(T)
Some heat from reaction
warms bomb
qbomb = (heat capacity, J/K)(T)

Total heat evolved = qtotal = qwater +


q

81

EXAMPLE 1:
Calculate heat of combustion of octane.
C8H18 + 25/2 O2 8 CO2 + 9 H2O
Burn 1.00 g of octane
Temp rises from 25.00 to 33.20 oC
Calorimeter contains 1200 g water
Heat capacity of bomb = 837 J/K

82

SOLUTION:
Step 1
Calc. heat transferred from reaction to
water.
q = (4.184 J/gK)(1200 g)(8.20 K) = 41,170 J
Step 2
Calc. heat transferred from reaction to
bomb.
q = (bomb heat capacity)(T)
= (837 J/K)(8.20 K) = 6860 J
Step 3
Total heat evolved
41,170 J + 6860 J = 48,030 J
Heat of combustion of 1.00 g of octane = -48.0 kJ
83

EXAMPLE 2:

A 1.8 g sample of glucose is


burnt in a bomb calorimeter
as pictured in the animation
below. 1 kg of water was
placed in the bomb
calorimeter.
C = 12, O = 16, H =1,
The heat capacity of water
is 4.2 J/g/C.
a) Is the above reaction an
exothermic or endothermic
reaction? Explain.
b) Calculate the enthalpy
change of the reaction
above.

84

Solution:
(a) The reaction is an exothermic reaction. Heat is given off.
(b) To obtain the change in enthalpy for the reaction below,
Step 1) find the number of joules produced.
1kg of water increased in temperature by 6.7 degrees celsius
The amount of energy required
= heat capacity X mass of water X temperature change
= 4.2 X 1000 X 6.7
= 28140 J or 28.4Kj.
Step 2) Mole of glucose added = 1.8 /180 = 0.01 mole
Step 3) Divide the amount of energy given out by the
number of moles to get the enthalpy change
= -28.40 / 0.01 = -2840kJ/mol
Note how the enthalpy change has a negative sign. This
indicates an exothermic reaction (heat given out).
85

Example 3:

When 0.540 g of benzoic acid is completely burnt in


a bomb calorimeter, it causes the temperature of
water in the calorimeter to increase by 1.38 K. The
combustion of 0.148g of butan-1-ol in the same
bomb calorimeter causes an increase of 0.51 K.
a) Calculate the calorimeter constant (heat
capacity of the calorimeter), in kJ K1.
b) Calculate the standard enthalpy change of
combustion of butan-1-ol.
[The standard heat combustion of benzoic acid is
-3230 kJmol-1. The Mr of benzoic acid & butan-1-ol
are 122 and 74 respectively]
86

Solution:
a.

b.

Heat liberated from the combustion of 0.540 g


benzoic acid
= (0.540/122) x 3230
= 14.30 kJ
Calorimeter constant = 14.30/1.38
= 10.36 kJ K-1
Number of moles of butan-1-ol
= 0.148/74 = 0.002 mole
Heat liberated from the combustion of butan-1-ol =
10.36 x 0.51 = 5.2836 kJ

Standard enthalpy change of combustion


= 5.2836/0.002 = 2641.8 kJ mol-1
87

Exercise :
Quick check 7.5
(p.10)

88

89

7.1d Std Entalphy Change of


Hydration, Hhyd

Hydration of X = Formation of bonding


between particle X with H2O.

Formation of strong bonding liberates high


hydration energy.

Formation of weak bonding liberates low


hydration energy.

When a substance is hydrated, it becomes


wet.
90

Hydration of anion
-

+
-

+
+

Ion-dipole
attraction

Anion

Wate
r
91

Hydration of cation
+
+

Ion-dipole
attraction

Cation

Wate
r

92

Hydration
of
fluoride
H
O
ion
H

H
O

F
H
O

H
H

O
93

Hhyd of F ion:

The size of F is very small.


It has an extremely high charge density
(Charge/radius).
Therefore, very strong F---H2O bond is
formed = ION-DIPOLE ATTRACTION
Formation of strong bonding liberates
high hydration energy.
94

95

Hneut

The amount of energy released when 1


mole of H+(aq) ions from an acid reacts
with 1 mole of OH-(aq) ions from an alkali
to form one mole of water molecules under
standard conditions.

H+(aq) + OH-(aq) H2O(l) Hneut

Hneut is always negative


96

H
for some acid-base
H
rxns:
Type of

neut

neut

Acid
HCl

Base

NaOH

(kJmol
1
)

neutralisation

57.3

Strong acid Strong base

HNO3

KOH

57.3

Strong acid Strong base

CH3COO
H

NaOH

55.6

Weak acid Strong base

CH3COO
Weak acid - Weak
NH3
50.4
base
Write
the thermochemical equations
for
H

the neutralisation reactions.

97

Thermochemical Equations
:

HCl(aq) + NaOH (aq) NaCl(aq) + H2O(l)

Hneut= 57.3 kJmol1

HNO3(aq)+ KOH(aq) KNO3(aq) + H2O(l)

Hneut= 57.3 kJmol1

CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(l)


Hneut= 55.6 kJmol1
CH3COOH(aq) + NH4OH(aq) CH3COONH4(aq) + H2O(l)
Hneut= 50.4 kJmol1

98

Strong acid + Strong


base

Strong acids and alkalis dissociate completely in


aqueous solution.

Hneut is constant, i.e. -57.3 kJ mol-1

E.g.:

NaOH(aq)+ HCl(aq) NaCl(aq) +


H2O(l)
Hneut = -57.3 kJ mol-1

What are Spectator ions?


99

When HCl (aq) [Strong acid] and NaOH (aq)


[Strong alkali] react,
Na+(aq) + Cl-(aq) +
H2O(l) H+(aq) + OH-(aq)
kJ mol-1

Na+(aq) + Cl-(aq) +
Hneut = -57.3

Na+(aq) & Cl-(aq) do not take part in


neutralisation.

Spectator ions: Na+ & Cl-

Hence, for strong acid-strong base reaction:


H+(aq) + OH-(aq) H2O(l)
1

Hneut = -57.3 kJmol100

Example:
Thermochemical equations for two reactions are
shown below:
1.

KOH(aq) + HNO3(aq) KNO3(aq) + H2O (l)

H1

2.

Ca(OH)2(aq) + 2HNO3(aq) Ca(NO3)2(aq) + 2H2O(l) H2

State the values of H1 and H2 .

101

Neutralisation involving
Weak acids/ Weak bases

Weak acids: HCN, CH3COOH, HCOOH, HF

Hneut for a weak acid and a strong alkali


or vice versa is lower (less negative)
than
-57.3 kJ mol-1

Less heat energy is liberated in this


reaction.

E.g.:

CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(l)


Hneut = -55.6 kJ mol-1
102

Weak acids and alkalis do not dissociate


completely

Part of the heat energy liberated during


neutralisation is reabsorbed to cause
dissociation of the weak acid/ base.

E.g.
CH3COOH

H+ + CH3COO

Acid dissociation is endothermic

103

Neutralisation involving
HF

HF is a weak acid. But during the neutralisation


between HF & NaOH, Hneut is more negative
than -57.3 kJ mol-1 (ie. -68.6 kJ mol-1). Why?

When hydrogen fluoride (HF) dissociates, the


small F- (high charge density) are hydrated,
releasing high amount of energy (very
exothermic).

I.e.:

HF (g)

H2 O

H+ (aq) + F- (aq)

- highly exothermic
104

H
of Strong
Polyprotic Acid

neut

More exothermic.
Eg:
NaOH(aq) + H2SO4(aq) NaHSO4(aq) + H2O(l)
H1 = -61.95 kJ mol-1

NaOH(aq) + NaHSO4(aq) Na2SO4(aq) + H2O(l)


H2 = -70.90 kJ mol-1
Hneut = (-61.95 + -70.90)/ 2 kJ mol-1
= -66.4 kJ mol-1 (per mole H2O formed)
> -57.3 kJ mol-1
Explanation: Heat is liberated when H2SO4 is diluted by
aqueous NaOH.
105

Heat energy is liberated when


polyprotic acid is diluted as the aq
alkali is added to the strong diprotic
acid.

106

Example:
200 cm3 of 0.50 mol dm-3 hydrochloric acid is
mixed with the same volume of 0.50 mol dm-3
sodium hydroxide at the same temperature. The
temperature of the mixture is raised to 3.4 K.
Calculate the enthalpy of neutralisation.
[Specific heat capacity of solution = 4.2 J g-1 K-1 ]
Answer: -57.12 kJ mol-1

Show complete
working.

107

SUMMARY (H

neut

Hneut is the heat released when one mole


of water is formed from the reaction between
acid and alkali, under standard conditions.
Strong acid + strong alkali
Hneut = -57.3 kJ mol1
Weak acid/ weak alkali
Hneut less exothermic
Because: Heat released from neutralisation
is reabsorbed to dissociate weak acid/ base
completely.
108

SUMMARY (H

neut

Sulphuric acid + strong alkali


Hneut more exothermic

Because: Heat released from dilution of


sulphuric acid is significant.

HF (weak acid) + strong alkali


Hneut more exothermic

Because: Hydration of F- ion (has high


charge density) is VERY exothermic.
109

110

7.1f Standard Bond


Dissociation Enthalpy

Endothermic

Definition:
The amount of energy required to break a
bond (in a substance in gaseous state) into
two gaseous atoms under standard
conditions.
Unit: kJ mol1
The greater the bond energy, the stronger
the bond.

111

Factors affecting bond energy & bond strength:


i. Atomic size: Bigger atom greater bond length
weaker bond strength smaller bond dissociation
energy
ii. Multiplicity of bond: Multiple bond is stronger
higher bond energy.
iii. # lone pair of electrons: If more lone pairs of
electrons are present on the bonded atoms the
greater the repulsion between the atoms less bond
dissociation energy.
iv. Greater electronegativity difference between
atoms greater bond polarity stronger bond
bond energy
eg: HF > HCl > HBr > HI,
112

Energy

AB bond is
broken

ALL reactants &


products are in
gaseous state.
113

E.g.:

(g)

C (g) + 4H (g)

H=+1662 kJ mol-1
H
Four CH bonds are broken.
i.e.: 1662 kJ is needed to break 4 (moles) of C
H bonds.
Then (1662 4) = 416 kJ is needed to break 1
(mole) of CH bonds.
The average bond entalphy of the CH bond =
+416 kJ mol-1
114

State the bonds that have


to be broken during a
reaction:

115

116

119

14.12 Standard Molar Enthalpy

Change of Atomisation, Hat


at

Endothermic

The heat energy absorbed when one mole of


gaseous atoms are formed from its element under
standard conditions

Element
(At 298 K, 1.0 atm)

Atom
(g
120

E.g.:

Na (s) Na (g)

Hat=+107 kJ mol-1

H2 (g) H (g)

Hat=+218 kJ mol-1

Hat for monoatomic gases (Noble gases) is zero


because no chemical occurred.

E.g.:

He (g) He (g)

Hat= 0 kJ mol-1

Ne (g) Ne (g)

Hat= 0 kJ mol-1
121

Atomisation
For diatomic gaseous:

Liquid
(covalent molecule)

Vaporisation + Bond Gaseous


dissociation
atoms
For metals (solid):

Metal (solid)

Melting + vaporisation
Elements at std
conditions

Gaseous
atoms
Gaseous atoms
122

About H

at

Hat for liquids = Hvap + Bond energy

Hat for solids = = Hfusion + Hvap

Hat for noble gases (monoatomic gas) = 0

123

Which of the following


equations represent
atomization? 7. NaCl (s) Na (g) +
1. Mg (s) Mg (g)
Cl (g)

2.

Na (s) Na (l)

3.

Cl2 (g) Cl (g)

8. N2 (g) N (g)

4.

Cl2 (g) 2Cl (g)

9. O2 (g) 2O (g)

5.

C (s) C (g)

6.

H2O(l) H2O(g)

10.H2O(l) H2(g) +
O2 (g)
124

125

The First Electron


Affinity

1st EA = Enthalpy change when one


mole of gaseous atoms accepts a mole
of electrons to form a mole of gaseous
uninegative ions
i.e.

M(g) + e

1st
EA
M (g)

1st EA is always exothermic


126

E.g:
H (g) + e H- (g)

H = -72.8 kJ mol-1

Cl (g) + e Cl- (g)

H = -364.0 kJ mol-1

The more exothermic the EA, the more


stable the anion formed.
Deduce definition for 2nd electron affinity?

127

Second Electron
Affinity
2 EA = Enthalpy change when one mole
nd

of gaseous uninegative ions accepts one


mole of electron to form one mole of
gaseous dinegative ions.

i.e.

2nd
EA
2-

M (g) + e M (g)
-

2nd EA is always endothermic


128

The Electron
Affinity
E.g.:

1.

O (g) + e O- (g)

HEA1=-142 kJ mol-1

2.

O- (g) + e O2- (g)

H EA2=+844 kJ mol-1

1st EA is always more exothermic/


negative than 2nd EA.
129

nd EA is less exothermic/
2nd
st
more endothermic than 1st
EA. Why?

Repulsio
n

A negatively charged ion will repel the


addition of 2nd electron
Energy must be absorbed to overcome the
repulsive forces between the 2 negatively
charged particles
130

131

First Ionisation Energy

1st IE = The minimum energy needed to


remove the most loosely held electron
from one mole of free gaseous atom to
form one mole of gaseous unipositive
ions under standard conditions.

i.e.

1 IE
st

M(g) M (g) + e
+

132

Spot the mistakes!


1. Na(s)

Na+(g) + e-

2. Na(g)

Na+(g) + e- st
1

3. Mg(g)
4. Mg(g)
5. H2(g)

1 IE

Mg2+(g) + 2e Mg+(g) + e-

H+(g) + e133

Second Ionisation
Energy
2 IE = The minimum energy needed to
nd

remove the most loosely held electron


from one mole of gaseous unipositive
ions to form one mole of gaseous
dipositive ions under standard
conditions.

i.e.

M (g) M
+

2+

2nd IE

(g) + e
134

135

7.1i Hydration Energies, Hhyd

Enthalpy change of hydration, Hhyd is


the heat liberated when one mole of free
gaseous ion dissolves in water to form
hydrated ions of infinite dilution under
standard conditions.

An Exothermic process.

Bonds are formed with water molecules.


136

Hhyd
Mn+(g) + H2O Mn+(aq)
Hhyd of the cation

Xn-(g) + H2O Xn-(aq)


Hhyd of the anion
137

What happens during


hydration?
+

Cation

Wate
r
138

+
+

+
-

Anion

Wate
r
139

H
H

H
O

F
H

H
ion-dipole
attractions
are
O
The stronger the ion-dipole
O
H
formed.
attractions, the more exothermic the
H
hydration energy.

140

Hydration energies depends on:


1.

Ionic radius, r

2.

Ionic Charge, Z

Charge density
= Z
r

The
And larger
hence,the
thecharge
more
density
(=Z/r),
the
exothermic
is the
stronger
the energy
water-ion
hydration
bond.
141

Try these:

Match the given Hhyd


with its ions:
hyd

Ion
Radius
(pm)
Hhyd

Li+

Na+

K+

Rb+

78

98

133

149

(kJ mol1)
-320

-410

-295

-520
142

Try these:

Match the given Hhyd


with its ions:
hyd

Ion

Na+

Mg2+

Al3+

Radius (pm)

78

98

133

Hhyd
(kJ mol1)
-410

-4680

-1930
143

SUMMARY

(Hhyd )

The higher the charge density


(charge/ Ionic radius), the
stronger the ion-dipole
attraction, the more
exothermic is the Hhyd
144

Depends on:
nature of solute (ionic/ covalent)
nature of solvent (polar/ nonpolar)
temperature
pressure (if involve gas)
145

Step 1:
The lattice breaks
up
H = -Lattice
energy

Step 2: Free ions are hydrated.


H = Hhyd(cation) + Hhyd(anion)

146

The process of solution can be


divided into 2 stages:

The breaking down of the crystal lattice


into gaseous ions

The solvation (hydration of separated


gaseous ions by water molecules)

147

Stage 1: Breaking down


the crystal lattice into ions
(g)
+ +
-

M X (s) M (g) + X (g)

H1= Endothermic (- Hlat )

+ + +
+ +
+ + +

Solid lattice

Free ions
148

Stage 2: Hydration of
ions(g) by water molecules

Mn+(g) + water Mn+(aq)


H2=exothermic

And:

Xn-(g) + water Xn-(aq)


H3=exothermic

149

150

Enthalpy Change of
Solution/ Solvation,
Hsol

Enthalpy

change when 1 mole of solid


ionic compound dissolves in water to form
a solution of infinite dilution under
standard conditions

Mn+Xn-(s) + H2O Mn+(aq) + Xn-(aq)


H= Enthalpy change of solution

Could be positive or negative


151

The enthalpy change of solution, Hsol


= (-lattice energy) + (enthalpy changes of
hydration of the cation and anion)
= LE + Hhyd(Cation) + Hhyd(Anion)
= (+ve) +

(-ve)

(-ve)

= +ve (insoluble) or -ve (soluble)


152

Is a compound soluble/
insoluble in water?
Given:
(A) | Hhyd | > | Hlat |
(B) | Hhyd | < | Hlat |

Sketch entalphy diagram


Hsol > 0 @ Hsol < 0 ?

Predict the solubility of (A) & (B)

154

Is a compound soluble/
insoluble in water?
(A) | Hhyd | > | Hlat |
Hsol < 0 (negative)
The salt is soluble

(B) | Hhyd | < | Hlat |


Hsol > 0 (positive)
The salt is insoluble
155

Energy

Solubility in water

Insoluble
Soluble

Lattice
energy

Compound

Enthalpy
of
hydration
156

Example 1:

The Hsol for magnesium chloride and


barium nitrate are -186 and +40 kJ mol1
respectively. Write balanced thermochemical
equations for the two process.

157

Example:

Calculate the Hsol for silver chloride from


the following data. Comment on your answer.
lattice energy of AgCl = -900 kJ mol1
hydration energy of Ag+ = -464 kJ mol1
hydration energy of Cl- = -364 kJ mol1

158

166

7.2

Hesss Law

Hesss Law states that the heat


liberated or absorbed during a
chemical reaction is independent of
the route by which the chemical
change occurs.

167

The Hesss Law can be illustrated by energy


diagram/ entalphy diagram.

Reactant
s
Energy

H2

Intermediat
e

H1

H3

Products
H2 +

H3

H1

168

Another way to draw the energy diagram/


entalphy diagram.

H2

Intermediat
e

H2 +

Reactant
s

Products

H3

H3

H1

H1
169

Example 1:
Given,

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

H 394kJmol

1
H 2 ( g ) O2 ( g ) H 2O(l ) H 2 286kJmol
2
5
C2 H 2 ( g ) O2 ( g ) 2CO2 ( g ) H 2O(l )
2

1
H 3 1300kJmol
Calculate H for the following reaction:

2C ( s ) H 2 ( g ) C2 H 2 ( g )
170

Entalphy/ Thermochemical
cycle
H=
1O2
2C + H2 +12
C
H
+
2
2
2
y
2
2
O2
-(394 x 2)
+
(-286) kJ

+1300kJ
-1300
kJ

2CO2+H2
Using Hesss Law,
O

y = [-(394 x 2) + (-286)] (-1300)


y = + 266 kJ
171

Method 2: Algebraic
method
2C + 2O2 2CO2
-394 kJ x 2
1O
2
2

H2 +
1

H2O

-286 kJ

1
2C + H2 + 2 O2 2CO2 + H2O
2

-1074kJ

Given,
C2H2 + 2 1O2
2

2CO2 + H2O

2 2CO2 + H2O C2H2 +

1
2 2O2

-1300 kJ

+1300 kJ
172

1 2C + H2 + 2 1 O2 2CO2 + H2O -1074 kJ


2

2 2CO2 + H2O C2H2 + 2 1 O2


2

+1300 kJ

1 + 2 :

2C + H2 C2H2

+226 kJ

Hence, the entalphy change for the reaction is


+226 kJ.
173

EXAMPLE 2:
Calculate the standard entalphy change
of the following reaction:

2C(s) + O2(g) 2CO(g)


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

-394 kJ

CO(g) + O2(g) CO2(g) -284 kJ

174

Quick Check 7.6 (p.20-21)

175

176

7.3a Lattice Energy


Definition:
The amount of energy liberated when one
mole of solid ionic crystalline is formed
from its gaseous constituent ions.

A (g) + xB (g) AyBx(s


x+

y-

177

+
+

+
+

Gaseous
ions

H = Lattice
energy

+ +
+ +
++ ++
+ ++ +
+ ++ +
++ ++
++ ++
+ ++ +
+ +
+ +

Solid
crystal
lattice
178

Eg:

Na+(g) + Cl-(g) NaCl (s)


Hlat=-788 kJ mol-1

K+(g) + Cl-(g) KCl (s)


Hlat=-701 kJ mol-1

Always -ve because the formation of


chemical bond (ionic) is exothermic.
179

Example:
1. The lattice energy for calcium fluoride,
barium oxide and silver oxide are -2600,
-2490 and -2910 kJ mol-1 respectively.
Write thermochemical equations to
represent the data.
2. The lattice energy for sodium chloride is
-771 kJ mol-1. What is the entalphy
change for the following reactions?
(a) 2Na+(g) + 2Cl-(g) 2NaCl(s)
(a) 2NaCl(s) 2Na+(g) + 2Cl-(g)
180

Factors affecting H

lattice

The magnitude of Hlat depends on:

The charge on the ions (attractive forces


between anion & cation), and

The distance between the ions

Hlat

Z x Z l
+
(r + r )
+

182

The greater the ionic charges,


endo-thermic? the
the more Exo/
exothermic
lattice energy.
Compound

Hlat(kJ mol-1)

NaCl

+1

-1

-770

Na2O

+1

-2

-2478

MgO

+2

-2

-3850

Al2O3

+3

-2

-15 920

183

The smaller the distance between


ions, the more exothermic the
lattice energy.
Ionic

r+

r-

Hlat

Compound
NaCl

(nm)
95

(nm)
181

(kJ mol-1)
-770

NaBr

95

196

-731

NaI

95

216

-684
184

The lattice energy give us some idea


about the strength of ionic bonds.
How?
Compound

Z+

Z-

Hlat(kJ mol-1)

NaCl
Na2O

+1
+1

-1
-2

-770
-2478

MgO
Al2O3

+2
+3

-2
-2

-3850
-15 920

The more exothermic the lattice


energy, the stronger the ionic bond.
185

QUICK CHECK 7.7 (p.22)


QUICK CHECK 7.8 (p.23)

186

7.3B The Born-Haber Cycle

A cycle of reactions used for


calculating the lattice energies of ionic
crystalline solids.

An application of Hess s Law.

187

It involves;
- enthalpy of atomisation
- ionisation energy
- electron affinity
- lattice energy
- enthalpy of formation

188

Important formula:

H f

H atom(1) + H atom(2)
+ H ionization
+ H e. affinity + H lat
189

190

191

Na(s) + Cl2(g) NaCl(s)


Hf=-411kJ mol-1
From the Born-Haber Cycle,
-411 = +107 + 122 +496 + (-349) + LE
Lattice energy = -787 kJ mol-1

192

Example:
Draw a Born-Haber cycle for rubidium
iodide, RbI(s). Hence use the data below to
calculate the enthalpy change of formation
of RbI(s).
Hat of rubidium = +86 kJ mol-1
Hat of iodine = +107 kJ mol-1
Hlattice of rubidium iodide = -609 kJ mol-1
IE of rubidium = +402 kJ mol-1
AE of iodine = -314 kJ mol-1
193

Energy (kJ mol-1)


Rb+(g) +
I(g)
Rb+(g) + I (g) +107

-314

Rb+(g) + I-(g)

+402
Rb(g) + I2(g)
Rb(s) + I2(g)
Hf

-609

+86

RbI(s)
194

Example:
Draw a Born-Haber cycle for calcium oxide. Hence
use the data below to calculate the enthalpy
change of formation of calcium oxide.
Enthalpy change of atomisation of calcium = +177 kJ
mol-1
Enthalpy change of atomisation of oxygen = +249 kJ
mol-1
Lattice energy of calcium oxide = -3409 kJ mol -1
1st Ionisation energy of calcium = +592 kJ mol -1
2nd Ionisation energy of calcium = +1100 kJ mol -1
Electron Affinity of oxygen = -140 kJ mol-1
Formation of O2- = +795 kJ mol-1
195

Answer

-636 kJ mol-1
QUICK CHECK 7.9
p.25-26
196

LATTICE ENERGY &


COVALENT CHARACTER
The value of lattice energy can be determined:
1.Theoretically:
Calculation
Assuming that ions are spherical and
distrbution of electrons in the ion is uniform
Taking into consideration the interionic forces
2.Experimentally:

From Born Haber cycle

197

Halide

NaCl

NaBr

NaI

AgCl AgBr

AgI

Experimental LE

-776

-740

-700

-910

-900

-865

Theoretical LE

-771

-734

-696

-770

-755

-734

The difference of electronegativity between


sodium ion and halide ion is large
Experimental and theoretical value of LE are
similar. Sodium halides are 100% ionic.
The difference of electronegativity between
silver ion and halide ion is small < 1.1
Experimental and theoretical value of LE are
different. Silver halides are ionic compound
with covalent character.
198

The more exothermic the


enthalpy change of formation,
the more stable the
compound.
The more exothermic the
lattice energy, the stronger
the ionic bond between cation
& anion.
199

QUICK CHECK 7.10


p.28

200