Chapter 14

Thermochemistry

Introduction
Every chemical change is accompanied by
energy change, principally in the form of HEAT ENERGY.

i.e: The evolution or the absorption of heat Exothermic reaction: Eheat is liberated
Temperature of rxn mixture increases

Endothermic reaction: Eheat is absorbed

Temperature of rxn mixture decreases

GENERALLY (For stable compounds)

Bond breaking is an endothermic

process.

Bond making/ formation is an

exothermic process.

TERMS & DEFINITION:

ENTHALPHY CHANGES:
enthalpy of reaction, formation, combustion, solution, neutralisation, atomisation, and lattice energy

Molar heat capacity Specific heat capacity

14.1 Entalphy changes of reactions

Enthalpy Changes
Entalphy = Total energy content of
reacting materials. Symbol: H

We cannot measure entalphy, we can

only measure the entalphy change.

 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

Lets start with something you know

Symbol: H

H = H Products

H Re actan ts

Endothermic Rxn - Energy Diagram

Heat is absorbed from the surroundings,
temp. decreases H has a positive value

Products
Energy H= +ve

Reactants

ENTHALPY CHANGE, H
Hrxn = HProducts - HReactants
If Hproducts > Hreactants

then H is positive

Process is ENDOTHERMIC

Exothermic Rxn Energy Diagram

Heat is given out to the surroundings, temp.
increases H has a negative value Reactants
Energy H= -ve

Products
11

ENTHALPY CHANGE, H
Hrxn = HProducts - HReactants
If Hproducts < Hreactants

then H is negative

Process is EXOTHERMIC

THERMOCHEMICAL EQUATION:
E.g.: CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

H = -890 kJ mol1
Standard conditions:

25 C/ 298 K
1 atm [aq] = 1.0 mol dm3
13

2 Basic Rules in using Thermochemical equations in calculations

14

Rule 1:
H is directly proportional to the quantity of reactants and products.

Enthalpy change/ Total amount of energy released or absorbed

The number of moles of the reactants used

15

Reactants

Products H

2(Reactants) 2(Products)(H x 2)

16

E.g:

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

H = -285.8 kJ

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

H = -571.6 kJ
17

Rule 2:
H for a reaction is equal in magnitude but opposite in sign to H for the reverse reaction.

A B B A

H -(H)
18

E.g.:

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

H =+90.7 kJ

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

H =-90.7 kJ
19

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?
20

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)
21

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

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

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

14.2

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.

25

 The Hesss Law can be illustrated by

energy diagram/ entalphy diagram.

Reactants
Energy

H2

Intermediate
H3

H1

Products
26

H2 + H3 = H1

 Another way to draw the energy diagram/

entalphy diagram.

Reactants
H2 H1

Intermediate

H3

Products

H2 + H3 = H1
27

14.3 Standard Entalphy change of Formation, Hf

Definition: the enthalpy change when one
mole of compound is formed from its elements under standard condition. H2(g) + O2(g) H2O(l)
Hf = -241 kJ mol-1 2H2(g) + O2(g) 2H2O(l) Hf =2 x -241 kJ

Examples of thermochemical equations for 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:

1 3 K(s) + N2(g) + O2(g) KNO3(s) 2 2

Hf= -x kJ mol1

 Hf of elements = 0
Eg:

H2 (g) H2 (g)
Na (s) Na (s)

Ne (g) Ne (g)
He (g) He (g)

30

Some typical Standard Entalphy change of formation, Hf (kJ mol 1)

Substance/ Compound Hf (kJ mol 1) * 298 K

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

0
+1.90 74.81

C3H6 (g), propene

CO (g), carbon monoxide CO2 (g), carbon dioxide HCOOH (l), methanoic acid CH3COOH (l), ethanoic acid

+ 20.42
110.92 395.01 424.72 484.5

C6H12O6 (s), glucose

1268

31

 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.

 Few compounds have positive standard

enthalpies of formation

They are called endothermic compounds

VERY ENDOTHERMIC Compounds are
unstable

33

 Hf

and Stability of a compound

34

Hf and Stability of a compound

Example 1 (At room 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.
35

Example 2 (At room conditions):

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

Hf = -188

1. Is H2O2 (l) stable energetically?

2. Does the above reaction occur spontaneously?
3. Given:
H2(g) + O2(g) H2O(l) Hf = 286 kJ mol
1

a) Which substance is more stable energetically, H2O2 (l) or H2O (l)? Explain. b) Find the value of the Hf of:
kJ O (l) H2mol2 1 H2O (l) + O2 (g)
36

Hf and the energetic stability of hydrogen halides (Page 462):

Hydrogen halides Hf (kJ mol1) HF (g) -271 HCl (g) HBr(g) -92 -36 HI (g) +26.5

Cl

Br

HF is a very exothermic compound. It energetically stable. increases Theissize of length ofatomsIt does not Thestrength of HX bonds increases The bond halogen HX decreases decompose easily upon heating.

37

 Hf

and Reactivity of halogens (Page 461)

38

 to Using Hf calculate H reaction

39

Standard entalphy change of reaction, H = n H (Pr oducts)

f f

rxn

m H (Re ac tan ts)

Example 14.6 (Pg 462) Example 14.7 (Pg 463)

40

41

42

43

44

Example:
Given,

C ( s) O2 ( g ) CO2 ( g ) H1 394kJmol

1 H 2 ( g ) O2 ( g ) H 2O (l ) 2 1 H 2 286 kJmol

5 C2 H 2 ( g ) O2 ( g ) 2CO2 ( g ) H 2O (l ) 2 1 H 3 1300 kJmol

45

Calculate H for the following reaction:

2C (s) H 2 ( g ) C2 H 2 ( g )
2 methods:

Algebraic method Entalphy diagram

46

Answer :

H = +226kJ

47

Method 1: Algebraic method

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

-394 kJ x 2 -286 kJ
+

O2 H2O

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

-1074kJ

Given,
C2H2 + 1300 kJ
1 2 2 O2

2CO2 + H2O
1 2

2CO2 + H2O C2H2 + 2 O2

+1300 kJ
48

1 2C + H2 +

1 2 2O2

2CO2 + H2O
1 2 2O2

-1074 kJ
+1300 kJ

2 2CO2 + H2O C2H2 + 1

+ 2

2C + H2 C2H2 +226 kJ
Hence, the entalphy change for the reaction: 2C + H2 C2H2 is +226 kJ.
49

Method 2: Entalphy cycle

2C + H2 + 2 O2
-(394 x 2) + (-286) kJ
1 2

H= y

C2H2 + 2 O2
+1300 kJ -1300 kJ

1 2

2CO2+H2O
Using Hesss Law,

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

y = + 266 kJ
50

Hf (CO2) = 394 kJ mol1 Hf (H2O) = 286 kJ mol1 Let: Hf (C2H2) = x kJ mol1 Thermochemical equation: Given,
Solution:

Method 3: Using formula

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

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

2

Hf(kJ mol1): x 0 2(394) (286) H = Hf(products) Hf(reactants) [2(394) + (286)] [x + 0] = 1300 x = +266 kJ mol1 51

 Quick check 14.2 (Pg 463)

52

 Definition: The enthalpy change when one

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

14.4 Standard Molar Enthalpy Change of Combustion, Hc

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.

 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
54

55

Hc is always exothermic

Hc can be determined by using a

bomb calorimeter

Which of the following are 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)
57

7. 2Fe (s) +

3 O2(g) 2

Fe2O3(s)

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

9. 2H2 (g) + O2 (g)

10. H2 (g) + O2 (g) 11. H2 (g) + O2 (g) 12. N2 (g) + O2 (g) 13. N2 (g) + 2O2 (g)

2H2O (l)
H2O (g) H2O (l) NO2 (g) 2NO2 (g)
58

Hc and molecular structure

Isomers usually have similar Hc. 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.
59

 E.g.: For the combustion of methane

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

H
H C H

O
C + 4H + 4O

Heat is absorbed

Energy

CH4 + 2O2

60

 E.g.: For the combustion of methane

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

C H H

O
C + 4H + 4O

Heat is released

Energy
CO2 + 2H261 O

 Hence, Hreaction
= Total of heat change = +(Heat absorbed) (Heat released)
C + 4H + 4O Energy CH4 + 2O2

CO2 + 2H2O
62

 If the quantity of absorbed heat >

released heat, the reaction becomes endothermic.

If the quantity of absorbed heat <

released heat, the reaction becomes exothermic.
63

Hc and bond strength:

Alkanes
Butane VS methyl propane 1-butene VS cyclobutane

64

Standard entalphies of combustion of the first ten (straight chain) alkanes

Alkane Hc (kJmol-1) Difference in Hc CH4 C2H6 C3H8 C4H10 890 1560 2220 2877
C9H20 C8H18

CH2 670 660 CH2 657 CH2

Hc (kJmol-1)

C3H8 CH4 C2H6

C5H12 C4H10

C7H16 C6H14

C10H22

3 4 5 6 7 8 9 10 Number of carbon atoms

65

 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
3 + 2 O2
650 kJ mol1

CO2(g) + H2O(l)
66

E.g. 1: Hc of butane & methyl propane

Hydrocarbon Butane, C4H10 H Structural formula H C H H C H H C H H C H Methylpropane, C4H10 H H H H H C H H C C H Hc (kJmol-1) Type of bonds C H H H

2877
Three CC bonds and ten CH bonds

2870
Three CC bonds & ten CH bonds 67

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

Hydrocarbon 1-butene, C4H8 H Structural formula H C H H C H H C H C H Cyclobutane, C4H8 H H H H Hc (kJmol-1) Type of bonds 2717 H

C
C

C
C

H H H

2800

Two CC bonds, one Four CC bonds & C=C bond & eight C eight CH bonds 68 H bonds

E.g. 1: Hc of butane & methyl propane

Hydrocarbon Butane, C4H10 H Structural formula H C H H C H H C H H C H Methylpropane, C4H10 H H H H H C H H C C H Hc (kJmol-1) Type of bonds C H H H

2877
Three CC bonds and ten CH bonds

2870
Three CC bonds & ten CH bonds 69

 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.

70

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

Hydrocarbon 1-butene, C4H8 H Structural formula H C H H C H H C H C H Cyclobutane, C4H8 H H H H Hc (kJmol-1) Type of bonds 2717 H

C
C

C
C

H H H

2800

Two CC bonds, one Four CC bonds & C=C bond & eight C eight CH bonds 71 H bonds

 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.
72

 C=C bond is shorter and stronger than CC

bond.

More heat is absorbed to break/ dissociate

a C=C bond.

Hence, the combustion of but-1-ene

releases less heat than cyclobutane.

73

Hc of 1-butene & cyclobutane

Energy
4C + 8H + 12O

Energy
4C + 8H + 12O

1-butene + 6O2

cyclobutane + 6O2

Hc

Hc
4CO2 + 4H2O
74

4CO2 + 4H2O

Your turn
Which bond is stronger, the CC bond or
C=C bond?

The formation of a stronger bond releases

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

The breaking of a stronger bond also

requires more energy. Hence, the dissociation of a C=C bond is more CC endothermic than a bond.
75

Example:
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 and butan-1ol are 122 and 74 respectively]

a. 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

Solution:

b.

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

Exercise :
Quick check 14.3

14.5

Standard Molar

Enthalpy Change of Neutralisation, Hneut

 Hneut

The enthalpy change 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. OR: The entalphy change when 1 mole of water is formed from the reaction between an acid and a base under standard conditions.

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

Hneut is always negative

Hneut for some acid-base rxns:

Acid HCl HNO3 CH3COOH Base NaOH KOH NaOH Hneut (kJmol1) 57.3 57.3 55.6 Type of neutralisation

CH3COOH

NH3

50.4

Strong acid - Strong base Strong acid - Strong base Weak acid - Strong base Weak acid - Weak base

Write the thermochemical equations for the neutralisation reactions. 81

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?

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

[Strong alkali] react,
Na+(aq) + Cl-(aq) + H+(aq) + OH-(aq) Na+(aq) + Cl-(aq) + H2O(l) Hneut = -57.3 kJ mol-1

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

neutralisation.

Hence, for strong acid-strong base reaction:

H+(aq) + OH-(aq) H2O(l) Hneut = -57.3 kJmol-1
83

Example:
Find the standard entalphy for the following reaction:

1. KOH(aq) + HNO3(aq) KNO3(aq) +

H2O (l)

H1

2. Ca(OH)2(aq) + 2HNO3(aq) Ca(NO3)2

(aq) + 2H2O (l) H2 Refer to example 14.14 on page 470.
84

Neutralisation involving Weak acids/ Weak bases 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

 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.

CH3COOH

Endothermic

H+ + CH3COO

Neutralisation involving HF
Neutralisation between HF (weak acid) &
NaOH, Hneut is more negative than -57.3 kJ mol-1 (ie. -68.6 kJ mol-1)

When HF dissociates, the process is highly

exothermic.

The small F- (high charge density) are

hydrated, releasing high amount of energy.

I.e.: HF (aq)

H+ (aq) + F- (aq)

highly exothermic

Hydration energy?
Hydration of X Formation of bonding Formation of strong bonding liberates high
hydration energy.
between particle X with H2O.

Formation of weak bonding liberates low

hydration energy.

When a substance is hydrated, it becomes

wet.

Hydration of anion
+

Anion

Water
-

Hydration of cation
+ + -

Cation

+
-

Water
+
90

Hydration of fluoride ion

H H

Hydration energy?
The size of F is very small. It has an extremely high charge

density. Therefore, strong F H2O bond is formed. Formation of strong bonding liberates high hydration energy.

Hneut of Strong Polyprotic Acid

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) > -57.2 kJ mol-1

 Heat energy is also liberated when

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

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

 Quick check 14.4

96

14.10 Standard Bond Dissociation Enthalpy

Endothermic

The energy absorbed to separate the

two atoms in a bond under standard

conditions

Energy

AB bond is broken

ALL reactants & products are in gaseous state.

 E.g.:

H C H (g) C (g) + 4H (g)

Four CH bonds are broken. i.e.: 1662 kJ is needed to break 4 (moles) of

H=+1662 kJ mol-1

CH 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

State the bonds that have to be broken during a reaction:

 Example 12 & 13.

14.11 Entalphy Change of Fusion & Vaporisation:

The standard entalphy change of fusion,
Hfusion, is the entalphy change when one mole of a solid changes to one mole of liquid at its melting point at standard pressure (1.0 atm).

E.g.: H2O (s) H2O (l)

Hfusion= +x kJmol1

 The standard entalphy change of

vaporisation, Hvaporisation, is the entalphy change when one mole of a liquid changes to one mole of gas at its boiling point at standard pressure (1.0 atm).

E.g.: H2O (l) H2O (g)

Hvaporisation= +y kJmol1

14.12 Standard Molar Enthalpy Change of Atomisation, Hat

Endothermic The heat energy absorbed when one mole of

gaseous atoms (Product) are formed from its element (Reactant) under standard conditions

Element (At 298 K, 1.0 atm)

Atom (g)

Atomisation
For diatomic gaseous:

Gaseous atoms For metals (solid):

Elements at std conditions

Gaseous atoms Gaseous atoms

106

 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) Ne (g) Ne (g)

Hat= 0 kJ mol-1
Hat= 0 kJ mol-1

 Hat for liquids include the enthalpy

change of vapourisation

About Hat

Hat for solids include the enthalpy

change of fusion & the enthalpy change of
vapourisation.

Hat for noble gases (monoatomic gas) is

always zero.

Which of the following equations represent atomization?

1. Mg (s) Mg (g) 2. Na (s) Na (l)

7. NaCl (s) Na (g)

+ Cl (g)

3. Cl2 (g) Cl (g)

4. Cl2 (g) 2Cl (g)

8. N2 (g) N (g) 9. O2 (g) 2O (g)

5. C (s) C (g)
6. H2O(l) H2O(g)

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

The First Electron Affinity

1st EA = Enthalpy change when a mole
of gaseous atom accepts a mole of electron to form a mole of gaseous uninegative ions i.e.

M(g) + e

-(g) M

st 1

EA

 E.g:

H (g) + e H- (g) Cl (g) + e Cl- (g)

H = -72.8 kJ mol-1
H = -364.0 kJ mol-1

The more exothermic the EA, the more

stable the anion formed.

Second Electron Affinity

2nd EA = Enthalpy change when a mole of
gaseous uninegative ions accepts a mole of electron to form a mole of gaseous dinegative ions.

i.e.
-(g) M

2nd EA

+ e

2-(g) M

The Electron Affinity

E.g.:

1. O (g) + e O- (g)
2. O- (g) + e O2- (g)
1

HEA1=-142 kJ mol-1
H EA2=+844 kJ mol-

2nd EA is endothermic, 1st EA is

exothermic.

nd 2

EA is endothermic
Repulsion

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

14.13 Lattice Energy

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

x+(g) A

y-(g) B

AyBx(s)

 + +

+ +

H = Lattice energy

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

Gaseous ions

Solid crystal lattice

 Eg:

+(g) Na

-(g) Cl

NaCl (s) Hlat=-788 kJ mol-1 Hlat=-701 kJ mol-1

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

Always -ve because the formation of

chemical bond (ionic) is exothermic.

Lattice dissociation Energy

Opposite reaction, crystal lattice is broken. Eg: NaCl (s) Na+(g) + Cl-(g)
Hlattice dissociation= +788 kJ mol-1

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

Hlattice dissociation = +701 kJ mol-1

Always +ve because the dissociation of

chemical bond is endothermic

Factors affecting Hlattice

The charge on the ions (attractive forces
between anion & cation), and The magnitude of Hlat depends on:

The distance between the ions

Hlat

+ (r

+ Z

x l -) + r
Z

 The greater the ionic charges,

the more Exo/ endo-thermic? the exothermic lattice energy.
Z+ +1 +1 +2 +3 Z-1 -2 -2 -2 NaCl Na2O MgO Al2O3 Compound Hlat(kJ mol-1) -770 -2478 -3850 -15 920

 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
NaI

95
95

196
216

-731
-684

 The lattice energy give us some idea

about the strength of ionic bonds. How?
Compound NaCl Na2O MgO Al2O3 Z+ +1 +1 +2 +3 Z-1 -2 -2 -2 Hlat(kJ mol-1) -770 -2478 -3850 -15 920

The more exothermic the lattice

energy, the stronger the ionic bond.

14.14 The Born-Haber Cycle

A cycle of reactions used for calculating
the lattice energies of ionic crystalline solids.

An application of Hess s Law.

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

Important formula:
Hatom(1) + Hatom(2) + Hionization + He. affinity + Hlat

H f =

Na(s) + Cl2(g) NaCl(s) Hf=-411kJ mol-1

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

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

Energy (kJ mol-1) Rb+(g) + I(g)

Rb+(g) + I2(g) +107 Rb+(g) + I-(g)

-314

+402 Rb(g) + I2(g)

-609

Rb(s) + I2(g)
Hf

+86

RbI(s)

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

Answer

-636 kJ

-1 mol

 The more exothermic the

enthalpy change of formation, the more stable the compound.

Test Yourself 16

14.15 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.

Hhyd
n+(g) M

+ H2O

n+(aq) M

Hhyd of the cation

n-(g) X

+ H2O

n-(aq) X

Hhyd of the anion

What happens during hydration?

+ + + -

Cation

Water
+

Anion

Water
-

Water-ion the water-ion bonds, the bonds are H formed. The stronger O energy. more exothermic the hydration Energy is liberated.

Hydration energies depends on:

1. Ionic radius, r
2. Ionic Charge, Z
The larger the charge And hence, the more density (=Z/r), the exothermic the hydration stronger the water-ion energy.Heh heh bond.

Try these:
Match the given Hhyd with its ions:

Ion Radius (pm) Hhyd (kJ mol1)

-320

Li+ 78

Na+ 98

K+ 133

Rb+ 149

-410

-295

-520

Try these:
Match the given Hhyd with its ions:

Ion

Na+

Mg2+

Al3+

Radius (pm) Hhyd (kJ mol1)

-410

78

98

133

-4680

-1930

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

The process of Solution:

Separated ions (g)

Lattice (solid)

Hydrated ions (aq)

The process of solution

The overall process of solution can be divided into 2 stages: The breaking down of the crystal lattice into gaseous ions Endothermic (= -Hlat) The solvation (hydration of separated gaseous ions by water molecules) Exothermic (Hydration energy of the cation and of the anion)

Stage 1: Breaking down the

crystal lattice into ions (g)
+X-(s) M

+(g) M

-(g) X

H1= Endothermic (- Hlat )

+ + + ++ ++ +
Solid lattice structure

Free ions (g)

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

n+(g) M

+ water
H2=exothermic

n+(aq) M

And:

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

H3=exothermic

The enthalpy change of solution, Hsol

= H1 + H2 + H3 = (-lattice energy) + (enthalpy changes of hydration of the cation and anion) = (+ve) + (-ve + -ve)

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

Is a compound soluble/ insoluble in water?

If Hhyd > Hlat Soluble If Hhyd < Hlat INsoluble

Energy

Solubility in water

Insoluble Soluble
Lattice energy Enthalpy of hydration

Compounds

Solubility of the Group II Sulphates - The solubility of the sulphates decreases down the group - Beryllium sulphate and magnesium sulphates are soluble in water - Calcium sulphate and strontium sulphate are sparingly soluble in water - Barium sulphate is insoluble in water - When a group 2 sulphate dissolves in water MSO4 (s) + water M2+(aq) + SO42-(aq)

 The dissolution process take place in 2

distinct stages (i) the breaking of ionic bonds MSO4 (s) M2+(g) + SO42-(g)

(ii) hydration of the gaseous ions by water molecules M2+(g) + SO42- (g) + aq M2+(aq) + SO42-(aq)

Going down Group 2:

Ionic radius increases Hlat and Hhyd decreases (becomes less exo) The drop off in the Hlat of Group 2 sulphates
is less rapid compared to the decrease in the enthalpy change of hydration. Ionic radius of SO42- is very large, the changing size of the much smaller cations makes very little difference to the value of (r+ + r-) No significant reduction in Hlat down Group 2 sulphate.

 But, the increasing size of the cations causes In short, decrease in solubility in Group
2 sulphate is due to the decrease of enthalpy of hydration of the metal ions considerable changes in Hhyd

Enthalpy of hydration must be greater

than lattice energy in order for the compound to dissolve in water

Energy

The Variation of Hlat and Hhyd: Group 2 sulphates

Insoluble Soluble
Lattice energy Enthalpy of hydration

BeSO4

MgSO4

CaSO4

SrSO4

BaSO4

 The solubility of gr. 2 hydroxides and fluorides

increases on going down the group The presence of covalent character causes the compounds to have higher Hlat than expected Solubility of covalent compound is determined by its polarity~ Like-dissolves-like Rule Non-polar compound dissolve in non-polar covalent solvent, naphthalene dissolves in benzene (v.d.w forces present in both comp.) Cannot dissolves in water because cannot overcome the strong attraction in water molecules

 Polar compound dissolves in polar solvent Hydroxyl group (-OH), carboxylic acid

group (COOH), amine group (NH2), sulphonic acid group (SO3H) promote the solubility of the compound in water by forming H-bonding with water More hydrophilic groups, more soluble and more H- bond formed in the water Hydrophobic groups, such as alkyl groups decrease the solubilities of organic compounds

Exercise: Checkpoint 15.6 Examination Ques. 15: Objectives,Structural Questions 1,2,3,4 & 5