Endothermic Exothermic

Thermochemical
reaction
Type of Enthalpy Born-Haber Cycle
Formation
Thermochemistry
Combustion
Neutralization
Atomization Calorimetry Hesss Law
Hydration
Solution (dissolution) q = mcT o Algebraic method
Ionization energy o Energy Cycle
Electron affinity
Lattice energy ionic charge, ionic radii
 Learning outcomes
At the end of this topic, students should be
able to:

a)Explain endothermic and exothermic

reactions using the energy profile diagrams.

a)State standard conditions of reaction and

define enthalpy and standard enthalpy.
c) Define enthalpy of
i. Formation
ii. Combustion
iii. Atomisation
iv. Neutralisation
v. Hydration
vi. Solution ( dissolution )

d) Write thermochemical equation for each

enthalpy
 Thermochemistry
- study of heat change in chemical reactions
- Almost all chemical reactions absorb or
produce (release) energy (in form of heat)
 Heat is energy transferred between two
bodies of different temperatures

System
Any specific part of the universe, usually
include substances involved in chemical and
physical changes.

Surroundings
The rest of the universe outside the
system
 Energy is the ability to do work
SI unit of energy is kg m2 s-2 or Joule (J)
Non SI unit of energy is calorie (Cal)
1 Cal = 4.184 J

Two types of chemical reactions:

Exothermic reaction
Endothermic reaction
- 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) H = ve

reactants
enthalpy
H = -ve

products

reaction pathway
energy profile diagram /Enthalpy diagram for
exothermic reaction
- Enthalpy of products > enthalpy of reactants,
- H is positive
- Energy is absorbed by the system from
surrounding
Consider the following reaction
A (g) + B (g) C(g) H = +ve

energy profile of diagram / Enthalpy diagram

endothermic reactions
 Enthalpy (H)
the total value of energy of a system
Its value cannot be determined experimentally.
Only changes in enthalpy, H can be
determined.
 Enthalpy of reaction, H :
The enthalpy change associated with a
chemical reaction.
Difference between enthalpy of products
& enthalpy of reactants
H = H products H reactants

Standard enthalpy, H
The enthalpy change for a particular
reaction that occurs at 298K and 1 atm
(standard state)
 Types of Enthalpies

1) Enthalpy of formation
2) Enthalpy of combustion
3) Enthalpy of atomisation
4) Enthalpy neutralisation
5) Enthalpy hydration
6) Enthalpy solution ( dissolution )
1) Enthalpy of Formation ( Hf )
-heat change when 1 mole of compound is formed
from its elements at stated condition.
H2 (g) + O2(g) H2O (l) H = 286 kJ mol 1

Standard enthalpy of formation, Hf

The heat change when 1 mole of compound is formed
from its elements at 298K and 1 atm (standard state)
The standard enthalpy of formation of any
element in its most stable state form is ZERO

H f (O2 ) = 0 H f (Cl2) = 0
2) Enthalpy of Combustion ( Hc )

-the heat released when 1 mole of substance

is burned completely in excess oxygen at stated
condition.

C (s) + O2(g) CO2(g) H = 393 kJ mol 1

Standard enthalpy, H
reaction occurs at
298K and 1 atm
3) Enthalpy of atomization ( Ha)
The energy required to form 1 mole of gaseous
atoms from the element under stated condition.
Na (s) Na (g) Hoa= +109kJmol-1
 1
Cl2(g) Cl (g) Hoa=+123kJmol-1
2

Standard enthalpy, H
reaction occurs at 298K and 1 atm
4) Enthalpy of neutralization
-The heat released when 1 mole of water, H2O
is formed from the neutralization of acid
& base under stated condition

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

H = -58 kJmol-1

Standard enthalpy, H
reaction occurs at
298K and 1 atm
5) Enthalpy of Hydration ( H hydr )
the heat released when 1 mole of gaseous ion
is hydrated in water under stated condition.

Na+ (g) Na+ (aq) H hydr= 406 kJ mol 1

Cl (g) Cl (aq) H hydr= 363 kJ mol 1

Standard enthalpy,
H
reaction occurs at
298K and 1 atm
6) Enthalpy of Solution ( Hsoln )
Heat change when 1 mole of substance dissolves in
water to form a very dilute solution under stated
condition.
NaCl(s) Na+(aq)+ Cl (aq) Hsoln
=+690 kJ/mol

Standard enthalpy, H
reaction occurs at 298K and 1 atm
 Thermochemical equation

- shows a balanced chemical equation and

the corresponding H
- stoichiometry coefficients refer to the number of
moles of the substance

Example 1

H2O(s) H2O(l) H = +6.01 kJ

-1 mole of liquid water is formed from 1 mole

of ice at 0 C & the enthalpy change is +6.01 kJ
- For reverse equation, the magnitude of H for
the equation remains the same but its sign
changes (opposite)

- when 1 mole of ice formed from 1 mole of

liquid water,

H2O(l) H2O(s) H = 6.01 kJ

Example:
 Write the thermochemical equation, if given:
1. H f Na2CO3 (s) 323 kJ / mol
2. H f CH 3COONa (s) 528 kJ / mol
3. H f CH 3COOMgBr (s) 228 kJ / mol
4. HcCH 3COOH (l ) 1130 kJ / mol
5. HcC3 H8 (g) 624 kJ / mol
6. H soln Na2O (s) 120 kJ / mol
7. H so ln K 2CO3 (s) 240 kJ / mol
8. Ha Br (g) 321 kJ / mol
 Learning outcomes
At the end of this topic, students should be
able to:
a) Define:
i. Heat capacity, C
ii. Specific heat capacity, c
b) Calculate heat change in a
i. Constant-pressure calorimetry
(simple calorimeter)
i. Constant- volume calorimetry
(bomb calorimeter)
Heat changes in physical & chemical processes
are measured with calorimeter

Specific heat (c) of a substance

amount of heat required to raise the temperature
of 1 gram of the substance by 1 degree Celsius
(Jg 1 C 1)

The heat capacity (C)

amount of heat required to raise the temperature
of a given quantity of the substances by 1 degree
Celsius (J C 1)
 Constant-pressure calorimetry
Simple calorimeter
Styrofoam cup
The outer Styrofoam cup
insulate the reaction mixture
from the surroundings (it is
assumed that no heat is lost to
the surroundings)
Heat release by the reaction is
absorbed by solution and the
calorimeter
Constant-Volume calorimetry
Bomb calorimeter
Basic Principle in Calorimeter
Heat released Heat absorbed
=
by a reaction by surroundings

Surroundings may refer to the:

i. Calorimeter itself or;
ii.The water and calorimeter

qreaction= mcT or CT
Heat released Heat absorbed
= by calorimeter
by substance

q = mcT
= CT
q = heat released by substance
m= mass of substance
c= specific heat capacity, Jg 1 C 1

T = temperature change
C = heat capacity, J C 1
Example
In an experiment, 0.100 g of H2 and excess of
O2 were compressed into a 1.00 L bomb and
placed into a calorimeter with heat capacity of
9.08 x 104 J0C 1. The initial temperature of the
calorimeter was 25.0000C and finally it
increased to 25.155 0C. Calculate the
amount of heat released in the reaction to
form H2O, expressed in kJ per mole.

Specific heat capacity of water = 4.18 Jg-1 C-1

Solution
Heat released from reaction = Heat absorbed by the calorimeter

q = CT
= (9.08 X 104 J0C-1) X (25.155 -25.000)0C
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ

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

mole of H2 = 0.100
2.016
= 0.0496 mol
moles of H2O = mole of H2

0.0496 mol of H2O released 14.1 kJ energy

14.1 kJ
H = 0.0496
=mol

= 284 kJ mol 1
- By using a bomb calorimeter filled with water, heat is
absorbed by both water & 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
Example:

Calculate the amount of the heat released from the

reaction which is carried out in an aluminium
calorimeter with a mass of 3087.0 g & contains 1700.0
mL of water. The initial T of the calorimeter is 25.0 C &
at the end, the T increased to 27.8 C

Given,
Specific heat capacity of aluminium = 0.553 Jg-1 C-1
Specific heat capacity of water = 4.18 Jg-1 C-1
Water density = 1.0 g mL-1
Solution

T = (27.8 -25.0 ) C = 2.8 C

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)(2.8 C )
= 24676.71 J
= 24.68 kJ
= 24.7 kJ
Exercise
A coffee-cup calorimeter contains of 94g of
water at 20oC. To it added 22 g of water
60oC. Assuming that the heat absorbed by
the calorimeter is negligible, calculate the
final temperature of water.
(Specific heat of water = 4.18 J/g oC-1)

Answer: 27.6oC
Example of Past Year UPS Questions (2005/2006)
A bomb calorimetric experiment is performed with
powdered xylose, C5H10O5 as the combustible
substance. The data obtained are:
mass of xylose burned = 1.183 g
heat capacity of calorimeter = 4.728 kJ0C-1
initial calorimeter temperature = 23.29 0C
final calorimeter temperature = 27.19 0C
i) Calculate the heat of combustion of xylose, in
kJmol-1? (Answer: 2337.14 kJmol-1)
ii) Write the thermochemical equation for combustion
of xylose.
Example of Past Year UPS Questions
(2006/2007)

A 0.1375 g of magnesium is burnt in a

constant volume bomb calorimeter that has a
heat capacity of 1769oC-1. If the calorimeter
contains 300 g of water and the temperature
increases by 1.126oC, calculate the heat of
combustion of magnesium in kJ/mol.
(Specific heat of water = 4.18 J/g oC-1)

Answer: 594 kJ/mol

 Learning outcomes
At the end of this topic, students should be able to:
(9.3 Hesss Law)
a) State Hesss Law
b) Apply Hesss law to calculate enthalpy changes using
the algebraic method and the energy cycle method.
(9.4 Born-Haber cycle )
a)Define lattice energy and electron affinity.
b)Explain the following effects on the magnitude of
lattice energy.
i. Ionic charges
ii. Ionic radii
- states that when reactants are converted to
products, the change in enthalpy is the same
whether the reaction takes place in one step or
in the series of steps

(enthalpy change depends only on the nature

of the reactants & products & is independent of
the route taken)
Example

H6
A B
H1 H4

P Q R
H2 H3

H1 + H6= H2 + H3 + H4
a) Algebraic method and energy cycle

The enthalpy changes can be calculated by

(i) Algebraic method

(ii) Energy cycle method
Example 1:
Find the standard enthalpy of formation
of ethane C2H6(g). Given the following data:

C (graphite) = 393 kJmol 1

Hc

H2(g) = 286 kJmol 1

Hc

Hc C2H6(g) = 1560 kJmol 1

Solution:

(i) Algebraic method

Write chemical eq. for the given enthalpy change

a. C (s) + O2 (g) CO2 (g) H = 393 kJ

b. H2 (g) + O2 (g) H2O(g) H = 286 kJ
c. C2H6 (g) + 7/2 O2 2CO2 (g) + 3H2O (g) H = 1560 kJ

Chemical equation for the formation of ethane

2C (s) + 3H2 (g) C2H6 (g) H = ?

-to obtain one equation containing C & H2 as
reactants & C2H6 as product, O2 , CO2 & 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(g) C2H6(g) + 7/2 O2(g) H = +1560 kJ

2C(s) + 2O2(g) 2CO2(g) H = 2( 393) kJ
3H2(g) + 3/2 O2(g) 3H2O(g) H = 3( 286) kJ

2C (s) + 3H2 (g) C2H6 (g) = +1560-786-858

= 84 kJ

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

(i) Energy cycle method

- Write the chemical equation for the required

enthalpy change.

- Look at the data given, if values are given,

complete the cycle by writing the combustion eq. If
values are given, elements must make up the cycle.

- Draw the cycle and add the values (multiplying by a

factor where necessary)

- Draw the energy cycle and apply Hesss Law to

calculate the unknown value.
 HOf
2C (s ) + 3H2 (g) C2H6 (g)

H O2 = 3(-286)
HO1 2O2 (g) 3/2 O2 (g)
7/2 O2 (g)
= 2(-393)
HO3 = - (-1560)

2CO2 (g) + 3H2O (g)


H f = 2( H1 ) + 3( H 2 ) + H 3
= 786 858 + 1560
= 84 kJ mol 1
 Example
Calculate the Hf for

CuS (s) + 2O2 (g) CuSO4 (s)

Given:
2Cu (s) + O2 (g) 2CuO (s) H = -310 kJ
2S (s) + 3 O2 (g) 2 SO3 (g) H = -790 kJ
CuO (s) + SO3 (g) CuSO4 (s) H = -220.0 kJ
Cu (s) + S (s) CuS (s) H = -48.5 kJ

Ans: -721.5 kJ
 Example
Find the standard enthalpy of formation of
methane CH4 (g) if the following data is
given:

Hc CH4 = -891 kJmol-1

Hf CO2 = -393 kJmol-1
Hf H2O = -286 kJmol-1

Ans= -74 kJmol-1

 Lattice Energy ( H lattice )

- the heat change when 1 mole of solid (ionic

compound) is formed from its constituent
gaseous ions

Na+ (g) + Cl (g) NaCl (s) H = -771 kJ mol 1

- Lattice energy changes are large & the values

are negative because energy is needed to
break apart the lattice
The lattice energy becomes more negative as
- the ionic charges increase
- the ionic radii decrease

There is a stronger attraction between small,

highly charged ions,so the H is more negative

MgO has a more negative H than Na2O

because

-Mg2+ is smaller in size & has bigger charge

than Na+. so, lattice E, MgO > Na2O
 Learning outcomes
At the end of this topic, students should be
able to:

c) Explain the dissolution process of ionic solids.

d)Construct Born-Haber cycle for simple ionic solids
using energy cycle diagram.
e)Calculate enthalpy changes using Born-Haber
cycle.
 The hydration process
of ionic crystal in water
- Water is a polar molecule

- When an ionic compound dissolves in water,

positive end of water molecule will attract the
negative ion & negative end of water will
attract the positive ion

- Electrostatic forces between the gaseous ions

& water molecules will release hydration
energy
Example

H
H H
H
O
O O
H H
+
Na H
H
O O
O
H H
H H
 Example:
O
H H O

H H

Cl-
H

H
H O
H
O
The dissolution Process for NaCl
 Hsolution
MX (s ) M+ (aq )+ X - (aq )

Hlattice
Hhyd

M+ (g ) + X - (g )

According to Hesss Law

Hhyd = Hsolution + Hlattice
Hsolution= Hhyd - Hlattice
Hhyd > Hlattice , Hsolution negative ,
crystal soluble in water

Hhyd < Hlattice , Hsolution positive,

crystal insoluble in water ----highly positive
soluble in water ------low/moderately high

Hhyd ~ Hlattice , Hsolution 0,

crystal soluble in water
- The process of ionic bond formation can be
broken down into stages

- At each stage the enthalpy changes are

considered

- The Born Haber cycle is often used to calculate

the lattice energy of an ionic compound

- Useful for predicting the stability or existence of

ionic compound.
 Formation of NaCl +

Ionization energy
+
+
Na(s) +
+
+
+
+
+
+
- -
- +
+
+
+ +
+
+ - -
+
-
Enthalpy of sublimation - +
e- + + +

/ atomization energy
- -
-
- - +

-
+ +
-
- -
- -
- Lattice
- -
Cl2(g) energy
- -
Atomization - -
energy Electron
affinity
 Example Born-Haber Cycle
H1
Na (s) + Cl2 (g) NaCl (s)
H2 H4
Na(g) Cl (g)
H3 H5 H6
Na+(g) + Cl (g)
H1=Enthalpy of formation of NaCl
H2=Enthalpy of sublimation / atomization energy of Na
H3=First ionization energy of Na
H4=Atomization energy of Cl
H5=Electron affinity of Cl
H6=Lattice energy of NaCl
 A Born-Haber cycle for NaCl

energy
Na+(g) + e + Cl(g)
IE of Na EA of Cl
Na+(g) + Cl- (g)
Na(g) + Cl(g)
HaCl
Na(g) + Cl2(g)
+ve Lattice
HaNa energy
Na(s) + Cl2(g)
E=0
Hf NaCl
-ve NaCl (s)
 Example :
Na(s) 1
2 Cl2(g) NaCl(s)
Given;
i. Enthalpy of formation NaCl = -411 kJmol-1
ii. Enthalpy of sublimation of Na = +108 kJmol-1
iii. First ionization energy of Na = +500 kJmol-1
iv. Enthalpy of atomization of Cl = +122 kJmol-1
v. Electron affinity of Cl = -364 kJmol-1
vi. Lattice energy of NaCl = ?
 H1
Na (s) + Cl2 (g) NaCl (s)
H2 H4
Na(g) Cl (g)
H3 H5 H6
Na+(g) + Cl (g)
From Hesss law

H1 = H2 + H3 + H 4 + H5 + H6
-411 = 108 + 500 + 122 + -364 + H6
-411 = 364 + H6
H6 = -411 - 364
-777 kJmol-1
=
 energy
Na+(g) + e + Cl(g)
IE of Na EA of Cl
Na+(g) + Cl- (g)
Na(g) + Cl(g)
HaCl
Na(g) + Cl2(g)
+ve Lattice
HaNa energy
Na(s) + Cl2(g)
E=0
Hf NaCl
-ve NaCl (s)

From Hesss Law : Hf NaCl = HaNa + HaCl +IENa +

EACl + Lattice Energy
 Calculation:
0
H f H S IE H a (Cl ) EA H lattice
0
H lattice H f H S IE H a (Cl ) EA
H lattice 411 108 500 122 364
H lattice 777kJ / mol
 Exercise 1
Construct a Born-Haber cycle to calculate the
lattice energy for Cadmium (II) iodide
H / kJ
Cd (s) + I2 (s) CdI2 (s) -201
Cd (s) Cd (g) +113
Cd (g) Cd2+ (g) + 2e- +2490
I2 (s) I2 (g) +19
I2 (g) 2I (g) +151
2I (g) + 2e- 2 I- (g) -628
 Exercise 2

H1 = -322 kJmol-1 Formation Enthalphy KCl

H1 =- -1
H3 = 108 kJmol K Atomization
411kJmol -1
H4 = 121 kJmol -1 K Ionization energy
H5 = -364 kJmol-1 Cl electron affinity

H6 = -776 kJmol-1 KCl Lattice energy

Calculate the value of in the Born-Haber

H2 cycle? Determine the type of enthalpy
involved.
 Exercise 3
H / kJmol-1
Enthalpy of atomization of potassium, K +90
Enthalpy of atomization of chlorine, Cl +121
First Ionization energy of K +418
Electron affinity of Cl -364
Enthalpy of hydration of K+ -322
Enthalpy of hydration of Cl- -364
Lattice energy of KCl -701
Calculate: 1. enthalpy of formation of KCl
2. enthalpy of solution of KCl
 NOTES
H formation more negative, the compound
is more stable.

Lattice energy more negative, the compound

is more stable ( can be exist ), melting point
is higher ( stronger ionic bond ).
 Exercises

1. Give the corresponding thermochemical

equation for enthalpy of formation of
each enthalpy change.

a. SO3 H0f = -395 kJ/mol

b. CuS H0f = -48.5 kJ/mol
c. CH3COOH H0f = -484.5 kJ/mol
d. CO2 H0f = -394 kJ/mol
2. When 0.36 g benzoic acid, C7H6O2 (H0c = 395
kJ/mol) is completely burnt in a bomb calorimeter,
the temperature of the water rises by 0.87 K. The
complete combustion of 0.90 g of oxalic acid,
C2H2O4 in the same calorimeter causes a
temperature rise of 0.23 K.

a) Determine the heat capacity of the calorimeter.

( Answer: 10.96 kJ)
b) Calculate the enthalpy of combustion of oxalic
acid. ( Answer: -252 kJ/mol)
3. A calorimeter contains 400 mL of water
at 250C. If 600 mL at 60 0C of water is
added to it, determine its final
temperature. Assume that the heat
absorbed by the calorimeter is negligible.

(Answer = 460C)
4. Given the following thermochemical equations:
H2(g) + O2(g) H2O (l) H = -286 kJ/mol
N2O5 (g) + H2O (l) 3HNO3 (l) H = -76.6 kJ/mol
N2(g)+3/2O2(g)+ H2HNO3(l) H = -174.6 kJ/mol

Calculate the enthalpy change,H for the reaction

2N2 (g) + 5O2 (g) 2 N2O5(g)

Answer = + 28.8 kJ
5. A beaker contains 0.50 kg of water at 20 C.
Calculate the minimum mass of methane gas
( CH4 ) that should be burn to increase the
water temperature to 100 C.
( Specific heat capacity of water = 4.18 Jg-1K-1
and H = 890.0 kJ mole-1 )

Mass = 3g
6. Refer to the combustion of ethanol below :
C2H5OH (l) + 3O2(g) 2CO2(g) + 3H2O (l)
H = -1366.8 kJ/mole

Enthalpy of formation of CO2 (g) and H2O (l) are

-393 kJ/mole and -285.5 kJ/mole. Calculate the
standard enthalpy of formation of ethanol.

-276.7 kJ/mole
7.Draw the Born-Haber cycle for the formation of
magnesium chloride, MgCl2 from magnesium metal and
chlorine gas. Calculate the enthalpy of MgCl2. Given:

Enthalpy of sublimation of Mg H1 = +149 kJ/mol

First ionization energy of Mg H2 = +740 kJ/mol
Second ionization energy of Mg H3 = +1456 kJ/mol
Enthalpy of atomization of Cl H4 = +240 kJ/mol
Electron affinity of Cl H5 = -369 kJ/mol
Lattice energy of MgCl2 H6 = -3393 kJ/mol

Answer: -1306 kJ/mol

Example of Past Year UPS Questions (2006/2007)
Based on the data given below:
H0 hydration Na+ = -390 kJ/mol
H0 hydration Cl- = -380 kJ/mol
H0 solution NaCl = +6 kJ/mol

i) Construct an energy cycle diagram to

represent the dissolution of NaCl.
ii) Calculate the lattice energy of NaCl.

Answer : -776 kJ/mol

 PSPM 2008/09
Calcium fluoride, CaF2, is a stable compound
in the solid state. The enthalpy of solution is
affected by the lattice energy and the
hydration energy of the ionic solid. Using CaF2
as an example, define standard enthalpy of
solution and lattice energy.
Construct a Born-Haber cycle for CaF2 in the solid state by
using the data below. Calculate the lattice energy of CaF2.
H (kJ/mol)
First ionization energy of Ca +590
Second ionization energy of Ca +1150
Standard enthalpy of atomization of Ca +178
Bond energy of FF +158
Electron affinity of F -328
Standard enthalpy of formation of CaF2 -1220
What would you expect the lattice energy of calcium chloride,
CaCl2, compared to that of CaF2? Explain your answer.

In terms of solubility in water, CaF2 is less soluble than CaCl2.

Explain the observation.