CHAPTER 1

Dr. Nurul Auni Zainal Abidin

Faculty of Applied Sciences
UiTM Negeri Sembilan
 At the end of the topic, students will be
able to:

1. relate enthalpy change with the amount of product or reactant

2. describe the basic concept in thermochemistry
3. measure heat changes during chemical reaction
4. apply Hess’s Law for enthalpy of formation
Thermodynamics is the study of heat and its transformations.

Thermochemistry is a branch of thermodynamics that deals with

the heat involved with chemical and physical changes.

the surroundings

the system
 Concept of Enthalpy
The heat content of the system is known as the
enthalpy of the system.
The total heat absorbed or liberated in a chemical
reaction is called the heat of reaction.
We cannot measure the absolute value of the enthalpy
of the system, but we can measure the change in
enthalpy.
The experimental technique for measuring enthalpy
changes is called calorimetry.
Calorimeter is a device for measuring quantities of
heat.
 SIMPLE
CALORIMETER

Figure: A simple calorimeter can be constructed

from two polystyrene cups. A thermometer and
stirrer extend through the cover into the reaction
mixture.
COMMERCIAL
SOLUTION
CALORIMETERS

Figure: Commercial solution calorimeters range from (a) simple, inexpensive

models for student use to (b) expensive, more accurate models for industry and
research.
 Concept of Enthalphy
 The symbol for the change in enthalpy is ∆H.
 Enthalphy (H) is measured in the units of kJ.

For a reaction A + B C + D,

∆H = Total enthalpy of the products – Total enthalpy of the

reactants
= H2 – H1

Where H2 = (HC + HD) and H1 = ( HA + HB)

 Exothermic Reaction
An exothermic reaction releases
heat to the surroundings and is
shown by a rise in temperature.
The enthalpy change of the reaction,
∆H has a negative value because the
heat content of the products is less
than the heat content of the
reactants.
Energy
Reactant
s
Heat liberated
( ∆H negative)
Products

The energy level diagram for an exothermic reaction.

 Endothermic Reaction
An endothermic reaction absorbs
heat from the surroundings and is
shown by a fall in temperature.
The enthalpy change of the
reaction, ∆H, has a positive value
because the heat content of the
products is higher than the heat
content of the reactants.

Energy Products

Heat absorbed
( ∆H positive)

Reactants

The energy level diagram for an endothermic reaction.

Exothermic and Endothermic Reactions
Endothermic vs Exothermic Reactions

The endothermic reaction is The exothermic reaction is

cooler than surroundings hotter than surroundings
 Dissolving
Nucleosynthesis of
ammonium
elements heavier
chloride in water
than nickel in stars

Photosynthesis
Endothermic
Evaporating liquid
Process Cracking
water alkanes

Melting ice
 The thermite A neutralization reaction
reaction (e.g., mixing an acid and a
base to form a salt and
Combustion of a water)
fuel

Exothermic Nuclear fission

Most polymerization
reactions Process
Corrosion of metal
(an oxidation Respiration
reaction)
 Energy Profile
The activation energy (Ea) is the energy barrier which the
reactant molecules must overcome if they are react successfully
to form the product molecules.
Ea = activation energy
Energy

Energy
∆H = enthalpy of reaction
reactants Ea
products

∆H Ea ∆H
reactants

products
Progress of reaction Progress of reaction
(a) Exothermic reaction (b) Endothermic reaction
 Standard Conditions for calculating
Enthalpy Changes
 The numerical value of enthalpy change is influenced by 5 factors:
(a)The temperature at which the experiment is carried out
(b)The physical states (solid, liquid, gas) of the reactants – for example,
the reaction between solid iodine and hydrogen is endothermic, but
the reaction between gaseous iodine and hydrogen is exothermic.
(c) The allotropic forms of the reactants
(d)The pressure of the gaseous reactants
(e)The concentration of the reactants.

The standard conditions for measuring enthalpies are:

1.Temperature of 25 oC (298 K)
2.Pressure of 1 atm (or 101 kPa)
3.Solutions having a concentration of 1.0 mol dm-3
 Calorimeter
Any device used to measure
temperature changes resulting from
enthalpy changes in chemical
reactions or physical changes is
called a calorimeter.
The experimental technique of using
a calorimeter to determine the
enthalpy change of a reaction is
called calorimetry.
 Determining the Heat of a Reaction

PROBLEM: 50.0 mL of 0.500 M NaOH is placed in a coffee-cup calorimeter at

25.00oC and carefully add 25.0 mL of 0.500 M HCl, also at 25.00oC.
After stirring, the final temperature is 27.21oC. Calculate qsoln (in J) and
Hrxn (in kJ/mol). d = 1.00 g/mL and c = 4.184 J/g*K
PLAN: Use volumes and density to find the mass of the water. Calculate the
moles of NaOH and HCl. Write balanced equations and determine the
limiting reactant. Calculate qsoln using the mass, c, and T and finally
dividing by the moles of water gives the heat per mole.
SOLUTION:
Mass(25.0 + 50.0) mL x 1.00 g/mL= 75.0 g of water
T = (27.21 – 25.00)oC = 2.21oC = 2.21 K q = mass x specific heat x T
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) = 75.0 g x 4.184 J/g*K x 2.21 K
H+(aq) + OH-(aq) H2O(l)
= 693 J
NaOH 0.500 M x 0.0500 L = 0.0250 mol OH-
(693 J/0.0125 mol H2O)(kJ/103 J)
HCl 0.500 M x 0.0250 L = 0.0125 mol H+ = 55.4 kJ/ mol H2O formed
HCl is the limiting reactant, so 0.0125 mol H2O.
Bomb
Calorimeter
A bomb calorimeter is a type
of constant-volume
calorimeter used in
measuring the heat of
combustion of a particular
reaction. 
 Calculating the Heat of Combustion

PROBLEM: A manufacturer claims that its new dietetic dessert has “fewer
than 10 Calories per serving.” To test the claim, a chemist at
the Department of Consumer Affairs places one serving in a
bomb calorimeter and burns it in O2 (the heat capacity of the
calorimeter = 8.151 kJ/K). The temperature increases 4.937oC.
Is the manufacturer’s claim correct?
PLAN: - q sample = qcalorimeter

SOLUTION: qcalorimeter = heat capacity x T

= 8.151 kJ/K x 4.937 K

= 40.24 kJ
Calorie (cal) 1 cal = 4.184 J
40.24 kJ kcal = 9.63 kcal or Calories
4.184 kJ
The manufacturer’s claim is true.
 Heat Capacity
When heat is supplied to a substance, the temperature of the substance
increase.
The magnitude of the increase depends on the heat capacity of the
substance.
The heat capacity (C) is the amount of heat needed to change the
temperature of substance by 1 oC. It is measured in J oC-1 or J K-1
The specific heat capacity (c) of a substance is the energy required to
raise the temperature of one gram (1 g) of the substance by 1 oC. The unit
is J g-1 oC-1

Heat capacity = specific heat capacity x mass

J oC-1 = (J g-1 oC-1) x g
 Heat Capacity
The formula used to calculate heat absorbed or evolved during a
reaction is as follows.

q = mc or q = C

where q = heat change (absorbed or liberated)

c = specific heat capacity of the substance
C = heat capacity of the substance
 = change in the temperature
m = mass
 Example
How much heat energy is released when 7.1 g of substance is cooled
from 100 oC to room temperature (25 oC) ?
(The specific heat of the substance is 0.460 J g-1 oC-1)

Solution:
Heat released (q) = mc = 7.1 g x 0.460 J g-1 oC-1 x (100-25) oC = 245 J
 Calculating Heat Change in Calorimeter
EXAMPLE:

250 cm3 of 0.50 mol dm-3 KOH solution at 31.0 oC is mixed with the same
volume of 0.50 mol dm-3 HCl at the same temperature in a polystyrene
beaker. Calculate the maximum temperature reached for the reaction. The
specific heat capacity of the solution = 4.2 J g-1 K-1 and the heat capacity of
the polystyrene beaker is very small and can be ignored.
Given: ∆H neut = -57.3 kJ mol -1
 Example
Solution:
Number of moles of OH- (aq) ions used = MV = 0.50 x 250 = 0.125 mol
1000 1000
 Number of moles of H+ (aq) used = 0.125 mol

For the reaction between a strong acid and a strong alkali

KOH (aq) + HCl (aq) KCl (aq) + H 2O (l) ∆H neut = -57.3 kJ mol -1

Heat liberated during neutralisation = 57.3 kJ mol -1 x 0.125 mol = 7.163 kJ

Let the maximum temperature reached = x oC

Q = mc
(7.163 x 1000) J = (250 + 250) g x 4.2 J g-1 oC-1 x (x – 31.0 ) oC
x = 34.4 oC
Stoichiometry Of Thermochemical
Equations
Stoichiometry Of Thermochemical
Equations
1
2
3
 Example
250 cm3 of 0.50 mol dm-3 NaOH initially at 27.5 oC is added
to 250 cm-3 of 0.50 mol dm-3 HCl, also at 27.5 oC, in a plastic
cup. The maximum temperature recorded is 30.9 oC.
Calculate the standard enthalpy of neutralization between
NaOH and HCl.

[Density of solution = 1.0 gcm-3; specific heat capacity of

solution = 4.2 J g-1 K-1].
 Solution
Answer:
NaOH (aq) + HCl (aq) → NaCl(aq) + H2O (l)

Heat evolved, q = m c 
= (250 + 250) g x 4.2 J g-1 K-1 x (30.9-27.5) oC
= 7140 J
Number of moles of NaOH = Number of moles of HCl
= 250 x 0.5
1000
= 0.125 mol
H = q = 7140 J = 57120 J mol-1 or 57.12 kJ mol-1
n 0.125 mol
The standard enthalpy of neutralization = - 57.12 kJ mol-1
4
5
 Hess’s Law
the magnitude of the enthalpy change of a chemical reaction depends only on the difference in the
enthalpy content of the products and the reactants, and does not on how the reaction is
completed.

The law states that the enthalpy change for a reaction that is carried out in a
series of steps is equal to the sum of the enthalpy changes for the individual
steps.

∆H1
A B

∆H3 ∆H2

∆H4
C D
By Hess’s Law:
∆H1 + ∆H2 = ∆H3 + ∆H4
 Hess’s Law
Consider the following enthalpy cycle.

∆H
A D

∆H1 ∆H3

∆H2
B C

What is the relationship between ∆H, ∆H1, ∆H2, and ∆H3?

Solution:
∆H = ∆H1 + ∆H2+ ∆H3
 Applications of Hess’s Law
C (s) + 2H2(g) →CH4 ∆H  f = ??
CH4 (g) + 2O2 (g) →CO2 (g) + 2H2O (l) ∆H  c [CH4]= -891 kJmol-1
C(s) + O2(g) → CO2(g) ∆H  f [CO2]= -393 kJmol-1
H2(g) + ½ O2 (g) → H2O (l) ∆H  f [H2O]= -286 kJmol-1
Method 1 : Algebraic method
CO2(g) + 2H2O (l) → CH4 (g) + 2O2 (g) ∆H1 = ∆H  c[CH4] (+891 kJmol-1)
C(s) + O2 (g) → CO2(g) ∆H2 = ∆H  f [CO2](-393 kJmol-1)
2H2(g) + O2 (g) → 2H2O (l) ∆H3 = 2∆H  f [H2O](-572 kJmol-1)
C(s) + 2H2 (g) → CH4 (g) ∆H  f [CH4] = ∆H1 + ∆H2+ ∆H3

= -∆H  c[CH4]+ ∆H  f [CO2]+ 2 ∆H  f [H2O]

= - (-891) + (-393)+ 2(-286)
= -74 kJmol-1
 Applications of Hess’s Law
Method 2 : Energy cycle method

∆H  f[CH4]
C (s) + 2H2(g) CH4 (g)

-393 2 x (-286) -891

CO2 (g) + 2H2O (l)

∆H  f [CH4] = (-393) + 2 x (-286) + (+891) = -74 kJmol-1

Standard enthalpy change of
atomization
The heat absorbed to form 1 mol of gaseous atoms from the element
under standard condition
Eg:
◦ ½ Cl2 (g) Cl2(g)
◦ Na (s) Na (g)
Standard ionization energy
The first ionization energy is the minimum heat energy required to
remove one electron from an isolated atom under standard condition.
Eg:
◦ M(g) M+ (g) + e-
◦ M+ M 2+ + e- (second ionization energy)

Generally, the bigger the size of an atom, the lower the ionization
energy.
Electron affinity

The first electron affinity is the heat energy liberated when a gaseous
atom receives an electron to form an anion under standard condition
Eg
◦ M(g) + e- M- (g)
◦ Cl(g) + e- Cl- (g)
◦ S- (g)+ e- S2- (g) (second electron affinity)

Generally, the smaller the atomic size, the more negative is the electron
affinity
Lattice energy
The lattice energy of an ionic compound is the heat energy released
when 1 mole of the ionic solid is formed from gaseous ion in standard
condition
Eg
◦ Na + (g) + Cl- (g) NaCl

The higher the charge or the smaller the size of the ions, the stronger is
the ionic bond and the more negative the lattice energy
 The Born-Haber Cycle
Lattice energy cannot be measured directly from experiments.
It can be obtained indirectly using Hess’ law and Born-Haber
Cycle

Born Haber Cycle:special thermochemical cycle for the formation

of ionic solids
 The standard enthalpy of formation of sodium chloride is -411kJmol-
1
 Na(s) + ½ Cl2(g) NaCl (s) ∆Hf = -411 kJmol-1

 This reaction can be thought of comprising the following steps:

 Atomization of sodium and chlorine
 Na(s) Na(g) ∆H = 108 kJmol-1
 ½ Cl2(g) Cl (g) ∆H = 121 kJmol-1

 First ionization of Na
 Na(g) Na+ + e- ∆H = 494 kJmol-1

 First electron affinity

 Cl (g) + e- Cl- ∆H = -364 kJmol-1
 Formation of NaCl, lattice energy
 Na+(g) + Cl-(g) NaCl(s) ∆H = lattice energy
Born-Haber Cycles
eg for sodium chloride:

Na+ (g) + e- + Cl (g)

enthalpy H
H first ionisation energy H first electron affinity

Na (g) + Cl (g)
Na+ (g) + Cl- (g)
H atomisation

Na (g) + ½ Cl2 (g)

H atomisation H lattice
Na (s) + ½ Cl2 (g) enthalpy

H formation
NaCl (s)
Born-Haber Cycles : applying Hess’s Law
There are two routes from elements to ionic compound

Na+ (g) + e- + Cl (g)

enthalpy H
H first ionisation energy H first electron affinity

Na (g) + Cl (g)
Na+ (g) + Cl- (g)
H atomisation

Na (g) + ½ Cl2 (g)

H atomisation H lattice
Na (s) + ½ Cl2 (g) association
Apply
Hess’s H formation
Law:
NaCl (s)

HatmNa + HatmCl + H1st IE + H1st EA + Hlattice = Hformation

Born-Haber Cycles: applying Hess’s Law

HatmNa + HatmCl + H1st IE + H1st EA + Hlattice = Hformation

Rearrange to find the lattice energy:

Hlattice = Hformation - (HatmNa + HatmCl + H1st IE + H1st EA)

Hlattice = -411 –( 108 + 121 + 494- 364)

= - 770 kJmol-1

So Born-Haber cycles can be used to calculate a measure of

ionic bond strength based on experimental data.
 BORN-HABER CYCLE
FOR
SODIUM CHLORIDE (HOW TO DRAW ENERGY DIAGRAM?)
kJ
+800

+700

+600

+500

+400

+300

+200
Na(g) + 1/2 Cl2(g)
+100
Na(s) + 1/2 Cl2(g)
H= +107kJmol-1
0

-100

-200

-300
Atomisation of sodium
-400
kJ
+800

+700

+600

+500

+400

+300
Na(g) + Cl(g)
+200
Na(g) + 1/2 Cl2(g)
H = +121kJmol-1
+100
0 Na(s) + 1/2 Cl2(g)

-100

-200

-300
Atomisation of chlorine
-400
kJ
+800
Na+(g) + Cl(g)
+700
ee- - -
+600
ee-
e- -
+500 e -
e -
+400 e -
H = +502kJmol-1 e-
+300
ee-
Na(g) + Cl(g)
+200
Na(g) + 1/2 Cl2(g)
+
+100
0 Na(s) + 1/2 Cl2(g)

-100
First Ionisation of sodium
-200

-300

-400
kJ
+800
Na+(g) + Cl(g)
+700

+600
H = -355kJmol-1
+500

+400
Na+(g) + Cl-(g)
+300
Na(g) + Cl(g)
+200

+100
Na(g) + 1/2 Cl2(g) - e-
0 Na(s) + 1/2 Cl2(g)

-100

-200
First electron affinity of chlorine
-300

-400
kJ
+800
Na+(g) +
+700 Cl(g)

+600

+500

+400
Na+(g) + Cl-(g)
+300
Na(g) + Cl(g)
- + -
+200 + - +
Na(g) + 1/2 Cl2(g)
+100 - + -
0 Na(s) + 1/2 Cl2(g)

-100

-200 H = -411kJmol-1

-300 Formation of sodium chloride

-400
NaCl(s)
kJ
+800
Na+(g) +
+700 Cl(g)

+600

+500

+400
Na+(g) + Cl-(g)
+300
Na(g) + Cl(g)
+200
Na(g) + 1/2 Cl2(g) - + -
+100
+ - +
0 Na(s) + 1/2 Cl2(g)
- + -
-100
H = -786 kJmol-1
-200

-300
Lattice enthalpy for sodium chloride
-400
NaCl(s)
EXERCISE
Construct the Born Haber cycle for calcium chloride, and use it to calculate
the lattice energy of calcium chloride