Forms of Energy and

Energy Changes
What we are learning under this topic

 Enthalpy and enthalpy changes

 Relationship between Lattice Energy, heat of solution and heat of hydration

 Entropy and entropy changes

 Free energy change and Gibb’s free energy at equilibrium

 First, second and third laws of thermodynamics

ENERGY

Energy is the
ability to do work
Forms of Energy

 Mechanical energy – potential and kinetic energies

 Heat or thermal Energy
 Light Energy
 Electrical Energy
 Sound or Vibrational Energy
 Chemical Energy
 Nuclear Energy
Note: Various forms of energy changes accompany
different chemical reactions.

For example;
 Reaction between a strong acid and strong base - Heat

 Burning of magnesium in air - light and heat

 Ignition of a mixture of hydrogen and oxygen - sound and

heat
Enthalpy and Enthalpy Change

 The heat content of a substance is known as its enthalpy. H

 The change in heat content when the substance

undergoes a reaction is known as enthalpy change or
heat of reaction. Denoted with ∆H

 Generally,
Heat of reaction,
∆H = H(product) – H(reactant)
Relationship between Lattice Energy,
heat of solution and heat of hydration
 When chemical reactions occur, it is accompanied by a series of
bond - breaking and bond – forming.
 Bond - breaking is endothermic (+ve)
 Bond - forming is exothermic (-ve)
 Endothermic change (∆H = + ve) occurs when
Bond-breaking energy(∆H = +ve) > Bond forming energy (∆H=-ve)
 Exothermic change (∆H = - ve) occurs when
Bond-breaking energy (∆H = +ve) < Bond forming energy (∆H=-ve)
The value of ∆H is accurately
determined experimentally with the aid
of a calorimeter

 Bomb Calorimeter – for nutrition studies

 Glass calorimeter - for most chemical reactions

 H = mcθ is then used to determine the heat change.

Terms have their usual meanings.
Standard Conditions for Measuring ∆H

 Temperature of 25oC or 298K

 Pressure of 1 atm (or 1.01 x 105 nm-2 or 760 mmHg) for gases

 Concentration of 1 moldm-3 if aqueous solutions are involved.

 Formation or burning of a mole of substance

Relationship between Lattice Energy,
heat of solution and heat of hydration
During the dissolution of an ionic solid in water, a two-step process occurs;

 Splitting of the ions in the crystal into free ions by water molecules.
Energy involved – Lattice energy (endothermic )

 Hydration of the free ions by water molecules.

Energy involved – Hydration energy (exothermic )

So, heat of solution is

Endothermic if Lattice energy < Hydration energy

But Exothermic if Lattice energy > Hydration energy

The Standard Heat of Solution

Is the amount of heat absorbed or evolved

when one mole of a substance is dissolved in
so much water that further dilution results in
NO detectable heat change.
Bond Energy and Lattice Energy

 Bond energy is the average amount of energy associated with making or

breaking 1 mole of a particular bond, in its gaseous state.
- helps to understand the stability of covalent molecules
 The lattice energy of an ionic crystal is the heat of formation of one mole
ionic compound from widely separated gaseous ions under standard
conditions.
- helps to understand the stability of ionic compounds
 Both bond energy and lattice energy can not be determined experimentally
but theoretically.
Entropy and entropy Change

 Entropy(S) is the degree of disorder or randomness of a system.

 ∆S is change in entropy.
 Mathematically;
∆𝐻
∆S = where H -= enthalpy change
𝑇
T = Temperature in kelvin
It is related to the Gibb’s free energy, ∆G by

∆G = ∆H - T ∆S
Gibb’s free energy, G, is the energy available to do work.
Thermodynamics

Thermodynamics is the study of the

relationship between heat and other
forms of energy.
Laws of thermodynamics

The first law of thermodynamics states that

energy can neither be created nor destroyed but
may be converted from one form to another.
It is also known as the law of conservation of energy.

Mathematically,
∆U = q + w
∆U = Change in internal energy
q = heat absorbed by the system
w = work done by the system
The second law of thermodynamics states that a
spontaneous process occurs only if there is an
increase in the entropy of a system and its
surrounding.

The third law of thermodynamics states that at

absolute zero temperature, the entropy of a
perfect crystal is zero
Implication of the signs of ∆G

A reaction is spontaneous when ∆G is negative

non-spontaneous when ∆G is positive
in a state of equilibrium when ∆G is zero

So, from ∆G = ∆H - T ∆S

It follows that for a reaction to be spontaneous, ∆G is negative and

∆S is positive
FREEE ENERGY CHANGE AND
EQUILIBRIUM CONSTANT
Gibbs free energy change under non- standard conditions,
∆G = ∆Gθ + RT lnK
Where K is equilibrium constant
R is universal gas constant = R = -8.314JK-1mol-1
T is absolute temperature (Kelvin)
At equilibrium, ∆G = 0
So that; ∆Gθ = -RT ln K
Or ∆Gθ = -2.303RT log10 K
This equation is known as the Van’t Hoff Isotherm
Equation
Equilibrium constant ∆Gθ is also related to
the standard electrode potential by the
equation
∆Gθ = - n F E θ
Where n is the number of moles of electrons
E is the standard electrode potential
and F is the Faraday’s constant.
So, that ,
∆Gθ = -RT ln K = - n F Eθ

And Eθ = RT ln K
nF
Example

Calculate ∆Gθ for the following equilibrium

reaction for which the equilibrium constant
at 25oC is 1.78 x 10-7 :
PCl5(g)  PCl3(g) + Cl2
(R = -8.314JK-1mol-1)
Solution

∆Gθ = -RT ln K
= -8.314 JK-1 mol -1 X 298K x ln (1.78 x 10-7)
= -8.314JK-1 mol -1 x 298 K x (-15.5415)
= +38,505.14 J K-1 mol -1
= + 38.51kJ mol-1
Equations to remember

∆U = q + w
∆𝑯
∆S =
𝑻
∆G = ∆H - T ∆S
∆Gθ = -RT ln K
∆Gθ = - n F E θ
Reflection Time

What have you learnt in the

last 30 minutes?
If the change in free energy of a system is -
899 Jmol-1 and the change entropy change is
10 Jmol-1K-1 at 25oC, calculate the enthalpy
change.

Answer = + 2081 J mol-1

In which? of the following is the entropy
positive

A.Thermal dissociation of ammonium chloride

B. Reaction between an acid and a base

C. Addition of concentrated acid to water

D. Dissolution of sodium metal in water

If a reaction is exothermic and there is a
great disorder, it means that
A. the reaction is static
B. the reaction is in a state of equilibrium
C. there will be a large increase in free energy
D. there will be a large decrease in free energy
In an endothermic reaction, if there is a
loss in entropy, the will

A. Be indeterminate
B. Be spontaneous
C. Not be spontaneous
D. Be at equilibrium
Further Practice
For the equilibrium reaction;
SO2(g) + NO2(g)  SO3(g) + NO(g)
The change in the standard free energy was
found to be -35.15 KJmol-1 at 25oC. Calculate
the equilibrium constant for the reaction at
this temperature.
Answer

K = 1.45 x 106
The solubility product of lead sulphide, PbS,
is 1.3 x 10-28 at 25oC, determine the solubility
of lead sulphide at this temperature

A. 11.4 x 10 -14 mol.dm-3

B. 1.3 x 10 -28 mol.dm-3
C. 1.14 x 10 -14 mol.dm-3
D. 1.3 x 10-14 mol.dm-3
E. 6.5 x 10-14 mol.dm-3