KYAMBOGO UNIVERSITY

FACULTY OF SCIENCE
DEPARTMENT OF CHEMISTRY
BACHELOR OF SCIENCE IN CHEMICAL ENGINEERING
PHYSICAL CHEMISTRY ASSIGNMENT

YEAR TWO SEMESTER ONE

GROUP MEMBERS REG. NUMBERS

1. MUTALYA GEOFFREY 15/U/5209/CHD/PD

It is the amount of heat evolved when one mole of an acid reacts with one mole of a base to form one
mole of water

H ₊( aq) +OH ₋(aq ) → H 2 0(l)

EXPERIMENT

Experiment to determine the enthalpy of neutralization for example NaOH and HCl

A fixed volume say 50 cm3 of 2M HCl is measured into a plastic beaker and its initial temperature T 1
recorded.

Also a fixed volume say 50 cm3 of 2M sodium hydroxide is measured into another plastic beaker and its
initial temperature T 2 recorded.

Then sodium hydroxide solution is transferred to the beaker containing hydrochloric acid as rapidly as
possible, the mixture stirred and the maximum temperature T 3 of the solution is recorded.

TREATMENT OF RESULTS

T 1+ ¿T2
Initial temperature = ( ¿ ) °C
2

Final temperature =T 3°C

T1+ T2
Temperature change (rise) ∆T = [T 3−( )]°C
2

Mass of solution = (50 +50) cm3 ₓ 1g/ cm 3(The density of the mixture is assumed to be 1g/cm 3)

=100g

Heat generated is used to heat the solution

Heat change= mc∆t

=100 ₓ 4.2 ₓ ∆t JOULES

=420∆t Joules

2 ₓ 50
Moles of acid used =
1ooo

= 0.10 moles acid.

0.1 moles liberate 420∆t Joules

=4200∆t Joules

The enthalpy of neutralization is – 4200∆t J mol−1

QUESTION

15 cm3 of 0.5M HCl was pipetted into a plastic bottle (calorimeter). The temperature of the acid solution
and also that of a 0.5M solution of NaOH in a beaker was taken as 16.0 and 16.2 ° C respectively.

And as rapidly as possibly, 15cm3 of the 0.5M NaOH Solution was transferred into plastic bottle using a
pipette , and the thermometer was transferred into plastic bottle using a pipette, and the thermometer
was used to stir the mixture, the maximum temperature was recorded as 29°C. Calculate the heat of
neutralization of the above reaction.

SOLUTION

16.0+16.2
Initial temperature =
2

= (16.1°C+273)

=289.1k

Final temperature = (29°C+273)

= 302 K

Temperature difference, ∆t = (302-289.1) k

=12.9k

Total volume of solution = (15+15)cm 3 =30cm3

Mass of solution = 30 ₓ 1 g/ cm3(assumed the density of solution = 1g/cm3)

= 30g

Heat change =mc∆t

=30 × 4.2 × 12.9

=1625.4 J
₊
H OH ₋(aq ) → H 2 0(l)
( aq ) +
1000 cm 3of acid contains o.5 moles

0.5
15cm3 of acid contains ( ₓ 15) moles
1000

=7.5x 10−3 moles

7.5x10 moles liberate ( 1625.4 )joules

1625.4
1 mole liberates ( 7.5 ×10−3 )
J/mol

= 216720 J/mol

Enthalpy of neutralization = -216.72KJ/mol

THE REACTION ISOTHERM

The Gibbs free energy of a substance is defined in terms of the standard Gibbs free energy, G i0 and the
0
activity of the substance a i as G i = G i +nRTIna i………(i)

Dividing this equation by n, the number of mole, we get μi = μ0i + RTIna i.......... (ii)

0
Where μi is the chemical potential, μi is the standard chemical potential (chemical potential at unit
activity of the substance) and a i is the activity of the substance.

We will write an expression for the change in free energy involved in any type of transformation,
physical or chemical.

Consider first a simple reaction consisting of only two reactants and two products.

The chemical equation is;

V 1 A1 +V 2 A 2 →V 3 A 3 +V 4 A 4…………… (iii)

The Gibbs energy change for the reaction (the reaction potential) is given by;

∆rG = V 3 μ 3 +V 4 μ4 -V 1 μ 1 - V 2 μ 2 ………. (IV)

We write the chemical potential of the reactant and products using equation (ii)

μ1= μ01+RTIna 1

μ2= μ02+RTIna 2
μ3= μ03+RTIna 3

μ4 = μ04 +RTIna 4

0 0 0 0
∆rG = ( v3 μ3 + v 4 μ 4 - v1 μ1 - v1 μ2)+RT(V 3Ina 3 + v 4Ina 4- v1 Ina 1 - v 2Ina 2)

av3 3 av4 4
∆rG = ∆ rG 0 + RTIn v1 v2 ………………(v)
a1 a2

When the activities of the substances, reactants and products, are all one, the second term of the
equation (v) is zero and ∆rG = ∆ rG 0. ∆ rG 0, the free free energy change of a reaction in the standard
state (standard reaction potential) is constant at any given temperature and completely independent of
pressure.

In general, the equation is given by;

0 =∑ v i A i……………(vi)
i

The Ai represents the chemical species of the reaction and vi s are the corresponding stoichiometric
coefficients, negative for reactants and positive for products. The free energy change of the reaction is
given by:

vi
∆rG=∆rG ° +RTIn ᴨ i (ai ) ……….(vii)

ᴨproducts ( ai )v i

∆rG = ∆rG ° +RTIn vi …………….. (viii)

This most fundamental thermodynamics equation (vii), (viii) is referred to as the reaction isotherm.
Reaction quotient a is;
vi
Q= ᴨ (ai ) …….. (ix)

∆rG= ∆rG °+RTIna………..(X)

Pure solids and liquids do not make any contribution to Q even though they may appear in the chemical
equation because their activities are one.

The term a i is interpreted as a fugacity f i, if Ai is a gas, activities of gaseous species are replaced by
fi
fugacities, by using a i = .
po
At equilibrium, ∆ rG=0. The activities have their equilibrium values. The reaction quotient, Q at
equilibrium is k, the thermodynamic equilibrium constant.

K=[ ᴨ i (a ) ]………………………. (xi)

While writing K, equilibrium values of activities would be used and for Q, the values at the specified
stage of the reaction. Equation (x) reduces to;

∆rG ° = -RTInk.

At equilibrium, as activities are dimensionless numbers, the thermodynamic equilibrium constant is also
dimensionless.

In elementary applications, the activities that occur in equation (xi) are often substituted by molarities or
molarities and fugacities by partial pressure.

Expressions obtained by substituting are approximate and in the case of ionic solutions, even when they
are very dilute, substantial approximation gets introduced.

The standard free energy change of reaction, ∆rG ° can be evaluated from standard free energies of
formation at the temperature of the reaction which are given in literature.