CHM101(3) – General Physical Chemistry

Atoms, Dalton’s Atomic Theory and Atomic Masses, Fundamenta

particles of the Atom and Atomic structure, Modern electronic theory of

atoms; Periodicity of the elements, Mole concept, Chemical formulae

equations and calculations, States of matter: gas, liquid and solid,

Energetics and Thermochemistry, Chemical kinetics, Equilibria and

Electrochemistry

Dr. S.O. Owalude

45h (T), C
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 CHEMICAL KINETICS

The study of chemical phenomenon can be approached from two

angles, THERMODYNAMICS and CHEMICAL KINETICS.

THERMODYNAMICS involves the driving potential which is a

measure of the tendency of a system to change from one state to
another.

CHEMICAL KINETICS deals with the rate of change from initial to

final state under non-equilibrium conditions.

The ultimate goal of chemical kinetics is a theory interrelating

energies, structures and time for the single chemical event.

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 Slow and fast reactions

(a) Slow reactions: these are reactions that proceed slowly and
their rates can be measured by conventional methods.

Example:
C12H22O11 + H2O C6H12O6 + C6H12O6

(b) Fast reactions: The rates of these reactions are too fast to be
measured by conventional methods. The half-lives of such
reactions are less than I second.
Example:
i. Organic substitution reactions

ii. Explosive reactions of O2 and H2 and HCs

iii. Many ionic reactions such as the neutralization of acids and

bases. 3
 REACTION RATES

The rate of a chemical reaction is defined as the change in

concentration of a reactant in a particular time interval.

The units of reaction rate are unit of concentration divided by the

unit of time.

Since concentration is normally measured in moles per liter (mol

L-1), the rate of reaction is specified as mol L-1 s-1 and if the time is
measured in minutes, the rate will become mol L-1 min-1.

Example:

2N2O5(s) 4NO2(g) + O2(g)

The rate for this reaction can be determined by measuring the

increase in the molar concentration of O2 in a given time interval.
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Suppose [O2]I = the molar concentration of O2 at initial time ti

[O2]f = the molar concentration of O2 at final time tf

Then, change in molar concentration = [O2]f – [O2]i = ∆[O2] and

time required for the change = tf – ti = ∆t.

Therefore; the rate of the reaction in terms of O2 formation can be

written as:

The rate of formation of

In a similar way, the rate can be measured in terms of N2O5

decomposition as:

The rate of formation of

The –ve sign appears because the change in molar concentration

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i.e. ∆[N2O5]f - ∆[N2O5]i; is negative since the molar concentration
of N2O5 is decreasing with time.

The relationship between the rate of decomposition of N2O5 and

the rate of formation of O2 can then be written as:

This is because from the equation for the reaction, the rate of
decomposition of N2O5 is twice as fast as the rate of formation of
O2. And for a similar argument:

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The rate of a chemical reaction or alternatively its speed or
velocity can therefore be defined as the rate at which
concentrations of reacting species change with time.

It is denoted by d[c]/dt where [ ] is the concentration of any

reacting species and t is the time.

Example: H2 + I2 2HI

Rate of the reaction =

FACTORS AFFECTING REACTION RATES

The results from experiments have indicated that the following

principal factors affect the rate of chemical reactions:

The nature of the reactants: Chemical reactions involve

breaking of old bonds and formation of new ones. 7
Therefore, the strength of these bonds and their environments in
the reacting molecules will affect the rate of the reaction.
Example:

NaOH + HCl NaCl + H2O (fast and instantaneous)

N2 + 3H2 2NH3 (slow and require a catalyst)

Effect of concentration (pressures): The rate of every chemical

reaction is directly proportional to the concentration (or pressures)
of the reactants except for zero-order reactions.

High concentration of reactants increases collisions and hence

reaction rates. 8
Effect of a catalyst: The presence of a catalyst can increase or
decrease the speed of a reaction.

E.g. H2 and O2 do not react ordinarily but in the presence of a

small quantity of Pt, they combine and the reaction occurs rapidly.

Similarly, a small amount of glycerine slows down the

decomposition of H2O2.

The reactions which occur in the presence of a catalyst are known

as catalyzed reaction.

Effect of temperature: Reaction rate negligibly slow at ordinary

temperatures may become appreciable and even explosive at
elevated temperatures.

A useful rule is that the rate is doubled for every 10 °C rise in

temperature. 9
 ORDER AND MOLECULARITY OF A REACTION

The ORDER of a reaction is defined as the sum of the powers of

the concentration terms in the balanced chemical equation for the
reaction.

e.g. consider the following reactions:

X Products (i)
X + Y Products (ii)
2X Products (iii)
2X + Y Products (iv)
X + 2Y Products (v)

The rate of reaction in (i) can be written as k[X] and the reaction is
said to be first-order.

In (ii) the rate is k[X][Y] and the reaction is second-order. 10

In (iii) the rate is k[X]2 and the reaction is second-order.

In (iv) & (v) the rate is k[X]2[Y] and k[X][Y]2 respectively and the
reaction is of third-order.

The order of a reaction is not always a whole no as determined

from the experiment but can be zero or fractional.

The MOLECULARITY of a reaction is given by the no of atoms or

molecules of all the species participating in the reaction as given
by the stoichiometric equation.
In the examples given above;

In (i) since only one molecule is involved in the reaction, the

reaction is UNIMOLECULAR.

Similarly in (ii) and (III) where two molecules are involved, these
reactions are BIMOLECULAR. 11
And in (iv) and (v) the reactions are TERMOLECULAR.

For these reactions, the ORDER is the same as the

MOLECULARITY, but this does not hold in all cases.

Consider the reaction:

C12H22O11 + H2O C6H12O6 + C6H12O6

Sucrose Glucose Fructose

The MOLECULARITY of this reaction is 2 i.e. the reaction is

bimolecular since two molecules are involved in the reaction.

But according to the experiment, the reaction is found to be first-

order with respect to sugar.

Thus, the ORDER of the reaction is not the same as the

MOLECULARITY. 12
 KINETICS OF ZERO-ORDER REACTIONS

A reaction is said to be of zero-order when the rate is independent

of the concentration of the reactants.

i.e. if the concentration of the reactants remain unaltered during

the course of the reaction, it is said to be of zero order.

This means that the rate of a zero-order reaction is constant.

ko
For the reaction: A P (i)

(ii)

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Equation (ii) can be re-arranged to give:

d[A] = -kodt (iii)

Let [A]o be the initial concentration of A and [A] its concentration at

any time t during the reaction. Equation (iii) can then be readily
integrated thus:
[𝐴] 𝑡
න 𝑑[𝐴] = −𝑘𝑜 න 𝑑𝑡
𝐴 𝑜
𝑜
Therefore,
(iv)
[A] = [A]o - kot

ko is the rate constant for a zero-order reaction. (v)

The unit of ko is mol/L/t.
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 HALF LIFE

The half life (t1/2) is defined to be the time required for the reactant
concentration to decay to half its initial value.

To derive an expression for half-life for a zero-order reaction, we

set the condition that t = t1/2 when x = a/2 (a = the initial
concentration of the reactants).

Using equation (v); , Hence (vi)

Therefore, t1/2 is directly proportional to a for zero-order reactions.

Examples:

1. CH3COCH3 + Br2 CH3COCH2Br + HBr (This reaction

proceeds at the same rate irrespective of bromine concentration)
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2. 2PH3 2P + 3H2 (At high pressure on the surface of
Mo or W, the decomposition of phosphine is zero order)

3. CH3COCH3 + I2 CH3COCH2I + HI (This reaction is

found to be zero-order in I2)

A plot of rate vs concentration for a zero-order reaction is

shown below:

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 WORKED EXAMPLES

1. The rate constant of a zero order reaction is 0.2 mol/L/h. What

will be the initial concentration of the reactant if after half an
hour its concentration is 0.05 mol/L?

Solution

From equation (v) ko = (co - c)/t; given ko = 0.2 mol/L/h, t = 1/2h,

c = 0.05 mol/L, therefore co = 0.15 mol/L

2. Find the order of the reaction and the rate constant of the
decomposition of NH3 on a W wire at 856 oC. Data obtained in an
experiment are given below:

Total pressure (torr) 228 250 273 318

Time (s) 200 400 600 1000
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Solution

From the table,

ΔP; 0 22 45 90

Δt; 0 200 400 800

ΔP/Δt; - 0.110 0.113 0.113

From the results, the rate of the reaction does not depend on the
concentration (partial pressure) of the reactant; therefore it is a
zero-order reaction.

Therefore,

dp/dt = 0.1125 torr/s 18

 KINETICS OF FIRST-ORDER REACTIONS

Consider a simple first-order reaction:

A B (i)
The rate law can be expressed as:

(ii)

i.e. (iii)

Equation (iii) can be re-arranged to give

(iv)
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Therefore,

(v)

Where [A]o = [A] at t = 0 and [A] = [A] at time t.

On integration equation (v) becomes:

(vi)

(vii)
Hence:

(viii)

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Equation (viii) can also be written in another alternate form. Let a
mol/L be the initial concentration of A.

After time t, let x mol/L of A have decomposed into the products.

Therefore, remaining concentration of A at time t = (a-x) mol/L

and substituting (a-x) for [A] in equation (iv) we have
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 (ix)

Consider the left hand side of equation (ix)

(x)

Because since a is a constant.

Therefore,
(xi)

or
(xii)
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Integrating both sides of equation (xii):

(xiii)

(xiv)

(xv)

Or

(xvi)

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 HALF-LIFE FOR A FIRST-ORDER REACTION

To find t1/2 for a first-order reaction we use equation (viii) with the
substitution [A] = [A]o/2 and t = t1/2.

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Note that t1/2 is independent of concentration for first-order
reactions.

TEST FOR FIRST-ORDER REACTIONS

Any reaction that satisfies equation (xv) or (xvi) is said to be a

first-order reaction. This can be verified in two ways:

1. The Integration method: The values of k1 calculated using

equation (xv) should be constant for a first-order reaction.

2. The graphical method: Equation (xv) can also be written as:

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A plot of log(a-x) against t for a first-order reaction should be a
straight line with a slope of –k1/2.303 and an intercept of log a on
the y axis.

3. Fractional life method: The fraction generally taken is one-half

of a given reactant. If t1/2 is the time required to reduce the
concentration of the reacting substance to half its initial value.

WORKED EXAMPLES
1. From the following data show that the decomposition of H2O2 in
aqueous solution is a first-order reaction.
Time (min) 0 5 10 20
KMnO4 (mL) 46.1 37.1 29.8 19.6
Solution

For this reaction,

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Here a = 46.1

t (a – x) k1

5 37.1

10 29.8

20 19.6

The constant value of k1 indicates the reaction is first-order.

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 EXAMPLES OF FIRST-ORDER REACTIONS

a. Inversion or hydrolysis of cane sugar: This is represented

by:

C12H22O11 + H2O C6H12O6 + C6H12O6

Sucrose Glucose Fructose

The above reaction is studied by measuring the angles of rotation

of the reaction mixtures at various times.

Let αo and α∞ be the angle of rotation at the start (t = 0) and when

the reaction is complete respectively, and αt the angle of rotation
at anytime t.

Then (αo - α∞) is proportional to the initial amount of sucrose i.e. a,

and (αt - α∞) to the amount of sucrose left at time t i.e. (a - x).
Therefore the rate equation becomes: 28
Example: The optical rotations of sucrose in 0.5 M HCl at various
time intervals are given below:

Time (min) 0 10 20 40 ∞
Rotation (degrees) +32.4 +28.8 +25.5 +19.6 -11.1

Show that the reaction is of first-order.

Solution:
For this reaction,

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Since αo - α∞ = 32.4 – (-11.1) = +43.5

t αt - α∞

10 39.9

20 36.6

40 30.7

Since k1 is constant then the reaction is first-order.

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b. Radioactive Decay

The process of radioactive decay of an unstable nucleus has been

shown to follow a first-order rate law.

Example Cu64 disintegrate according to the equation below:

Cu64 Zn64 + β-; (i)

Unstable stable

The probability of this occurrence in interval of time is given by:

(ii)

Where –dN is the number of copper nuclei that disintegrate in the

interval dt. 31
Equation (ii) is of the same form as the first-order rate law and
therefore can be integrated as:
(iii)

No = the number of Cu64 nuclei present at t = 0, N = number at

any time t. the decay constant λ is related to half-life by:

(iv)

The decay constant λ, unlike the chemical reaction rate constant,

is completely independent of any external influence like
temperature and pressure.

From equation (iii) and (iv), we have:

(v)
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 (vi)

(vii)

Equation (vii) shows that after the elapse of a period equal to two
half-lives, (1/2)2 = ¼ of the substance remains. After three half-lives
only 1/8 remains, and after four half-lives only 1/16 remains and so
on.

Radioactive decay

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c. Bacterial growth

Bacterial colony develops by cell division, in any colony the cell

division’s probability is proportional to the time interval dt; thus

(viii)

Where dN is the number of cells that divide in the time interval dt,
λg is a constant.

The growth law is very similar to the law of radioactive decay

except that the negative sign is missing. Thus:
(ix)

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The generation time is the time required for the population to
double (tg) i.e. when t = tg; N = 2No, equation (ix) thus becomes:

(x)

(xi)
or 35
 Using this value of λg in equation (ix),

(xii)

Equation (xii) is not applicable in the entire history of the colony.

Induction period followed by exponential growth rate between t1

and t2.

Then the population growth slows, and then stops;

And in the final phase the population drops as the bacteria die off
more rapidly than they produced.

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 WORKED EXAMPLES (CONTD)

1. From the following data, show that the decomposition of H2O2

in aqueous solution is a first-order reaction and hence determine
the half-life of the reaction.
Time (min) 0 5 10 20
KMnO4 (cm3) 46.1 37.1 29.8 19.6

Solution

The solution is the same as in example 1. For first-order reaction

the rate constant k1 is related to t1/2 by:

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2. The half-life of a first-order reaction is 30 min (a) calculate the
rate constant of the reaction (b) what fraction of the reactant
remains after 70 min?

Solution

(a)

(b)

Therefore,
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3. A first-order reaction is 40% complete at the end of 50 min,
what is the value of the rate constant in s-1. In how many minutes
will the reaction be 80% complete?

Solution

Let the initial concentration be a,

Therefore;

Hence;

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 = 1.70 x 10-4 s-1

At 80%;

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 = 9086.6 s

= 157.8 min

4. The half life for the first-order decomposition of N2O5 is 2.0 x

104 s. How long will it take for a sample of N2O5 to decay to 60%
of initial value?

Solution

and given that [N2O5] = 0.6[N2O5]o

Therefore;

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5. Zinc-65 has a half-life of 245 days (a) What % of the original
activity remains after 100 days? (b) How much time is required for
the activity to reduce to 5% of the initial activity?

Solution
(a)

= 2.83 x 10-3 day-1

(b)
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 HOME WORK

1. The decomposition of H2O2 was studied by titrating it at different

intervals of time with KMnO4. Calculate the velocity constant from
the following data, if the reaction is of first-order.

t (min) 0 10 30 40
KMnO4 (mL) 25.0 20.0 12.5 9.6

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2. The following observations were made during hydrolysis of
methyl acetate at 20 oC using 0.05 N HCl as catalyst. Show that
the reaction is of the first-order.

t (s) 0 75 119 183 ∞

Vol. of alkali (mL) 9.62 12.10 13.10 14.75 21.05

3. The optical rotations of cane sugar in 0.5 N HCl at 35 oC and at

various intervals are given below. Show that the reaction is of the
first-order.

t (min) 0 20 40 80 ∞
Rotation (deg) +32.4 +25.5 +19.6 +10.3 -14.1

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4. At 25 oC the half-life for the decomposition of N2O5 is 2.05 x 104
s and is independent of the initial concentration of N2O5. (a) What
is the order of the reaction? (b) What length of time is required for
80% of the N2O5 to decompose?

5. Calculate the half-life for N2O5 at 25 oC and the fraction

decomposed after 8 hours (k = 3.38 x 10-5 s-1).

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