CEMICAL KINETICS

1.1 RATE OF REACTION

The rate of reaction is a positive quantity that expresses how the concentration of a reactant or
product changes with time (m/s).
For the general equation
Reactants Products
The equation shows that for a reaction, reactants are consumed and products are formed. Therefore,
the progress of the reaction can be followed by monitoring either the decrease in the concentration
of reactants or increase in the concentration of products.
Generally, for the reaction
A B
−∆[𝐴] ∆[𝐵]
𝑟𝑎𝑡𝑒 = 𝑜𝑟
∆𝑡 ∆𝑡
Where Δ[ ] = change in concentration (moldm-3)
Δt = time required for the change (s) etc.
The concentration of A decreases during the course of the reaction, and rate of reaction is a positive
quantity, thus a negative sign is needed in the rate expression to make the rate positive.
These rates are average rates because they are averaged over a certain period, Δt.
The rate of reaction determined for a specific instant in time is called instantaneous rate of reaction
at that time.

1.1.1 REACTION RATES AND STOICHIOMETRY

For more complex reactions other that A B
e.g. 2A B,
the rate expression should take into consideration, the moles of reactants and products under
consideration
For the reaction
2A B
Two moles of A disappear for each mole of B that is formed;
i.e. the rate at which B forms, is one-half the rate at which A disappears. Thus, the rate can be
expressed as
 1 ∆[𝑨] ∆[𝑩]
𝑟𝑎𝑡𝑒 = − 𝑜𝑟 𝑟𝑎𝑡𝑒 =
2 ∆𝑡 ∆𝑡
For the general equation
aA + bB cC + dD
1 ∆[𝑨] 1 ∆[𝑩] 1 ∆[𝑪] 1 ∆[𝑫]
𝑟𝑎𝑡𝑒 = − = − = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡
Example 1
Write the expression for the following reactions in terms of the disappearance of the reactant and
appearance of the product.

a. I- + OCl- Cl- + OI-

b. 4NH3 + 5O2 4NO + 6H2O

Solution
∆[𝐼 − ] ∆ [ 𝑂𝐶𝑙− ] ∆[𝐶𝑙− ] ∆[𝑂𝐼 − ]
a. 𝑟𝑎𝑡𝑒 = − = − = =
∆𝑡 ∆𝑡 ∆𝑡 ∆𝑡
1 [𝑁𝐻3 ] 1 𝑂2 1 𝑁𝑂 1 𝐻2 𝑂
b. 𝑟𝑎𝑡𝑒 = − = − = =
4 ∆𝑡 5 ∆𝑡 4 ∆𝑡 6 ∆𝑡

PRACTICE QUESTIONS

1. Express the rate of the reactions in a and b in terms of Δ[CO2] and Δ[C2H6], respectively.
a. CH4 + 2O2 CO2 + 2H2O
b. 2C2H6 + 7O2 4CO2 + 6H2O

2. Consider the reaction

4NO2 + O2 2N2O5
If at a particular moment during the reaction, molecular oxygen is reacting at the rate of
0.024Ms-1;
a. at what rate is N2O5 being formed?
b. at what rate is NO2 being consumed/reacting?

1 ∆ [𝑁𝑂2 ] ∆ [𝑂2 ] 1 ∆ [𝑁2 𝑂5 ]

𝑟𝑎𝑡𝑒 = − = − =
4 ∆𝑡 ∆𝑡 2 ∆𝑡

3. Consider 4PH3 P4 + 6H2

If H2 is formed at a rate of 0.078Ms-1, calculate the rate at which PH3 is reacting and P4 is
formed.
4. Write a balanced equation for a gas-phase reaction whose rate is given by
1 ∆[𝑁𝑂𝐶𝑙] 1 ∆[𝑁𝑂] ∆[𝐶𝑙2 ]
𝑟𝑎𝑡𝑒 = − = =
2 ∆𝑡 2 ∆𝑡 ∆𝑡

1.2 FACTORS AFFECTING RATE OF REACTION

1. Concentration (or pressure of gas)
2. Temperature
3. Catalyst
4. Nature of reactant or surface area

1.2.1 REACTION RATE AND CONCENTRATION

The rate of a reaction is directly related to reactant concentration. The higher the concentration of
the starting materials, the more rapidly a reaction takes place.
Reactions occur as a result of collisions between reactant molecules. The higher the concentration
of molecules, the greater the number of collisions in unit time and hence the faster the reaction. As
reactants are consumed, their concentration drop, collision occurs less frequently and reaction rates
decrease. Thus, it is observed that reaction rate drops off with time and eventually goes to zero
when the limiting reactant is consumed.

1.3 RATE EXPRESSION AND RATE CONSTANT

The rate of reaction depends on and is directly proportional to the concentration.
i.e. Rate α concentration
Rate = k[X]
Where X is any reactant
The equation, rate = k [X] is referred to as the rate expression. It tells how the rate of the reaction
depends on the concentration of reactant. The proportionality constant k is called the rate constant.
While the rate of reaction depends on concentration, the constant, k, is independent of
concentration. The rate expression takes various forms depending on the nature of the reaction.
1.4 ORDER OF REACTION
1.4.1 ORDER OF REACTION INVOLVING A SINGLE REACTANT
For the process
A Products
The rate expression has the general form
Rate = k[A]m
The power to which the concentration of the reactant A is raised in the rate expression is called the
order of the reaction, m.
If m = 0, the reaction is said to be zero order
If m = 1, the reaction is said to be first-order
If m = 2, the reaction is said to be second-order, etc.
Ordinarily, the reaction order is integral
i.e. 0, 1, 2, 3,…
The order of reaction must be determined experimentally, it cannot be deduced from the
coefficients in the balanced equation. This is true because there can only be one reaction order but
many ways in which reaction equation can be balanced
e.g. N2O5 2NO2 + ½O2
2N2O5 4NO2 + O2
The above reaction is first-order no matter how the equation is written.
One way of finding the order of a reaction is to measure the initial rate (i.e. the rate at t = 0) as a
function of the concentration of reactant. For example, if two different reaction mixtures differing
only in the concentration of reactant A are made and the rates at the beginning of reaction and
before the reaction of A has decreased appreciably are measured. This gives two different initial
rates (rate1, rate2) corresponding to two different starting concentration of A, [A]1 and [A]2. From
the rate expression,
𝑚
𝑟𝑎𝑡𝑒2 = 𝑘[𝐴]2
𝑚
𝑟𝑎𝑡𝑒1 = 𝑘[𝐴]1
Dividing the second rate by the first
𝑟𝑎𝑡𝑒2 𝐾 [𝐴]𝑚
2 [𝐴]𝑚2 [𝐴]2 𝑚
= = = ( )
𝑟𝑎𝑡𝑒1 𝐾[𝐴]1𝑚 [𝐴]1𝑚 [𝐴]1
Because all quantities in the equation are known except m, the reaction order can be calculated.
Example 2
The initial rate of decomposition of acetaldehyde CH3CHO, at 600oC
CH3CHO(g) CH4(g) + CO(g)
was measured at a series of concentration with the following results:
[CH3CHO] (M) 0.20 0.30 0.40 0.50
Rate (moldm-3s-1) 0.34 0.76 1.4 2.1
Using these data, determine the reaction order.

Solution
𝑟𝑎𝑡𝑒 = 𝑘 [𝐶𝐻3 𝐶𝐻𝑂]𝑚
𝑟𝑎𝑡𝑒2 0.76
= = 2.2
𝑟𝑎𝑡𝑒1 0.34
[𝐶𝐻3 𝐶𝐻𝑂]2 0.3
= = 1.5
[𝐶𝐻3 𝐶𝐻𝑂]1 0.2
Hence, the relationship becomes
𝑚
𝑟𝑎𝑡𝑒2 [𝐴]2
= ( ) ;
𝑟𝑎𝑡𝑒1 [𝐴]1
2.2 = (1.5)𝑚
𝑚=2
The reaction is second order.
Try using any other two other experiments than the ones used above.
Once the order of a reaction is known, the rate constant, k, is readily calculated.

For the decomposition of acetaldehyde

𝑟𝑎𝑡𝑒 = 𝐾 [𝐶𝐻3 𝐶𝐻𝑂]2
When the rate was 0.34moldm-3s-1, the concentration was 0.2M
𝑟𝑎𝑡𝑒
𝐾=
[𝐶𝐻3 𝐶𝐻𝑂]2
0.34
𝐾= = 8.5 𝑑𝑚3 𝑚𝑜𝑙 −1 𝑠 −1
(0.2)2
With the order and rate constant known, the rate of reaction at any concentration can be calculated.
For example, what is the rate of decomposition of acetaldehyde when the concentration of
acetaldehyde was 0.6M
𝑟𝑎𝑡𝑒 = 8.5 × [𝐶𝐻3 𝐶𝐻𝑂]2
𝑟𝑎𝑡𝑒 = 8.5 × (0.6)2
𝑟𝑎𝑡𝑒 = 3.1 𝑚𝑜𝑙𝑑𝑚−3 𝑠 −1

1.4.2 ORDER OF REACTION WITH MORE THAN ONE REACTANT

For reactions involving more than one reactant
i.e. A and B
aA + bB Products
the general form of rate expression is
𝑟𝑎𝑡𝑒 = 𝐾 [𝐴]𝑚 × [𝐵]𝑛
In the rate expression, m is referred to as the order of reaction with respect to A and n, the order of
reaction with respect to B. The overall order of reaction is the sum of the expression, m + n.
If m = 1 and n = 2, then the reaction is first-order in A, second-order in B and third-order overall.

For more than one reactant, the reaction order is determined by holding the initial concentration of
one reactant constant while varying that of the other reactant. From rates measured under these
conditions, the order of reaction can be deduced with respect to the reactant whose initial
concentration is varied.
Consider the reaction between A and B referred to above. Suppose two different experiments were
conducted in which the initial concentration of A differ ([𝐴]1 , [𝐴]2 ) but that of B was held constant
at [B]. Then,
𝑟𝑎𝑡𝑒1 = 𝐾 [𝐴]1𝑚 × [𝐵]𝑛 ; 𝑟𝑎𝑡𝑒2 = 𝐾 [𝐴]𝑚
2 × [𝐵]
𝑛

Dividing the second equation by the first

𝑟𝑎𝑡𝑒2 𝐾 [𝐴]𝑚
2 [𝐴]𝑚2 [𝐴]2 𝑚
= = = ( )
𝑟𝑎𝑡𝑒1 𝐾[𝐴]1𝑚 [𝐴]1𝑚 [𝐴]1
Knowing the two rates and the ratio of the two concentrations, the value of m can be determined.
Example 3
Consider the reaction at 55oC
(CH3)3CBr + OH- (CH3)3COH + Br-
A series of experiments were carried out with the following results:
Expt 1 Expt 2 Expt 3 Expt 4 Expt 5
[(CH3)3CBr] 0.50 1.0 1.5 1.0 1.0
[OH-] 0.050 0.050 0.050 0.10 0.20
Rate (moldm-3s-1) 0.0050 0.010 0.015 0.010 0.010
Find the order of the reaction with respect to both (CH3)3CBr and OH-. Write the rate expression
for the reaction.
Solution

𝑟𝑎𝑡𝑒5 [(𝐶𝐻 ) 𝐶𝐵𝑟 ] 𝑚 0.015 1.5 𝑚

i. = ( [(𝐶𝐻3 )3 𝐶𝐵𝑟] 3) ; = (0.50)
𝑟𝑎𝑡𝑒1 3 3 1 0.0050

3 = 3m
m=1
𝑟𝑎𝑡𝑒5 [𝑂𝐻 − ] 𝑛 0.010 0.20 𝑛
ii. = ([𝑂𝐻 −]5) ; = (0.050)
𝑟𝑎𝑡𝑒2 2 0.010

1 = 4n
n=0

In this case, n = 0; the rate is independent of the concentration of OH-. The rate expression is
𝑟𝑎𝑡𝑒 = 𝐾 [ (𝐶𝐻3 )3 𝐶𝐵𝑟 ]

Example 4
For a reaction involving the decomposition of Y, the following data were obtained:
Rate (moldm-3min-1) 0.288 0.245 0.202 0.158
[Y] 0.200 0.170 0.140 0.110
a. Determine the order of the reaction
b. Write the rate expression for the decomposition of Y
c. Calculate K for the experiment above.
Solution
𝑟𝑎𝑡𝑒 = 𝑘[𝑌]𝑚
𝑟𝑎𝑡𝑒3 [𝑌]3 𝑚
= ( )
𝑟𝑎𝑡𝑒1 [𝑌]1
0.202 0.140 𝑚
= ( )
0.288 0.200
0.701 = 0.7𝑚
m=1
The order of the reaction is first-order
Rate expression: rate = k[Y]
rate = k[Y]
when rate = 0.288moldm-3min-1, [Y] = 0.200
0.288 = k x 0.2
k = 0.288/0.2
k = 1.44min-1
Summary
i. Rate law which is the expression relating the rate of a reaction to the rate constant and
concentrations of the reactant raised to some powers is always determined experimentally.
ii. Reaction order is always defined in terms of reactant (not product) concentration
iii. The order of a reaction is not related to the stoichiometric coefficients of the reactant in
the overall balanced equation.