Kinetics (Rates) Part 2

Rate law and Half Life

2021
Unit 1 Chemistry
 Objectives
● Construct Rate equation
● Deduce order of a reaction
● Interpret concentration against time and
concentration against rate graph for zero and
first order
● Perform calculations from rate data
● Find half life (limited to first order reaction)
 Rate Law (rate equation)
The rate law is experimentally determined and can be used to
predict the relationship between the rate of a reaction and the
concentrations of reactants.
Rate Equations

🞂 Rate =

🞂 k = rate constant which is temperature dependent, concentration

independent(units vary)

🞂 m in the order of reaction with respect to A, no units

🞂 n is the order of reaction with respect to B, no units

🞂 m+n is the overall order of reaction (can be positive, negative, zero,

whole number or fraction.) Temperature and concentration
independent.

The order of a reaction tells how the rate of a reaction varies with
changes in the concentration of the reactant.
 Rate constant
• The proportionality constant in the equation describes
–the relationship between the rate of a step in a chemical
reaction and the product of the concentrations of the
individual reactants consumed in that step

For the reaction:

A→ B + C
The rate equation is :
Rate: k[ A ]n
n is the order of reaction
 ORDERS OF REACTION
• The order of reaction with respect to a certain reactant, is
defined as the power to which its concentration term in
the rate equation is raised.
–For example, given a chemical reaction
A+B→C
with a rate equation Rate= k[A]x[B]y

▪ The reaction order with respect to A would be x and

with respect to B would be y,
▪ The total reaction order would be x + y
 ORDER OF REACTION
•ZERO-ORDER REACTIONS: (order = 0)
– These reactions have a constant rate.
– This rate is independent of the concentration of the reactants.
–The rate law is: rate = k
• with k having the units of mol dm-3 sec -1.

•FIRST-ORDER REACTIONS: (order = 1)

– These reactions have a rate proportional to the concentration
of one of the reactants.
• i.e. as concentration of the reactant double so does the rate of
reaction
•The rate law is:
rate = k[A] or rate = k[B]
with k having the units of sec-1
 ORDER OF REACTION

• SECOND-ORDER REACTIONS: (order = 2)

–Has a rate proportional to the concentration of the square of
a single reactant;
• i.e.
– the rate quadruples as the concentration doubles
– it is the product of the concentration of two reactants

– rate = k[A]2 or
– rate = k[B]2 or

– rate = k[A] [B]

Videos
• https://www.youtube.com/watch?v=wYqQCojg
gyM

https://www.youtube.com/watch?v=liGCU9gaLc
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 Rate Law
• The total order for a reaction is worked out by
adding all the individual orders together (m+n)

• The square brackets [A] means the concentration

of A (unit mol dm-3)
 Remember!
Calculating orders from initial rate data
• For zero order: the concentration of A has no effect on
the rate of reaction r = k[A]0 = k

• For first order: the rate of reaction is directly

proportional to the concentration of A r = k[A]1

• For second order: the rate of reaction is proportional

to the concentration of A squared r = k[A]2
 Calculating orders from initial rate data
• For second order: the rate of reaction is proportional
to the concentration of A squared r = k[A]2
Example
• If the [A] is x2 that rate would x22=x4
• If the [B] is x3 that rate would x32= x9
• If these changes happened at the same time
then the rate would x4x9= x 36
 Remember!
Calculating orders from initial rate data
• If conc. is doubled and rate stays the same: order= 0

• If conc. is doubled and rate doubles: order= 1

• If conc. is doubled and rate quadruples : order= 2

Calculating orders from initial rate data
• For reactant A, compare between experiments 1 and 2
• For reactant A, as the concentration doubles (B and C staying
constant) so does the rate(double). Therefore the order with
respect to reactant A is first order
Calculating orders from initial rate data
• For reactant B compare between experiments 1 and 3 :
• As the concentration of B doubles (A and C staying constant)
the rate quadruples.
• Therefore the order with respect to B is 2nd order
Calculating orders from initial rate data
• For reactant C compare between experiments 1 and 4 :
• As the concentration of C doubles (A and B staying constant),
the rate stays the same.
• Therefore the order with respect to C is zero order
Calculating orders from initial rate data
Rate =

m+n is the overall order of reaction

• The overall rate equation is r = k [A] [B]2

• The reaction is 3rd order overall and the unit
of the rate constant =mol-2dm6s-1

• How do we now this ?

 The rate constant (k)
1. The units of k depend on the overall order of reaction. It
must be worked out from the rate equation

2. The value of k is independent of concentration and

time. It is constant at a fixed temperature.

3. The value of k refers to a specific temperature and it

increases if we increase temperature
 The rate constant (k)
• For a 1st order overall reaction the unit of k is s-1

• For a 2nd order overall reaction the unit of k is mol-1dm3s-1

• For a 3rd order overall reaction the unit of k is mol-2dm6s-1

Finding Order of Reaction: Initial Rate Method

Consider the reaction

• 2NO + O2 →2NO2 and the following experimental data

• Exp. Initial [NO] Initial [O2] Rate of appearance NO2

• 1 1 x 10-3 1 x 10-3 7 x 10-6
• 2 1 x 10-3 2 x 10-3 14 x 10-6
• 3 2 x 10-3 1 x 10-3 28 x 10-6

a. Use the above data to write the rate law

b. What is the order wrt O2?
c. What is the order wrt NO?
d. What is the overall order of the reaction?
 Finding Order of Reaction and Rate Constant:
Initial Rate Method
Consider the reaction: P4 + 6 H2 → 4 PH3. A rate study of
this reaction was conducted at 298 K. The data that were obtained
are shown in the table.
[P4], mol/L [H2], mol/L Initial Rate, mol/(L .
s)
0.0110 3.20 x 10-4
0.0075
0.0110 6.40 x 10-4
0.0150
0.0220 6.40 x 10-4
0.0150
 Initial Rate Method

EXPERIME Initial Initial Initial rate of

NT concentration of concentration formation of
X/moldm-3 of Y/moldm-3 XY3/moldm-3s-1
1 0.100 0.100 0.00200
2 0.100 0.200 0.00798
3 0.100 0.300 0.01805
4 0.200 0.100 0.00399
5 0.300 0.100 0.00601

Find the rate constant

Working out the overall rate order
• What do you do with experimental data if they
change the concentration of both reactants
simultaneously .

?
 Working out the overall rate order
• In most questions it is possible to compare between
two experiments where only one reactant has its
initial concentration changed.

• If, however, both reactants are changed then the

effect of both individual changes on concentration
are multiplied together to give the effect on rate.
 Overall Rate order
• In a reaction where the rate equation is
r = k [A] [B]2

• If the [A] is x2 that rate would x2

• If the [B] is x3 that rate would x32= x9
• If these changes happened at the same time then
the rate would be multiplied by 2 x 9 = x 18
 Question
• Example: work out the rate equation for the reaction,
between X and Y, using the initial rate data in the table.
 Overall Rate order
• In a reaction where the rate equation is
r = k [X] [Y]2

• If the [X] is x2 that rate would x2

• If the [Y] is x2 that rate would x22= x4
• If these changes happened at the same time then
the rate would be multiplied by 2 x ‘N’ = x 8
 Explanation
• For reactant X: Compare experiments 1 and 2

• For reactant X: As the concentration doubles so does the

rate (Y stays constant)

• Therefore the order w.r.t. reactant X is first order

 Explanation
• Compare experiments 2 and 3 :
– Both X and Y double and the rate goes up by 8
– We know X is first order, so the rate doubles
– Note that rate is quadrupled by the effect of the
concentration of Y which doubles .
• Hence, Y must be second order

REMEMBER
• If conc. is doubled and rate quadruples : order= 2
 Explanation
• The overall rate equation is r = k [X] [Y]2
• The reaction is 3rd order overall and the unit
of the rate constant =mol-2dm6s-1
 Finding Rate constant(k) using initial
rate data
• Using the above example, choose any one of the
experiments and put the values into the rate equation
that has been rearranged to give k. Using experiment 3
r = k [X] [Y]2
k = r/[X] [Y]2
k = 2.40 x 10–6 /0.2 x 0.22
k = 3.0 x 10-4 mol-2dm6s-1
• Remember k is the same for all experiments done at
the same temperature.
• Increasing the temperature increases the value of the
rate constant k
 Question
The following data were obtained in series of experiment
for the rxn
2NO + 2H2 → N2 + 2H2O
Exp. Initial [NO] Initial[H2] Rate of appearance
of N2
1 0.210 0.122 0.0339
2 0.210 0.244 0.0678
3 0.210 0.366 0.102
4 0.420 0.122 0.136
5 0.630 0.122 0.305

1. What is the order wrt to the reactants.

2. Write the rate law for the reaction r=k[NO]2[H2]
3. Calculate the rate constant k
4.What is the overall order of the reaction.

5. How is the rate of this reaction affected by each of the

following change
• [H2] is quadruple
• [NO] is quadruple
• [H2] is doubled and simultaneously the conc.of NO
is tripled.
 Question
EXPERIME Initial Initial Initial rate of
NT concentration of concentration formation of
X/moldm-3 of Y/moldm-3 XY3/moldm-3s-1
1 0.100 0.100 0.00200
2 0.100 0.200 0.00798
3 0.100 0.300 0.01805
4 0.200 0.100 0.00399
5 0.300 0.100 0.00601

1. What is the order w.r.t to the reactants.

2. Write the rate law for the reaction. r=k[X][Y]2

The order of reaction can be determined
graphically
• https://youtu.be/urVl4TJRlpc
3. Calculate the rate constant k k=r/[X][Y]2
=0.002/0.1 x 0.12
=2 mol-2dm6s-1
4. What is the overall order of the reaction.

5. How is the rate of this reaction affected by each of the

following change:
• [X] is quadruple
• [Y] is quadruple
• [X] is doubled and simultaneously the [Y] is tripled.
Graphs of initial RATE against CONCENTRATION
shows different rate orders:
● The initial rate may have been calculated from taking
gradients from concentration/time graphs.
RATE vs CONCENTRATION Graph w.r.t. Different Reaction
Orders
Concentration vs Time graphs

N.B. The Gradient

of the Graph gives
the Rate
 Determining rate and order of reaction graphically

• Plot a rate graph using the Time [N2O5]

data below 0 1.8*10 -2
2N2O5 →4NO2 + O2 600 1.3*10-2
1200 9.3*10-3
• Determine the order wrt to 1800 7.1*10-3
N2O5. 2400 5.3*10-3
3000 3.9*10-3
• Determine the rate of
reaction from the graph 3600 2.9*10-3
4200 2.2*10-3
5400 1.2*10-3
 A mathematical quick check to find out the order of reaction a
reactant from experimental data to plot concentration versus time

• Is the graph above first order or second order?

• Video: https://youtu.be/plXbgRYW7B8
Concentration vs Time Graphs
Rate graphs: Rate vs Concentrations
 Half-life (t1/2)
• This is the time it takes for one-half of the original amount
of material to react assuming the compound in the question
is a limiting reactant.
• If the initial concentration of a reactant “A” is 0.100 mol. L-1,
the half-life is the time at which [A]=0.0500 mol. L-1.

• The rate of the reaction “r” is proportional to the rate

constant “k”;

• The faster the reaction, the shorter the half-life.

• The larger the rate constant, the shorter the half-life.

 Half-life
● If we plot the concentration of a reactant versus time, we can see
the differences in half lives for reactions of different orders in the
graphs

● We can identify a 0, 1st, or 2nd order reaction from a plot of [A]

versus time by the variation in the time it takes the concentration
of a reactant to change by half.
a. For a zero order reaction (Half life decreases with decreasing concentration.)

b. For a 1st order reaction (Half life is constant.)

c. For a second order reaction (Half life increases with decreasing concentration.
)
 Continuous rate data
● This is data from one experiment where the
concentration of one substance is followed throughout
the experiment.

● For this method to work the concentrations of the

reactants not being followed must be in large excess in
the experiment so their concentrations stay virtually
constant and do not affect rate

● This data is processed by plotting the data and

calculating successive half-lives.
1st Order
1st Order
2nd Order
Zero Order
,
 Half Life Calculation
• Half life calculations
• Please know the equations indicated.
• Syllabus is limited to first order reactions
 Half life equation
1. For a zero order reaction; A ⇒ products, rate = k:

t½ = [Ao] / 2k

2. For a first order reaction A⇒ products, rate = k[A]:

t½ = 0.693 / k
 Half life equation
3. For a second order reaction 2A products or A + B products
(when [A] = [B]), rate = k[A]2:

t½ = 1 / k [Ao]
 First Order Rate Reaction
• A first order rate equation exists when the overall
order is one. i.e. m+n =1
• Rate =

• Rate =

<= know
Integrated Rate Law
 1st Order Reactions
• Conc. vs Time • Rate vs Concentration

⚫ ln[A]t vs Time/s (from integrated rate law)

 Video: https://youtu.be/e4qci9b2d3U

Derivation of
First Order Half life Equation
<= know
• Half Life (t1/2)
This is the time taken for
the concentration of a
reactant to fall to half
its initial amount.

🞂 For a 1st order

reaction

<= know
 Worked Example
• In a first order reaction the rate constant (k) is 0.015
s-1 at 25°C.

– If the reaction starts with a concentration of

reactant at 0.36 mol dm-3, calculate the
concentration of reactant after 20 s

– Calculate the time taken for the concentration of

the reactant to reach 0.18 mol dm-3
Solution
 Try
• What is the rate constant, k, for the first order
decomposition of N205 (g) at room temperature if the
half life at room temperature is 4.03 x 10-4 s?

• The reaction FClO2 => FClO(g) + O(g) is first order

with a rate constant of 6.76 x 10-4/s at 322 C.
– What is the half life of the reaction at 322 C?
That's it
For now
☺