CHEMICAL KINETICS

• Chemical reactions take place at different

rates.
• Would like to predict how fast a reaction takes
place.
• Study the rate of a reaction.
 Factors That Affect Reaction Rates
• Physical state of the reactants
– Homogeneous reactions are usually faster.
– For heterogeneous reactions involving solids, the reaction is faster if
the surface are is increased. eg.a powder will react faster than a
tablet.
• Concentration of Reactants
– As the concentration of reactants increases, so does the likelihood
that reactant molecules will collide.
• Temperature
– At higher temperatures, reactant molecules have more kinetic
energy, move faster, and collide more often and with greater energy.
• Catalysts
– Speeds up the reaction by changing the mechanism.
 Reaction rate
Rates of reactions can be determined by monitoring
the change in concentration (∆[A]) of either
reactants or products as a function of time (∆t).
∆[A] vs ∆t
• The rate of a reaction is a positive quantity that tells
us how the concentration of a reactant or product
changes with time.
∆𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
• Rate =
∆𝑡𝑡
• Units: moldm-3s-1, moldm-3min-1, moldm-3hr-1
Example:
Consider the decomposition of dinitrogen
pentoxide (N2O5):

2N2O5(g) → 4NO2(g) + O2(g)

Time (minutes) 0 1 2 3 4

[N2O5] mol dm-3 0,160 0,113 0,080 0,056 0,040

 Average rate
• The average rate of the reaction over each
interval is the change in concentration divided
by the change in time:
∆[𝑁𝑁2𝑂𝑂5]
• Rate = ̶
∆𝑡𝑡
• where Δ[N2O5] = [N2O5]final - [N2O5]start
• Negative sign necessary to make the rate a
positive quantity.
Time minutes 0 1 2 3 4

[N2O5] mol dm-3 0,160 0,113 0,080 0,056 0,040

Average Rate 0,047 0,033 0,024 0,016

mol dm-3 min-1

𝟎𝟎.𝟏𝟏𝟏𝟏𝟏𝟏−𝟎𝟎.𝟏𝟏𝟏𝟏𝟏𝟏
Average Rate = ̶ = 0.047 mol dm-3 min-1
𝟏𝟏−𝟎𝟎
𝟎𝟎.𝟎𝟎𝟎𝟎𝟎𝟎−𝟎𝟎.𝟏𝟏𝟏𝟏𝟏𝟏
Average Rate = ̶ = 0.033 mol dm-3 min-1
𝟐𝟐−𝟏𝟏
𝟎𝟎.𝟎𝟎𝟎𝟎𝟎𝟎−𝟎𝟎.𝟎𝟎𝟎𝟎𝟎𝟎
Average Rate = ̶ = 0.024 mol dm-3 min-1
𝟑𝟑−𝟐𝟐
𝟎𝟎.𝟎𝟎𝟎𝟎𝟎𝟎−𝟎𝟎.𝟎𝟎𝟎𝟎𝟎𝟎
Average Rate = ̶ = 0.016 mol dm-3 min-1
𝟒𝟒−𝟑𝟑
Plot of conc vs time

Instantaneous rate at t = 0 (initial rate)

Instantaneous rate at t = 3 min

 Instantaneous rate
• A plot of concentration vs. time for this
reaction yields a curve.
• The slope of a line tangent to the curve at any
point is the instantaneous rate at that time.
 The instantaneous rate can be determined
for any particular time:

Time minutes 0 1 2 3 4

[N2O5] mol dm-3 0,160 0,113 0,080 0,056 0,040

Instantaneous 0,056 0,039 0,028 0,020 0,014

Rate
mol dm-3 min-1

• The reaction slows down with time because

the concentration of the reactants decreases.
 Relative Rates and Stoichiometry
C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)
• In this reaction, the ratio of C4H9Cl to C4H9OH
is 1:1.
• Thus, the rate of disappearance of C4H9Cl is the
same as the rate of appearance of C4H9OH.
-∆[C4H9Cl] ∆[C4H9OH]
Rate = =
∆t ∆t
Note that C4H9Cl is a reactant and is consumed during the
reaction, therefore a negative sign is necessary. C4H9OH is
a product and is formed during the reaction, therefore a
positive sign is required.
 Reaction rates and stoichiometry
• What if the ratio is not 1:1?

H2(g) + I2(g) 2 HI(g)

• 1 mole of H2 used results in 2 moles of HI.

Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

 Worked example 1
1.1 How is the rate of disappearance of the reactants
related to the rate of appearance of the products?

N2(g) + 3 H2(g) → 2 NH3(g)

1.2 If the rate of appearance of NH3 is 1.0 x 10-3 M/s, what is
the rate of disappearance of N2 and H2 ?

Solution:
1.1.

1.2 Rate of disappearance of N2 = 0.5 x 10-3 M/s

Rate of disappearance of H2 = 1.5 x 10-3 M/s
 Concentration and Rate
Each reaction has its own equation that gives its
rate as a function of reactant concentrations.

This is called its Rate Law.

To determine the rate law we measure the rate at

different starting concentrations.
• To determine the effect of the
concentration of each reactant on the rate
of the reaction, keep every concentration
constant except for one reactant and see
what happens to the rate.
• Then, change a different reactant. This is
repeated to see how each reactant has
affected the rate.
 Concentration and Rate

Compare Experiments 1 and 2: [NO2-] is kept constant,

shows how [NH4+] affects the rate.
When [NH4+] doubles, the initial rate doubles.
 Concentration and Rate

Likewise, compare Experiments 5 and 6: [NH4+] is kept

constant, shows how the [NO2-] affects the rate.
When [NO2-] doubles, the initial rate doubles.
 Concentration and Rate

This equation is called the rate law,

and k is the rate constant.
 Rate Laws
• A rate law shows the relationship between the reaction rate
and the concentrations of reactants.
– For gas-phase reactants use PA (partial pressure) instead of [A].

• k is a constant that has a specific value for each reaction.

• The value of k is determined experimentally.

• k changes with Temperature

 Rate Laws
• Exponents tell the order of the reaction with
respect to each reactant.
• This reaction is
First-order in [NH4+]
First-order in [NO2−]
• The overall reaction order can be found by adding
the exponents on the reactants in the rate law.
• This reaction is second-order overall.
 Example
Write down the rate law for the reaction, explain
your reasoning.
Overall order of the reaction?
Calculate the rate constant with correct units.

[A] M [B] M Initial rate M/s

1.0 1.0 1.0 x 10-3
2.0 1.0 4.0 x 10-3
1.0 2.0 1.0 x 10-3
 Solution
• Compare Experiments 1 and 2:
when [A] doubles, the initial rate increases by 22 or 4.
Thus the reaction is second order with respect to A.
• Compare Experiments 1 and 3:
when [B] doubles, the initial rate remains constant.
Thus the reaction is zero order with respect to B.
RATE = k[A]2[B]0 = k[A]2
Overall order is second order.
• Calculate the rate constant with correct units.
• RATE = k[A]2
-3 2
• Exp 1: 1.0 x 10 = k[1.0]
-3 -1 -1
k = 1.0 x 10 M s
-3 2
• Exp 2: 4.0 x 10 = k[2.0]
-3 -1 -1
k = 1.0 x 10 M s
-3 -1 -1
• Thus k = 1.0 x 10 M s
Units of k for second order reaction:

RATE = k[A]2
k = Rate/[A]2
𝑀𝑀𝑠𝑠 −1
= 2
𝑀𝑀
= 𝑀𝑀−1 s−1
 Exercise
For the reaction OCl − + I − → OI − + Cl − :

[OCl −] M [I −] M Initial rate M/s

1.5 x 10-3 1.5 x 10-3 1.36 x 10-4
3.0 x 10-3 1.5 x 10-3 2.72 x 10-4
1.5 x 10-3 3.0 x 10-3 2.72 x 10-4
(a) Determine the rate law. Give reasons for your
answer.
(b) Determine the rate constant k, indicate the units.
(c) Calculate the rate when [OCl − ] = 2.0 x 10-3 M and
[I − ] = 5.0 x 10-4 M.
 Integrated rate laws
First order reactions:
Rate = k [A]
Rate = −Δ [A] / Δt
k [A] = −Δ [A] / Δt
Rearrange : Δ [A] / [A] = − k Δt
Integrate: ln ([A] / [A]o) = − k t
Rearrange: ln [A] = − k t + ln [A]o
Note: this follows the equation of a line:
y = m x + b. A plot of ln [A] vs. t is linear.
Example

The first-order rate constant of the decomposition of N2O5

at 35 °C is 0.35 min-1. Calculate the concentration of N2O5
after 4 minutes, if the initial concentration was 0.16 M.
Solution

Since the reaction is first-order in N2O5,

ln[N2O5]𝑡𝑡 = −𝑘𝑘𝑘𝑘 + ln[N2O5]0

We need to calculate [N2O5]t.

ln[N2O5]𝑡𝑡 = −0.35 4 + ln 0.16 = − 3.23

[N2O5]t = 𝑒𝑒 −3.23 = 0.04 𝑀𝑀

 First order reactions:
ln[A]0

ln [A]t
ln[A] slope= -k1

time

A plot of ln [A] vs. t is linear.

 Example
In the decomposition of azomethane (CH3N2CH3 →
2CH3 + N2) at a pressure of 2.18x104 Pa and a
temperature of 576K, the following time dependent
azomethane concentrations were recorded:

t/min 0 30 60 90 120 150 180

[azometh 8.70 6.52 4.89 3.67 2.75 2.06 1.55
ane]/
moldm-3
t/min 0 30 60 90 120 150 180
ln [azomethane] 2.16 1.87 1.59 1.30 1.01 0.72 0.44

The plot is a good straight line confirming the first-order kinetics.

The slope is equal to -k, can be determined from the plot which
gives a rate constant (k) of 9.59x10-3 min-1.
 Calculation method
An alternative method to plotting the graph is to calculate the value of k for each
time, t and see if the k values are constant.
t/min 0 30 60 90 120 150 180

[azomethane]/ 8.70 6.52 4.89 3.67 2.75 2.06 1.55

moldm-3
k=
𝟏𝟏
ln ([A]o/[A] 9.61x10-3 9.60x10-3 9.59x10-3 9.60x10-3 9.60x10-3 9.58x10-3
𝒕𝒕

k values are constant, therefore reaction follows first order kinetics.

Determine the average k:

9.61x10−3 + 9.60x10−3 + 9.59x10−3 + 9.60x10−3 + 9.60 x10−3 + 9.58x10−3

𝟔𝟔

= 9.60x10-3 min-1
 Half-life
• Definition: The amount of time
it takes for one-half of a reactant
to be used up in a chemical
reaction.
• First Order Reaction:
 ln [A] = − k t + ln [A]o
 ln ([A]o/2) = − k t½ + ln [A]o
 − ln ([A]o/2) + ln [A]o = k t½
 ln ([A]o / [A]o/2) = k t½
 ln 2 = k t½ or t½ = 0.693/k
 Second order reactions
Reaction for A → Products
Rate = k [A]2
Rate = − Δ [A] / Δ t
k [A]2 = − Δ [A] / Δ t
Rearrange: Δ [A] / [A]2 = − k Δ t
Integrate : 1/[A] = 1/[A]o + k t
Example

Acetaldehyde, CH3CHO, decomposes by second-

order kinetics with a rate constant of 0.334 M⋅s-1 at
500 °C. If the initial concentration of acetaldehyde is
0.002 M, find the concentration after 20 minutes
(1200 seconds).
 1 1
= 0.334 1200 +
[𝐴𝐴]𝑡𝑡 0.002

1
= 400.8 + 500 = 900.8
[𝐴𝐴]𝑡𝑡

1
[𝐴𝐴]𝑡𝑡 = = 0.0011 𝑀𝑀
900.8
 Second order reactions
Reaction for A → Products

1 slope= k 2
[A]t
[A]
1
[A] 0

time

A plot of 1/[A] vs t is linear

 Determining rxn order
The decomposition of NO2 at 300°C is described by
the equation
NO2 (g) NO (g) + 1/2 O2 (g)
and yields these data:

Time (s) [NO2], M

0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
 Determining rxn order
A graph of ln [NO2] vs. t:

The plot is not a straight line,

so the process is not first-
order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 -4.610
50.0 0.00787 -4.845 Does not fit:

100.0 0.00649 -5.038

200.0 0.00481 -5.337
300.0 0.00380 -5.573
 Second-Order Processes
A graph of 1/[NO2] vs. t
gives this plot.

Time (s) [NO2], M 1/[NO2]

This is a straight
0.0 0.01000 100
line. Therefore, the
50.0 0.00787 127 process is second-
100.0 0.00649 154 order in [NO2].
200.0 0.00481 208
300.0 0.00380 263