Chemical Kinetics

CH4002

2017
 Kinetics
In kinetics we study the rate at which a
chemical process occurs.
Besides information about the speed at
which reactions occur, kinetics also sheds
light on the reaction mechanism (exactly
how on the molecular scale the reaction
occurs).
Factors That Affect Reaction Rates

Physical state of the reactants.

In order to react, molecules must come
in contact with each other.
The more homogeneous the mixture
of reactants, the faster the molecules
can react.
Factors That Affect Reaction
Rates
Concentration of
reactants.
As the
concentration of
reactants increases,
so does the
likelihood that
reactant molecules
will collide.
Factors That Affect Reaction Rates
Temperature
At higher temperatures, reactant
molecules have more kinetic energy,
move faster, and collide more often and
with greater energy.
Factors That Affect Reaction Rates
Presence of a catalyst.
Catalysts speed up reactions by
changing the mechanism of the
reaction.
Catalysts are not consumed during the
course of the reaction.
 Reaction Rates

Rates of reactions can be determined by

monitoring the change in concentration
of either reactants or products as a function
of time.
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

A plot of [C4H9Cl]
versus time for this
reaction yields a curve
like this.
The slope of a tangent
to the curve at any point
is the instantaneous
rate at that time.
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

Most reactions slow

down over time.
Therefore, the best
indicator of the rate of a
reaction is the
instantaneous rate near
the beginning of the
reaction.
 Reaction Rates
C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

In this reaction, the

ratio of C4H9Cl to C4H9OH is 1:1.
Thus, the rate of consumption of
C4H9Cl is the same as the rate
of appearance of C4H9OH
Rates most often expressed as
mol dm-3 s-1.

[C4H9Cl] [C4H9OH]
Rate = t = t
Reaction Rates and Stoichiometry

What if the ratio is not 1:1?

2 HI(g) H2(g) + I2(g)
In such a case,
1 [HI] [I2]
Rate = =
2 t t
Reaction Rates and Stoichiometry

To generalize, then, for the reaction

aA + bB cC + dD

1 [A] 1 [B] 1 [C] 1 [D]

Rate = a = b = c = d
t t t t
 Concentration and Rate
One can gain information about the rate of
a reaction by seeing how the rate changes
with changes in concentration.
 Concentration and Rate

NH4+(aq) + NO2(aq) N2(g) + 2 H2O(l)

If we compare Experiments 1 and 2, we see

that when [NH4+] doubles, the initial rate
doubles.
 Concentration and Rate

NH4+(aq) + NO2(aq) N2(g) + 2 H2O(l)

Likewise, when we compare Experiments 5

and 6, we see that when [NO2] doubles, the
initial rate doubles.
 Concentration and Rate
This means
Rate [NH4+]
Rate [NO2]
Therefore,
Rate [NH4+] [NO2]
which, when written as an equation, becomes
+
Rate = k [NH4 ] [NO2 ]
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.
The exponents tell the order of the reaction with
respect to each reactant.
Since the rate law is
Rate = k[NH4+] [NO2]
the reaction is
First-order in [NH4+]
and
First-order in [NO2]
 Rate Laws
Rate = k[NH4+] [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.
 Generally for a reaction such as

A+B C

rate laws are expressed as

Rate = k [A]n [B]m

Rate is expressed as mol dm-3 s-1

k is the rate constant (units depend on the rate law). It is constant at a given temperatur

(n + m) refers to the order of the reaction. It is often 0, 1 or 2

(n + m) indicated the number of molecules involved in the slow step of the reaction

It is impossible to know the values of k, n or m without experimental data

Generally for a reaction such as

A+B C

rate laws are expressed as

Rate = k [A]n [B]m

Also

d[C]/ dt = -d[A]/dt =-d[B]/dt = k [A]n [B]m

Each of these refers to the differential form of

the rate equation
Rate = -d[A]/ dt = k

Rate = -d[A]/dt =k[A]

Rate = -d[A]/dt =k[A]2

Rate = -d[A]/dt = k[A][B]

Rate = -d[A]/ dt = k

Rate = -d[A]/dt =k[A]

Rate = -d[A]/dt =k[A]2

Rate = -d[A]/dt = k[A][B]

Rate = -d[A]/ dt = k

Rate = -d[A]/dt =k[A]

Rate = -d[A]/dt =k[A]2

Rate = -d[A]/dt = k[A][B]

 Integrated Rate Laws
Using calculus to integrate the rate law
for a first-order process gives us

[A]t
ln = kt
[A]0
where
[A]0 is the initial concentration of A, and

[A]t is the concentration of A at some time, t,

during the course of the reaction.
 Integrated Rate Laws

Manipulating this equation produces

[A]t
ln = kt
[A]0
ln [A]t ln [A]0 = kt
ln [A]t = kt + ln [A]0
which is in the form

y = mx + b
 First-Order Processes

ln [A]t = kt + ln [A]0

Therefore, if a reaction is first-order, a

plot of ln [A] vs. t will yield a straight
line, and the slope of the line will be k.
First-Order Processes

Consider the process in

which methyl isonitrile is
converted to acetonitrile.

CH3NC CH3CN
 First-Order Processes
CH3NC CH3CN

This data were

collected for this
reaction at 198.9 C.
 First-Order Processes

When ln P is plotted as a function of time, a

straight line results.
Therefore,
The process is first-order.
k is the negative of the slope: 5.1 105 s1.
 the initial rate data for binding of glucose to an enzyme present at a
concentration of 1,34 mmol/dm3 were obtained:

C6 H12O6 0 (mmol/dm3) 1.00 1.54 3,12 4.02

V0 (mol/dm3,s) 5.0 7.6 15.5 20.0

what is the reaction order with respect to glucose and what is

the value of the rate constant

V0 kr ,eff glu
a
assume a rate law and test
0

log 0 log k r ,eff a log glu 0

 log 0 log k r ,eff a log glu 0

a=1

kr ,eff 10 0, 6968
mol/mmol,s

= 4975 s-1
 The following kinetic data in Table 2 were obtained for the reaction
2 ICl + H2 I2 + 2 HCl
[i] Write the rate law for the reaction.
[ii] Determine the value of the rate constant and its units.
[iii] Predict the reaction rate for Experiment no 4.
[iv] Write out one possible elementary step corresponding
to the slow step in the reaction that is compatible with
the rate law.
Table 2
Table 2

Initial reaction rates for

2 ICl + H2 I2 + 2 HCl
Experiment [ICl]o / M [H2]o / M Initial Rate / M s-1

1 1.5 x 10-3 1.5 x 10-3 3.7 x 10-7

2 3.0 x 10-3 1.5 x 10-3 7.4 x 10-7

3 3.0 x 10-3 1.5 x 10-3 22 x 10-7

4 4.7 x 10-3 2.7 x 10-3 ?

 The concentration of N2O5 varied with time as shown in Table 3.
(i) Confirm graphically that the reaction is first order, showing all relevant labels,
units and scales.

(ii) Calculate the rate constant and its units.

(iii) Calculate the reaction rate at the point where [N2O5] is 0.032 M .

Table 3
Rate data for the decomposition of N2O5

t/s 0 200 400 600 1000

[N2O5] / M 0.110 0.073 0.048 0.032 0.014

Half-Life

Half-life is defined
as the time required
for one-half of a
reactant to react.
Because [A] at t1/2 is
one-half of the
original [A],
[A]t = 0.5 [A]0.
 Half-Life
For a first-order process, this becomes
0.5 [A]0
ln
[A]0 = kt 1/2

ln 0.5 = kt1/2

0.693 = kt1/2
0.693
= t1/2
k
Note: For a first-order process, then, the half-life does not depend on [A]0.

2012 Pearson Education, Inc.

An insecticide decomposes in water with a
first order kinetics and
a rate constant of 6.8x10-3 day-1 at 10oC.

Calculate the half-life of the reaction.

If the initial concentration of insecticide is 0.15 M,
calculate the concentration after 1 year.
:
The half-life for the radioactive decay of 14C is 5730 years.

An archaeological sample (e.g. a knife with a wooden handle) contained

wood that had only 69% of the 14C found in living trees.

Assuming a first order process, how long ago was the wood cut from the
tree for incorporating into the knife handle?
The half-life for the radioactive decay of 14C is 5730 years.

An archaeological sample (e.g. a knife with a wooden handle) contained

wood that had only 69% of the 14C found in living trees.

Assuming a first order process, how long ago was the wood cut from the
tree for incorporating into the knife handle?
 Second-Order Processes
Rate = k [A]2
Similarly, integrating the rate law for a
process that is second-order in reactant
A, we get

1 1
= kt +
[A]t [A]0

also in the form

y = mx + b
2012 Pearson Education, Inc.
 Second-Order Processes
1 1
= kt +
[A]t [A]0
So if a process is second-order in A, a
1
plot of [A] vs. t yields a straight line, and
the slope of that line is k.

2012 Pearson Education, Inc.

The decomposition of NO2 at 300 C is described by
the equation
1
NO2(g) NO(g) + 2
O2(g)
and yields data comparable to this table:
DETERMINE THE REACTION ORDER USING
THE INTEGRATED FOR OF THE RATE LAWS

Time (s) [NO2], M

[NO2]
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
Time /s
The decomposition of NO2 at 300 C is described by
the equation
1
NO2(g) NO(g) + 2
O2(g)
and yields data comparable to this table:
DETERMINE THE REACTION ORDER USING
THE INTEGRATED FOR OF THE RATE LAWS

Time (s) [NO2], M

[NO2]
0.0 0.01000
50.0 0.00787
100.0 0.00649 Not zero order
200.0 0.00481
300.0 0.00380
Time /s
 Test for first order
Plotting ln [NO2] vs. t yields
the graph at the right.
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

100.0 0.00649 5.038

200.0 0.00481 5.337

300.0 0.00380 5.573

 Second-Order Processes
Plotting ln [NO2] vs. t yields
the graph at the right.
The plot is not a straight
line, so the process is not
first-order in [A]. ln[NO2]

Time (s) [NO2], M ln [NO2]

0.0 0.01000 4.610

50.0 0.00787 4.845

100.0 0.00649 5.038

200.0 0.00481 5.337

300.0 0.00380 5.573 Time / s

 Test for Second-Order
1
Plotting[NO2] vs.
t,
however, gives this
plot

Because this is a
Time (s) [NO2], M 1/[NO2]
straight line, the
0.0 0.01000 100
process is second-
50.0 0.00787 127
order in [A].
100.0 0.00649 154

200.0 0.00481 208

300.0 0.00380 263

 Half-Life
For a second-order process,
1 1
= kt1/2 +
0.5 [A]0 [A]0

2 1
= kt1/2 +
[A]0 [A]0

2 1 = 1 = kt
1/2
[A]0 [A] 0

1
= t1/2
k[A]0
for the reaction:

2HI ( g ) H 2 ( g ) I 2 ( g )

the following rate data were collected at 580 K:

t (s) 0 1000 2000 3000 4000

HI (mmol/dm3) 1.00 0,112 0,061 0,041 0,031

determine the reaction order and the rate constant

Integrated rate laws - first order

d A ln A ln A0 kr t
k r A
dt

Integrated rate
laws second
order

d A
k r A
2

dt

1 1
kr t
A A0
 assume a second order reaction:

1 d HI
slope = 7,7978

k r HI
2

2 dt

1 1
kr = 3,90*10-3 dm3/mol,s
2k r t
HI HI 0
The following data were collected for the reaction

2HCl (g) H2 (g) + Cl2 (g) at 580 K

t/s 0 1000 2000 3000 4000

[HCl] / M 1.00 0.112 0.061 0.041 0.031

Plot the data in an appropriate fashion to prove that the reaction is second
order. From the graph, determine the rate constant (include the units).
(i) Some results for the initial rate of a reaction between two substances, A and B,
are shown in the following table.

[A]/ mol dm-3 [B]/mol dm-3 Initial rate/mol dm-3 s-1

1.4 x 10-2 2.3 x 10-2 7.40 x 10-9
2.8 x 10-2 4.6 x 10-2 5.92 x 10-8
2.8 x 10-1 4.6 x 10-2 5.92 x 10-6

Given that the rate equation for the reaction is of the form

V = k[A] [B]

(a) determine the order with respect to A, the order with respect to B
(b) calculate the rate constant, k
(c) what are the units for the rate constant, k?
Summary of Rate Laws