Mata Kuliah : Kinetika Kimia

Kode/sks : MAK3211/3

WEEK 1
Kinetics Basic Concepts:
Reaction Order, Molecularity, Rate Laws

Dr.Muhdarina,M.Si
Lab.Riset Sains Material, Jurusan Kimia FMIPA UR
Email: muhdarina.m@lecturer.unri.ac.id
 Kinetics
Basic concepts: reaction order,
molecularity, rate laws

The branch of physical chemistry which deals with

the rate at which the chemical reactions occur,
the mechanism by which the chemical reactions
take place and the influence of various factors
such as concentration, temperature, pressure,
catalyst etc., on the reaction rates is called the
chemical kinetics.
Types of chemical reactions

On the basis of reaction rates, the chemical reactions

have been classified into the following three types:

(1) Very fast or instantaneous reactions: These

reactions occur at a very fast rate generally these
reactions involve ionic species and known as ionic
reactions. It is almost impossible to determine the
rates of these reactions.
Examples
• (i) AgNO3 + HCl → AgCl + HNO3 (Precipitation
reaction)
• (ii) HCl + NaOH → NaCl + H2O (Neutralization
reaction)
(2) Moderate reaction : These reactions proceed
with a measurable rates at normal temperature
and it is these reactions are studied in chemical
kinetics. Mostly these reactions are molecular in
nature.
Examples
(i) Decomposition of H2O2 :
2H2O2 –> 2H2O + O2

(ii) Decomposition of N2O5 :

2N2O5 –> 2N2O4 + O3
(3) Very slow reactions: These reactions are
extremely slow and take months together to
show any measurable change.
Examples
(i) Rusting of iron:
Fe2O3 + xH2O → Fe2O3 xH2O
Hydrated ferriokside

(ii) 2H2 + O2 room temperature 2 H2O

Rate law : Molecularity and Order of a reaction
Molecularity is the sum of the number of molecules
of reactants involved in the balanced chemical
equation.
Example :
NH4NO2 –> N2 + 2H2O (Unimolecular)
NO + O2 –> NO2 + O2 (Bimolecular)
2NO + O2 –> 2NO2 (Trimolecular)

Molecularity of a complete reaction has no

significance and overall kinetics of the reaction
depends upon the rate determining step.
Slowest step is the rate-determining step. This was
proposed by Van't Hoff.
• If reaction is in the form of reaction mechanism
then the order is determined by the slowest step
of mechanism.
2A + 3B –> A2B3

The mechanism are:

A + B → AB (fast)
AB + B2 –> AB3 (slow)
(Rate determining step)
AB3 + A → A2B3 (fast)
(Here, the overall order of reaction is equal to 2)
• Reaction mechanism is a series of elementary steps that
make up a complex reaction (which the reaction actually
occurs)
• Exp: NO-catalyzed oxidation of SO2 has been postulated to
occur by the following 2-step process:

O2 + 2 NO 2NO2 (1)

2 (NO2 + SO2 NO + SO3 ) (2)

2SO2 + O2 2SO3 (3)

• NO2 in the step (1) is intermediate species; NO is consumed

in (1) and regenerated in (2) is the catalyst…..the both them
does not contain in the overall reaction (3)
• Step (1) that is the intermediate species occurred, is a
reaction intermediate
• The sum of the elementary steps must give the overall
equation for the reaction.
• A valid mechanism must correctly predict the
experimentally determined rate equation and be
consistent with all related kinetic experimental data and
stereochemical observations. The rate equation for the
overall reaction is slow rate-determining step
• Each step in the mechanism of a reaction is called an
elementary reaction. A simple reaction consist of a
single elementary step. A complex (or composite)
reaction consist of two or more elementary steps.
• Molecularity of a reaction is derived from the
mechanism of the given reaction. Molecularity
cannot be greater than three because more than
three molecules may not mutually collide with
each other. Molecularity of a reaction can't be
zero, negative or fractional.
• The total number of molecules or atoms whose
concentration determine the rate of reaction is
known as order of reaction.
• The order of a reactant is not related to the
stoichiometric coefficient of the reactant in the
balanced chemical equation, but from the
experiment
• Order of a reaction may be zero, negative,
positive or in fraction and greater than three.
Infinite and imaginary values are not possible.

Order of reaction = Sum of exponents of the

concentration terms in rate law

To generalize: xA + yB –> Products

The rate law : Rate (R) = k [A]x [B]y

n = x + y is the overall order of reactions, where

x and y are the orders with respect to
individual reactants.
k : rate constant
 Reaction
F2 (g) + 2ClO2 (g) 2FClO2 (g)

R = k [F2]x[ClO2]y

Exp 1 & 3:
Double [F2] with [ClO2]
constant;
Rate doubles……xx = 11

Exp 1 & 2: R = k [F2][ClO2]

Quadruple [ClO2] with [F2] constant;
Rate quadruples…. y=
y =11
Run Initial [A] Initial [B] Initial Rate (v0)
([A]0) ([B]0)
1 1.00 M 1.00 M 1.25 x 10-2 M/s
2 1.00 M 2.00 M 2.5 x 10-2 M/s
3 2.00 M 2.00 M 2.5 x 10-2 M/s

What is the order with respect to A? 0

What is the order with respect to B? 1

What is the overall order of the reaction? 1

 Initial Rate
[NO(g)] (mol dm-3) [Cl2(g)] (mol dm-3)
(mol dm-3 s-1)
0.250 0.250 1.43 x 10-6
0.250 0.500 2.86 x 10-6
0.500 0.500 1.14 x 10-6

What is the order with respect to Cl2? 1

What is the order with respect to NO? -1

What is the overall order of the reaction? 0

Reaction Rates

Rates of reactions can be determined by

monitoring the change in concentration of
either reactants or products as a function
of time. [A] vs t
Δ : change in concentration or time
Reaction rate is the change in the concentration of
a reactant or a product with time (M/s).

A B

[A] Δ[A] = change in concentration of A over

R= -
t time period Δt
[B] Δ[B] = change in concentration of B over
R=
t time period Δt

Because [A] decreases with time, [A] is negative.

 A B

time

[A]
R= -
t

[B]
R=
t
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

[C4H9Cl] M
In this reaction, the
concentration of
butyl chloride,
C4H9Cl, was
measured at various
times, t.
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

Average Rate, M/s

The average rate of

the reaction over
each interval is the
change in
concentration divided
by the change in time:
Reaction Rates

C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• Note that the average

rate decreases as the
reaction proceeds.
• This is because as the
reaction goes forward,
there are fewer
collisions between
reactant molecules.
• The reaction slows down
with time because the
concentration of the
reactants decreases.
Reaction Rates
C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

• A plot of concentration
vs. time for this
reaction yields a curve
like this.
• The slope of a line
tangent to the curve at
any point is the
instantaneous rate at
that time.
Reaction 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]
R=- =
t t
Reaction Rates and Stoichiometry

• What if the ratio is not 1:1?

H2(g) + I2(g)  2 HI(g)

The reaction shows that 1 mole of H2

disappear for every 2 moles of HI formed
• Only 1/2 HI is made for each H2 consumed.

R = - [H2] = 1/2
[HI]
t t
Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

R = - 1/a [A] = - 1/b[B] = 1/c [C]= 1/d [D]

t t t t

Reactants (decrease) Products (increase)

 Problem
Calculate the rate at which HI disappears in the following reaction
at the moment when I2 is being formed at a rate of 1.8 x 10-6 moles
per liter per second:
2 HI(g) →H2(g) + I2(g)
Solution
The balanced equation for the reaction shows that 2 moles of HI
disappear for every mole of I2 formed. Thus, HI is consumed in
this reaction twice as fast as I2 is formed:

The balanced equation states that 2 moles of HI are consumed for

every mole of I2 produced. HI should therefore disappear (3.6 x
10-6 M/s) twice as fast as I2 is formed (1.8 x 10-6 M/s).
 Problem
Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)

Initial Rate R = k [S2O82-]x[I-]y

Experiment [S2O82-] [I-]
(M/s)
1 0.08 0.034 2.2 x 10-4 y=1
x=1
2 0.08 0.017 1.1 x 10-4
3 0.16 0.017 2.2 x 10-4 R = k [S2O82-][I-]
Double [I-], rate doubles (experiment 1 & 2)
Double [S2O82-], rate doubles (experiment 2 & 3)
R 2.2 x 10-4 M/s
k= = = 0.08/M•s
[S2O8 ][I ] (0.08 M)(0.034 M)
2- -
Integrated Rate Laws

There are two forms of a rate law for chemical

kinetics: the differential rate law and the
integrated rate law.
The differential rate law relates the rate of
reaction to the concentrations of the various
species in the system

Integration of the equation of differential produces

the corresponding integrated rate law, which
relates the concentration to time.
Integrated Rate Laws
Consider a simple 1st order reaction:
AB
R = k [A] Differential form:

How much A is left after time t? Integrate:

Integrated Rate Laws
The integrated form of first order rate law:

Can be rearranged to give:

[A]0 is the initial concentration of A (t=0).

[A]t is the concentration of A at some time, t,
during the course of the reaction.
 Integrated Rate Laws

Manipulating this equation produces…

…which is in the form

y = mx + b
First-Order Processes

If a reaction is first-order, a plot of ln [A]t vs. t

will yield a straight line with a slope of -k.

So, use graphs to determine reaction order.

First-Order Processes
Consider the process in
which methyl isonitrile is
converted to acetonitrile.

CH3NC CH3CN

How do we know this is

a first order reaction?
First-Order Processes

CH3NC CH3CN

This data was

collected for this
reaction at 198.9°C.

Does Rate
R =k[CH3NC]
for all time intervals?
First-Order Processes

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

straight line results ( [A]t diganti dengan P utk
gas)
▫ The process is first-order.
▫ k is the negative slope: 5.1  10-5 s-1.
Buktikan hasil ini

Second-Order Processes
Similarly, integrating the rate law for a
process that is second-order in reactant A:

Buktikan hasil ini

Rearrange, integrate:

also in the form y = mx + b

Second-Order Processes

So if a process is second-order in A, a plot of

1/[A]t vs. t will yield a straight line with a
slope of k.
 Zero-Order Reactions

rate = k [A]0 = k Half life for zero order

[A]
rate = - t½ = t when [A] = [A]0/2
t
[A]0
t½ =
[A] - [A]0 = kt 2k
Determining reaction 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 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
Determining reaction order
Graphing ln [NO2] vs. t yields:

• The plot is not a straight

line, so the process is not
first-order in [A].

Does not fit:

Determining reaction order
Time (s) [NO2], M 1/[NO2]
0.0 0.01000 100
50.0 0.00787 127
100.0 0.00649 154
200.0 0.00481 208
300.0 0.00380 263

• This is a straight
line. Therefore,
the process is
A graph of 1/[NO2] vs. t second-order in
gives this plot. [NO2].
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-1st order

For a first-order process, set [A]t=0.5 [A]0 in

integrated rate equation:

NOTE: For a first-order

process, the half-life does
not depend on [A]0.
Half-Life- 2nd order
For a second-order process, set
[A]t=0.5 [A]0 in 2nd order equation.
 Summary of the Kinetics and Order
Of Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 R=k [A] - [A]0 = - kt t½ =
2k
ln 2
1 R = k [A] ln[A] - ln[A]0 = - kt t½ =
k
1 1 1
2 R = k [A]2 - = kt t½ =
[A] [A] k[A]0
0
Problem 1

• Show that rate constant k for the reaction

aA + bB cC
is:
Problem 2
• The time constant for the radioactive isotope,
226Ra, is 2338 years. Calculate the number of

atoms of 226Ra that decay each minute in a 2.00 g

sample of 226Ra. (We know that the nuclear decay
is a first order process)
Problem 3
• The stoichiometric equation for the oxidation of
bromide ions by hydrogen peroxide in acid
solution is:
2Br– + H2O2 + 2H+ → Br2 + 2H2O
Since the reaction does not occur in one stage,
the rate equation does not correspond to this
stoichiometric equation but is
υ = k[H2O2][H+][Br–]
Problem 3 (continued)
a.If the concentration of H2O2 is increased by a factor of 3,
by what factor is the rate of consumption of Br– ions
increased?
b.If the rate of consumption of Br– ions is 7.2 × 10–3 mol
dm–3 s–1, what is the rate of consumption of hydrogen
peroxide? What is the rate of formation of bromine?
c.What is the effect on the rate constant k of increasing the
concentration of bromide ions?
d.If by the addition of water to the reaction mixture the
total volume were doubled, what would be the effect on
the rate of change of the concentration of Br–? What
would be the effect on the rate constant k?