CHEMICAL KINETICS

Chapter 13

1
 2

Chemical Kinetics
• 13-1 the rate of the reaction
• 13-2 the rate low
• 13-3 the relation between reactant
concentration and time
• 13-4 activation energy and temperature
dependence of rate constants
• 13.5 reaction mechanisms
• 13-6 catalysis
 3
Reaction of molecular

bromine and formic

acid

Haber Process

Ostwald process for the

production of nitric acid

Enzyme Catalysis
Projects Chemistry
in
action

4
Determination the age of the
shroud of Turin

Femtochemistry

5
13-1 the rate of the reaction
• Chemical kinetics – is the area of chemistry concerned
with the speeds, or rates at which a chemical reaction
occurs
• Reaction rate is the change in the concentration of a
reactant or a product with time (M/s).
A B
D[A] D[A] = change in concentration of A over
rate = -
Dt time period Dt
D[B] D[B] = change in concentration of B over
rate =
Dt time period Dt
Because [A] decreases with time, D[A] is negative.

Dr. Laila Al-Harbi

 A B

time product
Reactant

[B] increases with time

D[A]
rate = -
Dt

Dr. Laila Al-Harbi

D[B]
rate =
Dt
[A] decreases with time
Reaction of molecular bromine and formic acid
Br2 (aq) + HCOOH (aq) → 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

Dr. Laila Al-Harbi

Br2 (aq)

393 nm
393 nm Detector
light
 k = slope

D[Br2] [Br2]final – [Br2]initial

average rate = - =-
Dt tfinal - tinitial

0.0101 – 0.0120
1st 50 sec, average rate =- = 3.80 x 10-5 M/s
50 - 0.0
instantaneous rate = rate for specific instance in time
rate a [Br2] ….. rate =k [Br2]
K is not affect by the concentration of Br2 ,
the ratio rate/[Br2] remain [Link] at constant temperature
Laila Al-Harbi
Decomposition of Hydrogen Peroxide
2H2O2 (aq) 2H2O (l) + O2 (g)

D[O2]
rate =
Dt

PV = nRT

n
P= RT = [O2]RT
V
1
[O2] = P
RT

D[O2] 1 DP
rate = = measure DP over time
Dt RT Dt
Dr. Laila Al-Harbi
Reaction Rates and Stoichiometry

aA + bB cC + dD

2A B 1 D[A]
rate = -
a Dt
1 D[B]
1 D[A] rate = -
rate = - b Dt
2 Dt
1 D[C]
rate =
c Dt
D[B]
rate =
Dt 1 D[D]
rate =
d Dt

Dr. Laila Al-Harbi

 Example 13-1
Write the rate expression for the following reaction:
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g)

D[CH4] 1 D[O2] D[CO2] 1 D[H2O]

rate = - =- = =
Dt 2 Dt Dt 2 Dt

Dr. Laila Al-Harbi

Write the rate expression for the following reaction:
4NH3 (g) + 5O2 (g) →4 NO (g) + 6H2O (g)

rate = - 1 D[NH3] 1 D[O2] 1 D[NO] 1 D[H2O]

=- = =
4 Dt 5 Dt 4 Dt 6 Dt
Example 13-2
• Consider the reaction
4NO2 (g) + O2 (g) 2N2O5 (g)
• Is reacting rate of 0.024 M/s a) at what rate is N2O5 being
formed ? B) at what rate is NO2 reacting?

rate = - -1 D[NO2] -D[O2] = 1 D[N2O5]

=
4 Dt Dt 2 Dt
D[O2]
= - 0.024 M/s
Dt
D[O2] -1 D[NO2] =4( - 0.024) = -0.096 M/s
= Dt
Dt 4

D[N2O5]
D[O2] = 1 =2( - 0.024) = 0.048 M/s
Dt
Dt 2 Dr. Laila Al-Harbi
Which expression correctly states the rate of reaction?

N2(g) + 3 H2(g) 2 NH3(g)

13-2 the rate low
• The rate law expresses the relationship of the rate of a reaction to
the rate constant and the concentrations of the reactants raised to
some powers.

aA + bB → cC + dD 4NO2 (g) + O2 (g)→2N2O5 (g)

Rate = k [A]x[B]y Rate = k [NO2]2[O2]

reaction is xth order in A reaction is 2nd order in [NO2]

reaction is yth order in B
reaction is 1st order in [O2]
reaction is
reaction is 3rd order overall
(x +y)th order overall

Dr. Laila Al-Harbi

 F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2]x[ClO2]y

In 1,2 [F2] is constant we will see the effect of [ClO2] on the initial rate

[ClO2]2/ [ClO2]1 = 0.04/0.01 = 4

Rate 2/Rate 1 = 4.8 ×10-3/1.2 ×10-3 = 4

In 1,3 [ClO2] is constant we will see the effect of [F2] on the initial rate

[F2] 3/ [F2] 1 = 0.2/0.1 = 2

Rate 3/Rate 1 = 2.4 ×10-3/1.2 ×10-3 = 2

Dr. Laila Al-Harbi

In 1,2 [F2] is constant we will see the effect of [ClO2] on the initial rate

Quadruple [ClO2] with [F2] constant → Rate quadruples

→Reaction is 1st order in [ClO2] → y = 1

In 1,3 [ClO2] is constant we will see the effect of [F2] on the initial rate

Double [F2] with [ClO2] constant→ Rate doubles → Reaction is

1st order in [F2]→ x = 1
rate = k [F2][ClO2] reaction is 2nd order overall
Calculation of k
rate
k=
[F2][ClO2]

1.2 x 10-3 M/s

k= rate = 1.2 [F2][ClO2]
(0.10 M)(0.010 M)

k = 1.2 / M s
Dr. Laila Al-Harbi
 EXAMPLE 13-3
Determine the rate law and calculate the rate constant for the following reaction from the following
data:
2 NO (g) + 2 H2 (g) → N2 (g) + H2O (g)

Initial
Experime
[NO] [H2] Rate
nt
(M/s)
1 0.005 0.002 1.3 x 10-5
2 0.01 0.002 5 x 10-5
3 0.01 0.004 10 x 10-5
In 1,2 [H2]is constant we will see the effect of [NO] on the rate

[NO ]2/ [NO ]1 = 0.01/ 0.005 = 2

Rate 2/Rate 1 = 5 x 10-5/ 1.3 x 10-5= 4= 22
In 2,3 [NO] is constant we will see the effect of [H2] on the initial rate
[H2]3/ [H2]2 = 0.004/0.002 = 2
Rate 3/Rate 2 = 10 x 10-5/ 5 x 10-5= 2
y [NO]= 2
x [H2], = 1
rate 1.3 x 10-5 M/s
k= = = 2.2 x 10-4 M•s
[H2][NO]2 (0.02 M)(0.005 M)

rate = k [H2][NO]2

reaction is 3rd order overall

rate = 2.2 x 10-4 [H2][NO]2

Dr. Laila Al-Harbi

 W + X  Y + Z
The rate of a chemical reaction is affected by: Rate = k[W]
a. the concentration of the reactants. The order of this reaction with respect to X
b. the temperature of the reaction. is:
c. the presence of a catalyst. a. zeroth.
d. all of the above. b. first.
c. second.
d. third.

If tripling the concentration of reactant A A + B  C + D

multiplies the initial rate of the reaction by Rate = k[A][B]
nine, the reaction is _______ order in A. The overall order of this reaction is:
a) zeroth a. first.
b) First
b. second.
c) second
d) third c. third.
d. fourth.
13-3 the relation between reactant concentration and time

First-Order Reactions D[A]

rate = -
A → product Dt
rate M/s
rate = k [A] k= = = 1/s or s-1
[A] M
D[A] D[A]
- = k [A] -∫ = k ∫ Dt
Dt [A]
if we integrate from time t to 0, we get the following:

[A]
Integrate: ln =-kt ln [A] = - k t + ln [A]0
[A]0

[A] is the concentration of A at any time t

[A]0 is the concentration of A at time t=0
Dr. Laila Al-Harbi
A plot of ln[A]t versus t gives a straight line

Y = mX + b

ln[A]t = - kt + ln[A]o

where [A]t = M of A at time = t & [A]o = M of A at t = 0

b Intercept
Slope (m) = - k
ln[A]t

Time, t

Dr. Laila Al-Harbi

 Example 13.4
• The reaction 2A → B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it
take for A to decrease from 0.88 M to 0.14 M ?

[A]0 = 0.88 M
ln[A] = ln[A]0 - kt
[A] = 0.14 M
kt = ln[A]0 – ln[A]
[A]0 0.88 M
ln ln
[A] 0.14 M
t = ln[A]0 – ln[A] = = = 66 s
k k 2.8 x 10-2 s-1

Dr. Laila Al-Harbi

• For gas-phase reactions we can replace the con.
Term with pressures of the gaseous reactant.
A → product

[A] = P/RT

[A]
Substituting : ln =-kt

Dr. Laila Al-Harbi

[A]0

P/RT
Substituting : ln =-kt
P/RT 0
P
ln =-kt ln P = - k t + ln P 0
P0
 Half-life of First-Order Reactions
The half-life, t½, is the time required for the concentration of a
reactant to decrease to half of its initial concentration.

[A]
ln =-kt t½ = t when [A] = [A]0/2
[A]0

[A]0
ln
[A]0/2 ln2 0.693
t½ = = =
k k k
What is the half-life of N2O5 if it decomposes with a rate constant of
5.7 x 10-4 s-1? The decomposition
Ln 2 0.693 is first order
t½ = = = 1200 s = 20 minutes because the unit
k -4
5.7 x 10 s -1
of k (s-1)
Dr. Laila Al-Harbi
Dr. Laila Al-Harbi
 Second-Order Reactions
D[A]
A product rate = - rate = k [A]2
Dt
D[A]
rate M/s - = k [A]2
k= = 2 = 1/M•s Dt
[A]2 M

1 1
Integrate: = + kt
[A] [A]0
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0
1 1
= kt +
[A] [A]0
y = mx + b
1
t½ = t when [A] = [A]0/2 t½ =
k[A]0
The reaction 2A B
is second order with a rate constant of 51 / [Link] at 24°C.
a)Starting with [A] = 0.0092 M, how long will it take for [A] = 3.7 x 10-3 M?
b)Calculate the half-life of the reaction.

a) 1 1
= + kt
[A] [A]0
1 1 .min) t
= + (51 /M
3.7 x 10-3 M 0.0092 M

t = 3.2 min
b) 1 1 = 2.2 min
t½ = =
k[A]0 51/[Link] x 0.0092 M
Dr. Laila Al-Harbi
 Zero-Order Reactions
D[A]
A product rate = - rate = k [A]0 = k
Dt
D[A]
rate - =k
k= 0
= M/s Dt
[A]

Integrate: [A] = [A]0 - kt

[A] is the concentration of A at any time t

[A]0 is the concentration of A at time t=0

t½ = t when [A] = [A]0/2 [A]0

t½ =
2k

Dr. Laila Al-Harbi

 Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time Equation Units

Order Rate Law Half-Life of k

[A]0
0 rate = k [A] = [A]0 - kt t½ = M s-1
2k

ln[A] = ln[A]0 - kt ln2 s-1

t½ =
1 rate = k [A]
k
1 1 1
2 rate = k [A]2 = + kt t½ = M-1 s-1
[A] [A]0 k[A]0

Dr. Laila Al-Harbi

The time needed for half of the reactant to be consumed is called
the __________ of the reaction.
a. midpoint
b. equivalence point
c. half-rate
d. half-life

The half-life of a first-order reaction is equal to _________,

where k is the rate constant.
a. 0.693/k
b. 0.693k
c. k/2
d. 2k

The rate-determining step is the __________ step in a reaction

mechanism.
a. first
b. last
c. fastest
d. slowest
 13-4 activation energy and temperature dependence of rate constant

• Collision Theory
• Before atoms, molecules, or ions can react, they must first
collide.
• An effective collision between two molecules puts enough
energy into key bonds to break them.

Dr. Laila Al-Harbi

• The activation energy (Ea) is the minimum energy that must
be supplied by collisions for a reaction to occur.
• The configuration of the atoms of the colliding species at the
time of the collision is called the transition state.
• The transitory species having this configuration is called the
activated complex.
A Reaction Profile
CO(g) + NO2(g)  CO2(g) + NO(g)

Dr. Laila Al-Harbi

 Effect of Temperature on
the Rates of Reactions
In 1889, Svante Arrhenius proposed the following expression for the
effect of temperature on the rate constant, k:
k = Ae–Ea/RT
The constant A, called the frequency factor, is an expression of collision
frequency and orientation; it represents the number of collisions per
unit time that are capable of leading to reaction.
The term e–Ea/RT represents the fraction of molecular collisions
sufficiently energetic to produce a reaction

ln k = ln A + ( –Ea/R) 1/T
Y = b + m x
 Arrhenius equation
k = A • exp( -Ea/RT )
(Arrhenius equation)

Ea is the activation energy (J/mol)

R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
-Ea 1
A is the frequency factor Ln k = - + lnA
R T

Non-graphical method:
If you have 2 sets of conditions,
solve for k1, k2, T1, T2 or Ea using

Dr. Laila Al-Harbi

Dr. Laila Al-Harbi
 13.6 catalyst
A catalyst is a substance that increases the rate of a chemical reaction without itself being
consumed.

Ea

uncatalyzed catalyzed

ratecatalyzed > rateuncatalyzed

Dr. Laila Al-Harbi
 Homogeneous Catalysis
• Homogeneous catalyst- catalyst and reactants are
in the same phase, usually liquid
Acid catalysts
Base catalyses

• Advantage

Low cost
Carried out under atmospheric conditions
Selective for particular reaction
Dr. Laila Al-Harbi
Example
CH3COOC2H5 +H2O →CH3COOH + C2H5OH
Rate (un-catalysed) = K[CH3COOC2H5]

In presence of [HCl]acid (catalyst)

CH3COOC2H5 +H2O →CH3COOH + C2H5OH

Rate (catalysed) = Kc[CH3COOC2H5][H+]

Kc > K ( reaction become faster)

Heterogeneous Catalysis
• Heterogeneous catalyst- the reactants and the catalyst are in
different phases. catalyst = solid reactants = liquid/gas
• The most important type of catalyst in industrial chemistry
• Four steps in heterogeneous catalysis:
• Reactant molecules are adsorbed.

Dr. Laila Al-Harbi

• Reactant molecules diffuse along the surface.
• Reactant molecules react to form product molecules.
• Product molecules are desorbed (released from the surface).
Examples
 Haber synthesis of ammonia
 Ostwald process for the production of nitric acid
 Catalytic converters
 Haber Process

N2 (g) + 3H2 (g) → 2NH3 (g) DH = -92.6 kJ

Exothermic and slow at room temperature

Fe/Al2O3/K2O
N2 (g) + 3H2 (g) →
catalyst
2NH3 (g) T = 500 0C

 Reactant molecules are adsorbed.

 Reactant molecules dissociate along the surface.
 Reactant molecules react to form product molecules.
 Product molecules are desorbed (released from the surface).

Dr. Laila Al-Harbi

Ostwald process for the production of nitric acid

4NH3 (g) + O2 (g) →4NO (g) + 6H2O (g)

2NO (g) + O2 (g) →4NO2 (g)

2NO2 (g) + H2O (ℓ) →HNO2 (aq) + HNO3 (aq)

3HNO2 (aq) →HNO3 (aq)+ H2O (ℓ)+ 2NO (g)

The NO generated can be recycled to produce NO2 in 2nd step.

 Catalytic converters
• Inside a running car engine
N2 (g) + O2 (g) → 2NO(g)

New cars are equipped with catalytic converters

catalytic converters is a mixture of Pd, Pt, and Rh, which are embedded in
ceramic honeycombs.
These metals catalyze the following reaction, which converts toxic gases (NO
& CO) to non-toxic CO2 and N2:
2CO(g) + 2NO(g)  2CO2(g) + N2(g)
 Enzyme Catalysis
• Enzymes are biological catalyst.
• increase the rate of reaction 106-108, highly specific

• The reactant substance, called the substrate (S), attaches itself to an area
on the enzyme (E) called the active site, to form an enzyme-substrate
complex (ES). ( lock-and-key theory) –Emil Fischer

Dr. Laila Al-Harbi

• The enzyme–substrate complex decomposes to form products (P), and the
enzyme is regenerated.
 Factors Influencing Enzyme Activity
• The rates of enzyme-catalyzed reactions are influenced by factors such as
concentration of the substrate, concentration of the enzyme, acidity of
the medium, and temperature.
• Mechanism
k1
E + S ↔ ES
k2

Dr. Laila Al-Harbi

ES ↔ E+P

Rate = ∆P/ ∆ t = k2 [ES]

A catalyst increases the rate of a
reaction by:

a. causing the molecules to move more rapidly.

b. causing the molecules to collide more
frequently.
c. lowering the energy of activation.
d. all of the above.
Self study

13.5 , 13.7, 13.15, 13.19,

13.27 , 13.29, 13.39 ,
13.41 13.45, 13.51

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