Chemical

Kinetics
Part 3
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

Recall
k change with respect to the overall order of the reaction to
ensure that the reaction rate has the correct units

1
 Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

A product

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k

1 rate = k [A] ln[A] = ln[A]0 - kt t½ = ln2

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

Check your understanding

2
Check your understanding

Check your understanding

3
 Euler’s Method
To determine the time evolution
in concentration predicted by
kinetic model
A

P
k
⎯
⎯→
d d
A t

A t
[ ] = − k [ ] ⇒ Δ[ ] = − k [ ]
A

A
Δ
A

Δ[ ] = Δ (− k [ ])
∆t, step size;
the smaller the better
A

A A

A t

[ ]+ =[ ] + Δ[ ]
t
Δ
t

= [ ] − kΔ [ ]
t

Numerical Approach
Predicting accurate reaction order and rate
constant from set of kinetics data
Only applicable for uniform sampling interval
d
C d

-
3
C

4
C Δ

⋅ + ⋅ −
A

A
0

A
1

A
2
t

2
t

Initial point =
⋅
t0

C Δ
d
C d

−
A
i
1

A
i
1
A

Intermediate ︵ +︶ ︵ −︶
t

2
t

=
point ⋅
ti
d
C d

4
C 2

3
C

− ⋅ + ⋅
A

A
3

AΔ
4

A
5
t

Last point =
⋅
t5

4
 Example
Determine the order of reaction and specific reaction rate
from batch data for reaction
AB

t (s) [A] (M)

0 4
Plotting [A] vs. t, or ln [A] vs. t
3 2.89 or 1/[A] vs. t?
5 2.25
8 1.45
Tedious; the order of reaction
10 1 could be a fraction or negative
12 0.65 values.
15 0.25
17.5 0.07 What to do??

Middle point approach

Number of n data reduces
t (s) [A] (M)
-d[A]/dt [A]av ln(-d[A]/dt) ln[A]av
0 4
0.370 3.445 -0.994 1.237
3 2.89
0.320 2.570 -1.139 0.944
5 2.25
0.267 1.850 -1.322 0.615
8 1.45
0.225 1.225 -1.492 0.203
10 1
0.175 0.825 -1.743 -0.192
12 0.65
0.133 0.450 -2.015 -0.799
15 0.25
0.072 0.160 -2.631 -1.833
17.5 0.07
d d
C t

k
C
αA
A

rate = − =
A
d d
C t
l
n

α
l
n
C
l
n
k

⎛ ⎞
A

⎜− ⎟= +
A

⎝ ⎠

5
 0.000

d d
C t
-2.000 -1.000 0.000 1.000 2.000

l
n

α
l
n
C
l
n
k
⎛ ⎞

A
-0.500
⎜− ⎟= +

A
-1.000
⎝ ⎠
y = 0.528x - 1.6373
-1.500
y = 0.5283x - 1.6327 Thus,
-2.000
R2 = 0.9978
Reaction order=0.528;
-2.500
k=e-1.6373=0.195 M0.47s-1
-3.000
Rate = 0.195[A]0.528

Example
Dinitrogen pentoxide (N2O5) decomposes to NO2 and
O2 at relatively low temperatures in the following Time (s) [N2O5] (M)
reaction: 0 0.0365

600 0.0274
2N2O5 (soln) → 4NO2 (soln) + O2 (g)
1200 0.0206

1800 0.0157
This reaction is carried out in a CCl4 solution at 45°C.
2400 0.0117
The concentrations of N2O5as a function of time are
3000 0.00860
listed in the following table. Determine the reaction
3600 0.00640
order (α), rate law and calculate specific reaction rate
(k).

6
 Example

1,3-Butadiene (CH2=CH—CH=CH2; C4H6) is a

volatile and reactive organic molecule used in Time (s) [C4H6] (M)
the production of rubber.
0 1.72 × 10−2
Above room temperature, it reacts slowly to form
products. 900 1.43 × 10−2

1800 1.23 × 10−2

Concentrations of C4H6 as a function of time at
326°C are listed in the following table. 3600 9.52 × 10−3

Determine the reaction order in C4H6, the rate 6000 7.30 × 10−3
law, and the rate constant for the reaction.

Numerical Approach
Number of n data remains by numerical approach

t [A] -d[A]/dt ln [A] ln (-d[A]/dt)

0 0.0365 1.71E-05 -3.31 -10.98

600 0.0274 1.33E-05 -3.60 -11.23

1200 0.0206 9.75E-06 -3.88 -11.54

1800 0.0157 7.42E-06 -4.15 -11.81

2400 0.0117 5.92E-06 -4.45 -12.04

3000 0.0086 4.42E-06 -4.76 -12.33

3600 0.0064 2.92E-06 -5.05 -12.75

Middle point approach can still be used

7
 d d
C t
l
n

α
l
n
C
l
n
k
-10
⎛ ⎞

A
-6.00 -5.00 -4.00 -3.00 -2.00 -1.00 0.00
⎜− ⎟= +

A
⎝ ⎠
-11

y = 0.987x - 7.69
y = 0.9872x - 7.6923
R2 = 0.9954 -12 Thus,
Reaction order=0.987;
-13
k=e-7.69=0.00046 M0.013s-1
Rate = 0.00046[A]0.987

Example
The rate constant for the reaction of hydrogen with iodine is
2.45 × 10–4 M–1 s–1 at 302°C and 0.950 M–1 s–1at 508°C.
a) Calculate the activation energy and Arrhenius pre-
exponential factor for this reaction.
b) What is the value of the rate constant at 400°C?

At 552.3 K, the rate constant for the thermal decomposition of

SO2Cl2 is 1.02 × 10–6 s–1. If the activation energy is 210 kJ
mol–1, calculate the Arrhenius pre-exponential factor and
determine the rate constant at 600 K.

8
 Reaction
Mechanisms

Reaction Mechanisms
The sequence of events that describes the actual
process by which reactants become products is called
the reaction mechanism.

™ Reactions may occur all at once or through several

discrete steps.

™ Each of these processes is known as an elementary

reaction or elementary process.

9
 Elementary Steps
The overall progress of a chemical reaction can be
represented at the molecular level by a series of simple
elementary steps or elementary reactions.

NET EQUATION

2NO (g) + O2 (g) 2NO2 (g)

N2O2 is detected during the reaction
REACTION MECHANISM

1.Elementary step: NO + NO N2O2

+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2

Intermediates and Molecularity

™ Intermediates are species that appear in a reaction
mechanism but not in the overall balanced equation.

™ An intermediate is always formed in an early elementary

step and consumed in a later elementary step.

™ Molecularity of a reaction is the number of molecules

reacting in the rate determining elementary step.

i. Unimolecular reaction – elementary step with 1 molecule

ii. Bimolecular reaction – elementary step with 2 molecules
iii. Termolecular reaction – elementary step with 3 molecules

10
 Rate Laws and Elementary Steps
™ The rate-determining step is the slowest step in the sequence of
steps leading to product formation.
™ The rate-determining step should predict the same rate law that is
determined experimentally.

Molecularity Elementary Step Rate Law Example

Unimolecular A → Products rate=k[A] N2O4(g) → 2NO2(g)

2
Bimolecular A+A → Products rate=k[A] 2NOCl → 2NO(g)+CO2(g)

A+B → Products rate=k[A][B] CO(g)+NO3(g) → NO2(g)+CO2(g)

3
Termolecular A+A+A → Products rate=k[A]

2
A+A+B → Products rate=k[A] [B] 2NO(g)+O2(g) → 2NO2(g)

A+B+C → Products rate=k[A][B][C] H+O2(g)+M → HO2(g)+M

The reaction rate and rate law can be determined

from the stoichiometry (coefficients) of the slowest
elementary step in the mechanism.

11
The experimental rate law for the reaction between NO2
and CO to produce NO and CO2 is rate = k[NO2]2. The
reaction is believed to occur via two steps:

Step 1: NO2 + NO2 NO + NO3

Step 2: NO3 + CO NO2 + CO2

What is the equation for the overall reaction?

NO2+ CO NO + CO2
What is the intermediate?

NO3
What can you say about the relative rates of steps 1 and 2?

Given rate = k[NO2]2 is the rate law for step 1

so step 1 must be slower than step 2

Series Reaction

Also called consecutive reactions

The reactant forms an intermediate product, which

react further to form another product.

kB kc
A B C

E.g. Reaction between ethylene oxide and ammonia

to produce mono-, di-, and triethanolamine.

12
 Parallel Reaction
Also called competing reactions

The reactant is consumed by 2 different reaction

pathways to form different products

B
kB

A
kc C

E.g. Oxidation of ethylene to ethylene oxide

Complex Reaction

Simultaneous series and parallel reactions

A+B C+D

A+C E

E.g. formation of butadiene from ethanol

13
 Independent Reaction

Occur in feed stocks containing many reactants.

A B

C D+E

E.g. cracking of crude oil to form gasoline

Mechanisms in Parallel Reactions

Single reactant become variety of products
B
A

C
k

kB
C
B

⎯⎯→ ⎯⎯→
r2

k
[
A
]

A
r1

kB
[
A
]

=
C

=
kc C
d
[
] t
A
d
[
] t
A

k
[
A
]
kB
[
A
]

⎛ ⎞ ⎛ ⎞
d
d

−⎜ ⎟ = −⎜ ⎟ =
C

⎝ ⎠ ⎝ ⎠
d
[
] t
A

kB
[
A
]
k
[
A
]

kB
k
A

=︵− + ︶[ ]
d

=− −
C

14
 For reactant A

d
[
] t
A

kB
k
A

A
e
+ ︶[ ]

k
k
t
=︵− [ ]=[ ]
d

−( )

C
C
+

0
d
A
/
d
t
k
A

A
e
k
tA
[ ] =− [ ] [ ]= [ ] −

0
Compare with

For product B
t Integrate
0
;
A

0
[ ]

k BkB
[
A
] 0kC
d
[
B
]

= =
0

[
B
]

1
e
kB
[
A
]
kB
[
A
]0
e

(− )

k
k

t
k
k

︵− + ︶

C
︵− + ︶
B

C
d
t

= = =
+

Ratio Product Concentration

For product C
Integrate
t
0
;
A

k kB
[
A
] 0k C

= [ ]0 =
d
[
C
]

[
C
]

1
e
k
[
A
]
k
[
A
]0
e

(− )
k
k

t
C
k
k

︵− + ︶
B

︵− + ︶
=
d
t

= =
C

At any time during the reaction,

[
B
] C
k Bk C
[
]

15
 Example

™ The rate law for this reaction is found (experimentally) to

be

™ Because termolecular processes are rare, this rate law

suggests a two-step mechanism.

™ A proposed mechanism is

™ Step 1 includes the forward and reverse reactions.

™ The rate of the overall reaction depends upon the rate of

the slow step.

™ The rate law for that step would be

™ But how can we find [NOBr2]?

16
™ NOBr2 can react two ways:

™ With NO to form NOBr

™ By decomposition to reform NO and Br2

™ The reactants and products of the first step are in

equilibrium with each other.
Because Ratef = Rater ,

k1 [NO] [Br2] = k−1 [NOBr2]

Solving for [NOBr2] gives us

k1
k−1 [NO] [Br2] = [NOBr2]

Substituting this expression for [NOBr2] in the rate law for

the rate-determining step gives

17
 Summary

Reaction Rates How we measure rates.

How the rate depends on amounts

Rate Laws of reactants.
How to calc amount left or time to
Integrated Rate Laws reach a given amount.
How long it takes to react 50% of
Half-life reactants.

Arrhenius Equation How rate constant changes with T.

Link between rate and molecular

Mechanisms scale processes.

18