CHEM 101 – Chemistry for

Scientists and Engineers

“Chemistry: Science of Change”
by Oxtoby, Freeman, Block

Chapter 14: Chemical Kinetics

Sesil Agopcan Çınar, Çimen Özgüç Önal

 Outline
• Rates of Chemical Reactions
• Reaction Rates and Concentrations
• The Dependence of Concentrations on Time
• Reaction Mechanisms
----------------------------------------------------------------
• Reaction Mechanisms and Rate Laws
• The Effect of Temperature on Reaction Rates
• Kinetics of Catalysis
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 Chemical Kinetics

• Study of the rates of reactions

• Find the mechanisms of reactions from experiments

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 Factors Affecting Reaction Rates
• Temperature
• Concentration
• Catalyst
• Physical state steel nail steel wool

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 Reaction Rate
• Determine reaction rates: change in
concentration of either reactants or
products as a function of time.

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 Reaction Rate
• Average reaction rate: divide change in
concentration of a reactant (or product) by the
time interval over which the change occurs.

NO2 (g) + CO (g)  NO (g) + CO2 (g)

[NO]
Average rate 
t

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 Reaction Rate
NO2 (g) + CO (g)  NO (g) + CO2 (g)
Time [NO] (mol L-1) Average rate (mol L-1 s-1)
0 0
31 x 10-5
50 0.0155
16 x 10-5
100 0.0223
5.8 x 10-5
150 0.0262
200 0.0287
250 0.0304

[NO] (0.0155  0) mol L1

Average rate    31 x 10-5 mol L1s 1
t (50  0) s
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 Reaction Rate
NO2 (g) + CO (g)  NO (g) + CO2 (g)

31 x 10-5 mol L1s 1

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 Problem 14-2
A reaction generates CO2 in a vessel of constant
volume at a temperature of 25 C. The partial
pressure of the CO2 (g) is 0.520 atm at 11:00 A.M. and
0.645 atm at 11:30 A.M. the same day. Compute the
average rate of appearance of CO2 (g) during this
period of time (in mol L-1s-1).
Solution:

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Reaction Rates and Stoichiometry
NO2 (g) + CO (g)  NO (g) + CO2 (g)
[NO2 ] [CO] [NO] [CO2 ]
Rate     
t t t t

2 NO2 (g) + F2 (g)  2 NO2F (g)

 1  [NO2 ] [F2 ]  1  [NO2F]

Rate      
 2  t t  2  t

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Reaction Rates and Stoichiometry
aA + bB  cC + dD
1 [A] 1 [B] 1 [C] 1 [D]
Rate     
a t b t c t d t

Example:

2 H2CO(g) + O2(g)  2 CO(g) + 2 H2O(g)

1 [H2CO] [O2] 1 [CO] 1 [H2O]

Rate     
2 t t 2 t 2 t
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 Outline
• Rates of Chemical Reactions
• Reaction Rates and Concentrations
• The Dependence of Concentrations on Time
• Reaction Mechanisms
----------------------------------------------------------------
• Reaction Mechanisms and Rate Laws
• The Effect of Temperature on Reaction Rates
• Kinetics of Catalysis
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 Order of a Reaction
N2O5 (g)  2 NO2 (g) + ½ O2 (g)
The rate of decomposition of N2O5
is proportional to its concentration.
Rate = k [N2O5]
Rate law - reaction rate and
concentration
Rate constant (rate coefficient)
proportionality constant

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 Order of a Reaction
a A  Products
Rate = k [A]n Rate = k [A]0 = k
Zeroth order
n → order of a reaction from experimental data

N2O5 (g)  2 NO2 (g) + ½ O2 (g)

Rate = k [N2O5] → First order

C2H6 (g)  2 CH3 (g)

Rate = k [C2H6]2 → Second order 14
 Problem 14-16
The following data were obtained at 750 K for the reaction:
C4H8 (g)  products

[C4H8] (mol L-1) Rate (mol L-1s-1)

0.0095 3.42 x 10-5
0.0070 2.52 x 10-5
0.0025 9.0 x 10-6

(a) Write the rate law for this reaction.

(b) Calculate the rate constant.

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 Solution (Pb. 14-16)
[C4H8] (mol L-1) Rate (mol L-1s-1)
0.0095 3.42 x 10-5
0.0070 2.52 x 10-5
0.0025 9.0 x 10-6

The reaction is first order in C4H8(g) since a reduction

of the concentration of the C4H8(g) causes a
reduction in the observed rate in direct proportion.
(a) n = ? and Rate law = ?
(b) k = ?

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 Example 14-2
At high temperatures, HI reacts according to:
2 HI (g)  H2 (g) + I2 (g)
At 443C, the initial rate of the reaction increases with the
concentration of HI, as shown in the table:
Experiment No. [HI] (mol L-1) Initial Rate (mol L-1s-1)
1 0.005 7.5 x 10-4
2 0.01 3.0 x 10-3
3 0.02 1.2 x 10-2

(a) Determine the order of reaction with respect to HI and

write the rate law.
(b) Calculate the rate constant and give its units.
(c) Calculate the instantaneous rate of the reaction when
[HI] = 0.002 M. 17
 Solution (Ex. 14-2)
2 HI (g)  H2 (g) + I2 (g)
Rate = k [HI]n
Experiment No. [HI] (mol L-1) Initial Rate (mol L-1s-1)
1 0.005 7.5 x 10-4
2 0.01 3.0 x 10-3
3 0.02 1.2 x 10-2

(a) n = ? and Rate law = ?

(b) k = ?
(c) Rate = ?
when [HI] = 0.002 M
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 Rate Law
Rates that depend on two or more concentrations:
a A + b B  Products
Rate = k [A]m[B]n

mth order in A
nth order in B
m + n  overall reaction order

H2PO2− (aq) + OH− (aq)  HPO32- (aq) + H2 (g)

Rate = k [H2PO2−][OH−]2 19
 Example
Nitrogen monoxide reacts rapidly with oxygen to give
nitrogen dioxide:
2 NO (g) + O2 (g)  2 NO2 (g)
The initial rate of the reaction is measured three times at
the same temperature but with different initial
concentrations of NO and O2:

Exp. no. [NO] (mol L-1) [O2] (mol L-1) Initial Rate (mol L-1s-1)
1 1.0 x 10-4 1.0 x 10-4 2.8 x 10-6
2 1.0 x 10-4 3.0 x 10-4 8.4 x 10-6
3 2.0 x 10-4 3.0 x 10-4 3.4 x 10-5

Determine the rate law and the value of the rate constant.
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 Solution
2 NO (g) + O2 (g)  2 NO2 (g)

Exp. no. [NO] (mol L-1) [O2] (mol L-1) Initial Rate (mol L-1s-1)
1 1.0 x 10-4 1.0 x 10-4 2.8 x 10-6
2 1.0 x 10-4 3.0 x 10-4 8.4 x 10-6
3 2.0 x 10-4 3.0 x 10-4 3.4 x 10-5

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 Outline
• Rates of Chemical Reactions
• Reaction Rates and Concentrations
• The Dependence of Concentrations on Time
• Reaction Mechanisms
----------------------------------------------------------------
• Reaction Mechanisms and Rate Laws
• The Effect of Temperature on Reaction Rates
• Kinetics of Catalysis
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 Dependence of
Concentrations on Time
Integrated Rate Law for First-Order Reactions
N2O5 (g)  2 NO2 (g) + ½ O2 (g)
[N2O5 ]
Rate    k[N2O5 ]
t

d[N2O5 ]
= -kdt
[N2O5 ]

ln[N2O5]t = ln[N2O5]0 – kt
y = mx + b (linear equation)
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Integrated Rate Law for First-Order Reactions

A  Products
ln [A]t = ln [A]0 – kt

[A]t can be used with any concentration units

ln = -kt if [A]t and [A]0 have the same units.
[A]0

Recall: M = P / RT Pt
ln  kt P = Pressure
P0
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First-Order Reactions
CH3NC (g)  CH3CN (g)

k = - slope = 5.1 x 10-5 s−1

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 Half-Life (t1/2)
t1/2
[A] [A]/2
ln[A]t – ln[A]0 = –kt

 [A]t 
ln   kt
 [A]0 

 [A]0 
 
ln 
2 
 kt1 / 2
[A]0

ln 2
t1 / 2 
k
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 Example (Problem 14-27)
Chloroethane decomposes at elevated temperatures
according to the equation:
C2H5Cl (g)  C2H4 (g) + HCl (g)
This reaction obeys first-order kinetics. After 340 s at
800 K, a measurement shows that the concentration of
C2H5Cl (g) has decreased from 0.0098 mol L-1 to 0.0016
mol L-1. Calculate the rate constant and the half-life
(t1/2) at 800 K.

Hint: ln[C2H5Cl]t = ln[C2H5Cl]0 – kt

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 Solution (Pb. 14-27)
  C2 H5Clt 
ln    kt Integrated Rate Law for 1st order reaction
  C2 H5Cl 
 0 

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 Dependence of
Concentrations on Time
Integrated Rate Law for Second-Order Reactions
NO2 (g)  NO (g) + ½ O2 (g)

[NO2 ]
Rate    k[NO2 ]2
t Slope = k
1 1
 kt 
[NO2 ]t [NO2 ]0

Derive this equation

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 Example: Graphing Data to
Determine the Order of a Reaction
The data listed in the Table below were obtained
for the decomposition reaction A  products.
(a) Establish the order of the reaction. (b) What
is the rate constant? (c) What is the half-life, t1/2,
if [A]0 = 0.01 M?
Time (s) [A] (M)
0 0.01000
50 0.00787
100 0.00649
200 0.00481
300 0.00380 30
 Solution
Time (s) [A] ln [A] 1/[A]
0 0.01000 -4.610 100
50 0.00787 -4.845 127
100 0.00649 -5.038 154
200 0.00481 -5.337 208
300 0.00380 -5.573 263

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 Solution

Derive t1/2 using the integrated rate law for 2nd order reactions.

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 Outline
• Rates of Chemical Reactions
• Reaction Rates and Concentrations
• The Dependence of Concentrations on Time
• Reaction Mechanisms
----------------------------------------------------------------
• Reaction Mechanisms and Rate Laws
• The Effect of Temperature on Reaction Rates
• Kinetics of Catalysis
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 Reaction Mechanisms
• Reactions occur at one or more steps.
• Each step is an elementary step.
• The number of reacting species in an elementary
step is the molecularity of the step.

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 Reaction Mechanisms
NO2 (g) + NO2 (g)  NO3 (g) + NO (g) Elementary
NO3 (g) + CO (g)  NO2 (g) + CO2 (g) steps
2 NO2 (g) + NO3 (g) + CO (g)  NO3 (g) + NO (g) + NO2 (g) + CO2 (g)

NO2 (g) + CO (g)  NO (g) + CO2 (g) Overall reaction

NO3 → Reaction intermediate

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 Example 14-7
Consider the following reaction mechanism:
Cl2 (g)  2 Cl (g)
Cl (g) + CHCl3 (g)  HCl (g) + CCl3 (g)
CCl3 (g) + Cl (g)  CCl4 (g)
(a) Determine the molecularity of each elementary
step.
(b) Write the equation for the overall reaction.
(c) Identify the reaction intermediate(s).

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 Problem 14-36
Identify each of the following elementary reactions
as unimolecular, bimolecular or termolecular, and
write the rate law.
(a) BrONO2 (g)  BrO (g) + NO2 (g)

(b) HO (g) + NO2 (g) + Ar (g)  HNO3 (g) + Ar (g)

(c) O (g) + H2S (g)  HO (g) + HS (g)

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 Problem 14-38
Consider the following reaction mechanism:
NO2Cl (g)  NO2 (g) + Cl (g)
Cl (g) + H2O (g)  HCl (g) + OH (g)
OH (g) + NO2 (g) + N2 (g)  HNO3 (g) + N2 (g)

(a) What is the molecularity of each elementary step?

(b) Write the overall equation for the reaction.
(c) Identify the reaction intermediate(s).

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TO BE
CONTINUED…

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