CHEMICAL KINETICS

CHEMICAL KINETICS

•Area of chemistry concerned with the

speeds (or rates) at which a chemical
reaction occurs
•It also sheds light on the reaction
mechanism
 FACTORS AFFECTING
REACTION RATES
• Concentration of reactants
oAs the concentration of reactants increases, the probability that
reactant particles will collide increases
• Temperature
oAt higher temperatures, reactant particles have more kinetic
energy, move faster, and collide with more often and with greater
energy
oCatalysts
oSpeeds up the reaction without taking part of it
REACTION RATES
 REACTION RATES
• Reaction rates can be determined by monitoring the
change in concentration of either reactants or
products as a function of time.
∆ 𝐴 𝑣𝑠 ∆𝑡
∆[𝐴]
Rate =
∆𝑡
 REACTION RATES
• C4H9Cl(aq) + H2O(l)  C4H9OH(aq) + HCl(aq)

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)

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)

 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
particles.
 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
• C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

• The reaction slows

down with time because
the concentration of the
reactants decreases.
 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
disappearance of C4H9Cl
is the same as the rate
of appearance of
C4H9OH.
 REACTION RATES
• C4H9Cl(aq) + H2O(l) C4H9OH(aq) + HCl(aq)

- ∆[C4H9Cl] ∆[C4H9OH]
Rate = =
∆𝑡 ∆𝑡
 REACTION RATES AND STOICHIOMETRY

• What if the ratio is not 1:1?

H2(g) + I2(g) 2 HI(g)
• Only 1/2 HI is made for each H2 used.
 REACTION RATES AND STOICHIOMETRY

•To generalize, for the reaction

aA + bB cC + dD

Reactants (decrease) Products (increase)

 REACTION RATES AND STOICHIOMETRY

Sample Exercise:

Write the rate expression for the following reaction:

CH4 + 2 O2  CO2 + 2 H2O

 REACTION RATES AND STOICHIOMETRY

SEATWORK#1:

Write the rate expression for the following reactions in

terms of the disappearance of reactants and appearance
of products:

1.I- + OCl-  Cl- + OI-

2.3 O2  2 O3
3.4 NH3 + 5 O2  4 NO + 6 H2O
 RATE LAW
• Expresses the relationship of the rate of the reaction to the rate
constant and concentrations of the reactants raised to some
powers. (for gas-phase reactants, PA can be used instead of [A])

aA +bB  cC + dD

Rate Law: rate = k [A]x [B]y

*Note: the values of x and y are experimentally determined.
The variable “k” is the rate law constant.
 RATE LAW

aA +bB  cC + dD
Rate Law: rate = k [A]x [B]y
x – order of the reaction with respect to reactant A
y – order of the reaction with respect to reactant B
x + y = over-all order of the reaction
*Note: the values of x and y specify the relationships
between the concentrations of the reactants A and B
and the reaction rate.
 RATE LAW

The reaction of nitrogen monoxide with hydrogen gas at

1280℃ is
2 NO(g) + 2 H2 (g)  N2 (g) + 2 H2O (g)
From the following data collected at this temperature,
determine the rate law and calculate the rate constant.
EXPERIMENT [NO] [H2] INITIAL RATE (M/s)
1 5.0 x 10-3 2.0 x 10-3 1.3 x 10-5
2 10.0 x 10-3 2.0 x 10-3 5.0 x 10-5
3 10.0 x 10-3 4.0 x 10-3 10.0 x 10-5
Seatwork #2 RATE LAW
The reaction of peroxydisulfate ion (S2O82-) with iodide
(I-) is
S2O82- + 3 I-  2 SO42- + I3-
From the following data collected at a certain
temperature, determine the rate law and calculate the
rate constant. [S O ]
EXPERIMENT 2 8
2- [I ]
- INITIAL RATE (M/s)
1 0.080 0.034 2.2 x 10-4
2 0.080 0.017 1.1 x 10-4
3 0.16 0.017 2.2 x 10-4
 THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

Given a first-order reaction

aA  products

the rate is

∆𝐴
𝑟𝑎𝑡𝑒 = −
∆𝑡
also from the rate law of the first-order reaction,

𝑟𝑎𝑡𝑒 = 𝑘[𝐴]
 THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

Equating the two expressions, we get

∆𝐴
− = 𝑘[𝐴]
∆𝑡
Applying calculus, the expression is written as

[𝐴]
𝑙𝑛 = −𝑘𝑡
[𝐴]0

*Note: [A] – final concentration of A

[A]0 – initial concentration of A
 THE INTEGRATED RATE LAW
FIRST-ORDER REACTION
The equation can be rearranged as

ln 𝐴 = −𝑘 𝑡 + ln[A]0
(y = m x + b)
Practice Exercise
THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

The conversion of cyclepropane to propane in the gas phase is a first-

order reaction with a rate constant of 6.7x10-4 s-1 at 500℃.

 CH3-CH=CH2

a. If the initial concentration of cyclepropane was 0.25M, what is the

concentration after 8.8 minutes?
b. How long will it take for the concentration of cyclopropane to
decrease from 0.25M to 0.15M?
c. How long will it take to convert 74% of the starting material?
Practice Exercise
THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

The rate of decomposition of azomethane is studied by monitoring the

partial pressure of the reactant as a function of time:
CH3-N=N-CH3 (g)  N2 (g) + C2H6 (g)
The data obtained at 300℃ are shown below.
TIME (s) Partial Pressure of
C2H6N2 (mmHg) Are these values consistent
0 284 with the first-order kinetics? If
100 220 so, determine the rate constant.
150 193
200 170
250 150
SW#3
THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

At 500°C cyclopropane (C3H6) rearranges to propene (CH3CHCH2).

The reaction is first-order with a rate constant of 6.7×10-4 s-1.
a. Calculate the molarity of cyclopropane after 25 minutes if the initial
concentration is 0.25M.
b. How many minutes does it take for the concentration of
cyclopropane to drop from 0.150M to 0.050M at 500°C?
c. How long does it take for the concentration to drop to 25% of the
original concentration at 500°C?
 THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

Half-life (t1/2):
- the time required for the concentration of a reactant to decrease to ½
of its initial concentration
1 [𝐴]0
𝑡 = 𝑙𝑛
𝑘 [𝐴]

[𝐴]𝑜
At 𝑡1 2 , 𝐴 =
2
1 [𝐴]0 𝒍𝒏𝟐 𝟎.𝟔𝟗𝟑
𝑡1 2 = 𝑙𝑛 [𝐴]0 or 𝒕𝟏 𝟐 = =
𝑘 𝒌 𝒌
2
Practice Exercise
THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

The decomposition of ethane (C2H6) to methyl radicals is a

first-order reaction with a rate constant of 5.36x10-4 s-1 at
700℃:

C2H6 (g)  2 CH3 (g)

Calculate the half-life of the reaction in minutes.

SW#4
THE INTEGRATED RATE LAW
FIRST-ORDER REACTION

The half-life for a first order reaction is 50 s when

[A] o = 0.84 M. What is the time needed for the concentration
of A to decrease to one-fourth of its original concentration?
 THE INTEGRATED RATE LAW
SECOND-ORDER REACTION

Given a second-order reaction

aA  products

the rate is

∆𝐴
𝑟𝑎𝑡𝑒 = −
∆𝑡
also from the rate law of the first-order reaction,

𝑟𝑎𝑡𝑒 = 𝑘[𝐴]2
 THE INTEGRATED RATE LAW
SECOND-ORDER REACTION
Equating the two expressions, we get

∆𝐴
− = 𝑘[𝐴]2
∆𝑡

Applying calculus, the expression is written as

1 1
= 𝑘𝑡 +
[𝐴] [𝐴]0

*Note: [A] – final concentration of A

[A]0 – initial concentration of A
 THE INTEGRATED RATE LAW
SECOND-ORDER REACTION
The equation can be rearranged as

1 1
= 𝑘𝑡 +
[𝐴] [𝐴]0
(y = m x + b)
 THE INTEGRATED RATE LAW
SECOND-ORDER REACTION

Half-life for a second-order reaction can be calculated using

the formula

𝟏
𝒕𝟏 =
𝟐 𝒌[𝑨]𝟎
Practice Exercise
THE INTEGRATED RATE LAW
SECOND-ORDER REACTION

Iodine atoms combine to form molecular iodine in the gas phase. This reaction
follows second-order kinetics and has the high rate constant 7.0x109 M-1s-1 at
23℃.

a. If the initial concentration of [I]0 was 0.086M, calculate the concentration after
2.0 minutes.
b. Calculate the half-life of the reaction if the initial concentration of [I]0 is 0.60M.
SW#5
THE INTEGRATED RATE LAW
SECOND-ORDER REACTION

Iodine atoms combine to form molecular iodine in the gas phase. This reaction
follows second-order kinetics and has the high rate constant 7.0x109 M-1s-1 at
23℃.

a. If the initial concentration of [I]0 was 0.120M, calculate the concentration after
3.50 minutes.
b. What is the initial concentration if 50.0% of the iodine atoms has been
converted to molecular iodine after1.59x10-10s ?
c. Calculate the half-life of the reaction if the initial concentration of [I]0 is 0.85M.
 THE INTEGRATED RATE LAW
SUMMARY
1st Order 2nd Order

Rate Law Rate = k[A] Rate = k[A]2

Integrated Rate Law ln 𝐴 = −𝑘 𝑡 + ln[A]0 1 1

= 𝑘𝑡 +
[𝐴] [𝐴]0
Unit of ‘k’ s-1 M-1s-1

Plot needed to Give a Straight Line ln [A] vs t 1

vs time
[𝐴]

Half-Life 𝒍𝒏𝟐 𝟎. 𝟔𝟗𝟑 𝟏

𝒕𝟏 = = 𝒕𝟏 =
𝟐 𝒌 𝒌 𝟐 𝒌[𝑨]𝟎
TEMPERATURE DEPENDENCE OF RATE
CONSTANT
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

•Generally, as temperature
increases, so does the reaction
rate.
•This is because k is temperature
dependent.
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

•Collision Theory
•In a chemical reaction, bonds are
broken and new bonds are formed.
•Molecules can only react if they
collide with each other.
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

•Collision Theory
•Furthermore, molecules must collide with
the correct orientation and with enough
energy to cause bond breakage and
formation.
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

•Collision Theory
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

•Activation Energy (Ea)

 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

•Activation Energy (Ea)

•Minimum amount f energy
required to initiate a chemical
reaction
TEMPERATURE DEPENDENCE OF RATE
CONSTANT
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

• It shows the energy of

the reactants and
products.
• The high point on the
diagram is the transition
state.
• The energy gap between the reactants and the activated
complex is the activation energy barrier.
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT
• The Arrhenius Equation:
𝐸𝑎
−
𝑘= 𝐴𝑒 𝑅𝑇

𝐸𝑎
ln 𝑘 = − + ln 𝐴
𝑅𝑇

A – collision frequency/ collision factor

Ea – activation energy
T – Temperature (in Kelvin)
𝐽
R – gas constant (8.314 )
𝑚𝑜𝑙𝑒∙𝐾
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

• At two temperatures
𝐸𝑎
ln 𝑘1 = − + ln 𝐴
𝑅𝑇1

𝐸𝑎
ln 𝑘2 = − + ln 𝐴
𝑅𝑇2
 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

• At two temperatures

𝑘1 𝐸𝑎 1 1
ln = −
𝑘2 𝑅 𝑇2 𝑇1
Practice Problem TEMPERATURE DEPENDENCE OF RATE
CONSTANT

The decomposition of hydrogen

iodide, 2HI  H2 + I2, has rate
-9 -1 -1
constants of 9.51x10 M s at 500.K
-5 -1 -1
and 1.10x10 M s at 600.K.
Calculate for the activation energy.
SW#6 TEMPERATURE DEPENDENCE OF RATE
CONSTANT

The first-order rate constant for the

reaction of methyl chloride (CH3Cl)
with water to produce methanol
(CH3OH) and hydrochloric acid (HCl)
-10 -1
is 3.32x10 s at 25.0℃. Calculate
the rate constant at 40.0℃ if the