20 PHYSICAL CHEMISTRY II

CHEMICAL KINETICS JAN 2018

 20B PHYSICAL CHEMISTRY II
INTEGRATED RATE LAWS JAN 2018
WHY DO YOU NEED TO KNOW THIS MATERIAL?

“Integrated rate laws” are the solution of the differential equations that describe the
rate laws. They are used to predict the concentration of species at any time after the
start of the reaction and to provide procedures for measuring rate constants. This
topic explores simple yet very useful integrated rate laws that appear throughout the
chapter.

You need the integrated law if you want to predict the composition of a reaction
mixture as it approaches equilibrium. It is also used to determine the rate law and
rate constants of a reaction, which is a necessary step in the formulation of the
mechanism of the reaction.
CONTENTS

What you will learn:

First-order reactions
Second-order reactions
20B1. FIRST-ORDER REACTIONS
First-order rate law
dA
= −𝑘𝑟 𝐴 (20B.1a)
d𝑡

Integrated first-order rate law

𝐴
ln = −𝑘𝑟 𝑡 𝐴 = 𝐴 0 𝑒 −𝑘𝑟 𝑡 (20B.1b)
𝐴0
20B1. FIRST-ORDER REACTIONS

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

yield a straight line with a slope of -k.
Plot of ln[R]t versus t:

So, use graphs to determine reaction order. slope

ln[R]t = -k

t
20B1. FIRST-ORDER REACTIONS
Consider the process in which
methyl isonitrile is converted to
acetonitrile.

CH3NC CH3CN

How do we know this

is a first order rxn?
20B1. FIRST-ORDER REACTIONS
CH3NC CH3CN
This data was collected
for this reaction at
198.9°C.

Does
rate=k[CH3NC]
for all time intervals?
20B1. FIRST-ORDER REACTIONS

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

line results.
 The process is first-order.
 k is the negative slope: 5.1  10-5 s-1.
20B1. FIRST-ORDER REACTIONS
First-order reaction Half-life
1
𝐴0 1
𝑘𝑟 𝑡1/2 = − ln 2 = − ln = ln 2
𝐴0 2

2
𝑡1/2 = ln (20𝐵. 2)
𝑘𝑟
HALF-LIFE OF REACTIONS
 20B1. FIRST-ORDER REACTIONS
Half-life is known as t1/2 , is the
amount of time it takes for the
concentration to drop to one-half of
it’s initial conc:
At  1 A0
2

For the equation of first order

reaction: 1
A  0 1
ln 2   kt 1 , ln   kt 1 ,
0.693
A 0 2 2 2

t 1  1
ln
2 k
t1  2 Plot of [A] vs t
2 k
20B1. FIRST-ORDER REACTIONS
First-order reaction Time constant
1
𝐴0 1
𝑘𝑟 𝜏 = ln 𝑒 = − ln = 1
𝐴0 𝑒

1
𝜏= (20𝐵. 3)
𝑘𝑟
EXERCISE
Carbon-14 (14C) is a radioactive isotope with a half-life of 5.73 x
103 years. It decays following the first order reaction. The amount
of 14C present in an object can be used to determined its age.
Calculate the rate constant for decay of 14C and determine how
long is required for 90% of the 14C in a sample to decompose.
EXERCISE
The first-order reaction 2A  2B + C is 35% complete after 325s.
(a) Calculate k, kA.
(b) How long will it take for the reaction to be 70% complete?
(c) How long will it take for the reaction to be 90% complete?
EXERCISE
SO2Cl2 SO2 + Cl2
- first order reaction, k = 2  10-5 s-1 at 320 C.
(a) What percentage of SO2Cl2 is decomposed on heating at 320
C for 90 mins.
(b) What is the half life of SO2Cl2 when [SO2Cl2]0 = 1.70 M.
EXERCISE
The variation in the partial pressure of azomethane with time
was followed at 600 K, with the results given below. Confirm
that the decomposition CH3N2CH3 (g) CH3CH3 (g) + N2 (g) is
the first order in azomethane, and find the rate constant, half-
life and time constant at 600 K.

t (s) 0 1000 2000 3000 4000

p (Pa) 10.9 7.63 5.32 3.71 2.59
EXERCISE
20B1. FIRST-ORDER REACTIONS
Various Plots for First Order Reactions
20B2. SECOND-ORDER REACTIONS
Second-order rate law
dA 2
= −𝑘𝑟 𝐴 (20B.4a)
d𝑡

Integrated second-order rate law

1 1
− = 𝑘𝑟 𝑡 (20B.4b)
[𝐴] 𝐴0
20B2. SECOND-ORDER REACTIONS
Second-order reaction Half-life

1
𝑡1/2 = (20𝐵. 5)
𝑘𝑟 𝐴 0
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
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
300.0 0.00380
Graphing ln [NO2] vs. t yields:

• The plot is not a straight

line, so the process is not
first-order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 -4.610
50.0 0.00787 -4.845 Does not fit:

100.0 0.00649 -5.038

200.0 0.00481 -5.337
300.0 0.00380 -5.573
 A graph of 1/[NO2] vs. t
gives this plot.

Time (s) [NO2], M 1/[NO2] • This is a straight

0.0 0.01000 100
line. Therefore,
the process is
50.0 0.00787 127
second-order in
100.0 0.00649 154
[NO2].
200.0 0.00481 208
300.0 0.00380 263
20B2. SECOND-ORDER REACTIONS
Various Plots for Second-order Reactions
20B2. SECOND-ORDER REACTIONS FIRST-ORDER
REACTIONS
Various Plots for Second-order Reactions

SECOND-ORDER
REACTIONS
 First order

ln[A]0
lnAt  - kt  lnA0
slope = -k
y  mx  b
ln[A]

Plot:
ln[A] vs. time

time
 Second order

1 1
 kt 
At A0 slope = k

y  mx  b
1
[A]
Plot:
1
1 vs. time [A]o
[A]
time
 Zero order

At  - kt  A0
[A]0

slope = -k
y  mx  b
[A]

Plot:
[A] vs. time

time
 First order Second order Second order

Rate
Laws

Integrate
d Rate complicated
Laws

Half-life complicated
GRAPHICAL METHOD FOR ZERO-
ORDER REACTION
- [R]
Rate  k
t
[R] = -kt, and [R]t = [R]0 = kt;

A plot of [R]t versus t yields a straight

line with k = -slope.
GRAPH OF ZERO-ORDER REACTIONS
Plot of [R]t versus t:

slope = -k
[R]t

t
VARIOUS PLOTS FOR ZERO ORDER
REACTIONS
 CHECKLIST OF EQUATIONS
Equation
Property Equation Comment
number
ln([A]/[A]0) = krt
Integrated rate law First order, A  P 20B.1
or A = [A]0 e−𝑘r𝑡
Half-life t1/2 = (ln 2)/kr First order, A  P 20B.2
Time constant t = 1/kr First order 20B.3
1/[A]  1/[A]0 = krt or
Integrated rate law Second order, A  P 20B.4
[A] = [A]0/(1 + krt[A]0)
Half-life t1/2 = 1/kr[A]0 Second order, A  P 20B.5
t1/2 = (2n1  1)/(n  1)kr[A]0n1 nth order, n  0,1 20B.6
ln{([B]/[B]0/([A]/[A]0)} = ([B]0 
Integrated rate law Second order, A + B  P 20B.8
[A]0)krt
 CHECKLIST OF CONCEPTS
Integrated rate law – is an expression for the concentration of a reactant or product as
a function of time
Half-life – of a reactant is the time it takes for its concentration to fall to half its initial
value