Integrated Rate

Law
Review!

1 It is the study of the rate of chemical reactions.

Chemical Kinetics

2 The change in the concentration of a reactant (reagents) or product per

change of time.
Rate of Reaction

3 Expressed the rate of reaction of this hypothetical equation

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
1 ∆𝐴 1 ∆𝐵 1 ∆𝐶 1 ∆𝐷
Rate = − = − = =
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡
4 It is a mathematical expression that shows how the rate of reaction
depends on the concentration of the reactants
Rate Law

5 It dictates how the rate responds to the variations in the concentration

of the reactant.
Order of the Reaction / Reaction Order

6 Expressed the rate law of this hypothetical equation

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷

𝑟𝑎𝑡𝑒 = 𝑘 [𝐴]𝑥 [𝐵]𝑦

 Integrated
Rate Law
Form of rate law that relates the
concentrations of reactants and time.
The most useful aspect of the integrated
rate law is that it can be rearranged to
have the general form of a
straight line.
Zero-order
reaction
The rate is independent of the
concentration of the reactant.
 Zero-order reactions
1 Integrated rate law: [𝐴]𝑡 = −𝑘𝑡 + [𝐴]0

𝑦= 𝑚 𝑥+ 𝑏 Equation of a straight line

2 Graph:
 Zero-order reactions
[𝐴]𝑡 𝑖𝑛 𝑀
[A]0 or initial concentration
1.20
[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 1.08
𝑦 = 𝑚𝑥 + 𝑏 0.96
Slope (m) = -k
0.84
time concentration
0 1.2 0.72
20 1.075
40 0.95 0.60
60 0.825
0.48
80 0.7
100 0.575 0.36

0.24

0.12

0 𝑡 in sec
20 40 60 80 100
 Zero-order reactions
1 Integrated rate law: [𝐴]𝑡 = −𝑘𝑡 + [𝐴]0

𝑦= 𝑚 𝑥+ 𝑏 Equation of a straight line

2 Graph:
3 Half-life (𝑡1/2) It is the time it takes for an initial
[𝐴]0 = initial concentration amount of a reactant to be
reduced to half.

Slope (m) = -k
[𝐴]𝑡 The half life depends on
[𝐴]0 the initial concentration
(𝑡1/2 ) =
2𝑘 and the rate constant of a
zero-order reaction.

𝑡
 Zero-order reactions
[𝐴]𝑡 𝑖𝑛 𝑀
[𝐴]0 or initial concentration
1.20

1.08
time concentration
0.96
0 1.2 Slope (m) = -k
20 1.075 0.84
40 0.95
60 0.825 0.72
80 0.7
0.60
100 0.575
0.48

0.36

0.24

0.12
Half-life
0 𝑡 in sec
20 40 60 80 100
 Zero-Order Reaction (Example)

Determine the rate constant of a zero-order reaction if the initial concentration of

substance A is 1.5 M and after 120 seconds the concentration of substance A is 0.75 M.

[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 [𝐴]𝑡 − [𝐴]0

Given: [𝐴]𝑜 = 1.50 M 𝑘=
−𝑡
[𝐴]𝑡 = 0.75 M [𝐴]𝑡 − [𝐴]0 = −𝑘𝑡
t = 120 secs. −𝑡 −𝑡 0.75 𝑀 − 1.5 𝑀
𝑘=
− 120 𝑠𝑒𝑐
Find: Rate constant (k) [𝐴]𝑡 − [𝐴]0
𝑘=
Formula: [𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 −𝑡
𝑘 = 6.25 𝑥10−3 𝑀/𝑠
 Zero-Order Reaction (Example)
How long (in seconds) will it take for the concentration of substance A to decrease
from 1.20 M to 0.75 M? The reaction is in zero-order and the rate constant of the
reaction is 6.25 𝑥10−3 𝑀/𝑠.

[𝐴]𝑡 = −𝑘𝑡 + [𝐴]0

Given: [𝐴]𝑜 = 1.20 M [𝐴]𝑡 − [𝐴]0
𝑡=
[𝐴]𝑡 = 0.75 M [𝐴]𝑡 − [𝐴]0 = −𝑘𝑡 −𝑘
k = 6.25 𝑥10−3 𝑀/𝑠 −𝑘 −𝑘 0.75 𝑀 − 1.20 𝑀
𝑡=
− 6.25 𝑥10−3 𝑀/𝑠
Find: Time (t) in seconds [𝐴]𝑡 − [𝐴]0
𝑡=
Formula: [𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 −𝑘 𝑡 = 72 𝑠
 Zero-Order Reaction (Example)

What is the half-life of the zero-order reaction if the initial concentration is 1.20 M and
the rate constant is 6.25 𝑥10−3 𝑀/𝑠 ?
𝑃𝑟𝑜𝑣𝑒:
[𝐴]0
Given: [𝐴]𝑜 = 1.20 M 𝑡1/2 =
2𝑘 [𝐴]𝑡 = −𝑘𝑡 + [𝐴]0
k = 6.25 𝑥10−3 𝑀/𝑠
1.20 𝑀 [𝐴]𝑡 = − (6.25 𝑥10−3 𝑀/𝑠) (96 s) + 1.20 𝑀
𝑡1/2 =
2 (6.25 𝑥10−3 𝑀/𝑠) [𝐴]𝑡 = −0.6 𝑀 + 1.20 𝑀
Find: Half-life (𝑡1/2 )
1.20 𝑀
[𝐴]0 𝑡1/2 = [𝐴]𝑡 = 0.6 𝑀
Formula: 𝑡1/2 = 0.0125 𝑀/𝑠
2𝑘
(𝑡1/2 ) = 96 𝑠
 Questions?
Clarifications?
 First-order
reaction
The rate increases in the same order as the
concentration of the reactant.
 First-order reactions
1 Integrated rate law: ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0

𝑦= 𝑚 𝑥+ 𝑏 Equation of a straight line

2 Graph:
 First-order reactions
[𝐴]𝑡 𝑖𝑛 𝑀
0.0365

0.0329
time concentration
0 0.0365 0.0292
300 0.0316
600 0.0273 0.0256
900 0.0237 0.0219
1200 0.0205
1500 0.0177 0.0183
1800 0.0153
2100 0.0133 0.0146
2400 0.0115
0.0110

0.0070

0.0037

0 𝑡 in sec
300 600 900 1200 1500 1800 2100 2400
 First-order reactions
𝑙𝑛[𝐴]𝑡 𝑖𝑛 𝑀
−3.30
ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0
−3.50
time concentration ln [A]
−3.60
0 0.0365 -3.31044
300 0.0316 -3.45460
−3.75
600 0.0273 -3.60087
900 0.0237 -3.74228 −3.90
1200 0.0205 -3.88733
1500 0.0177 −4.05 [𝐴]𝑡 𝑖𝑛 𝑀
-4.03419
1800 0.0153 -4.17990
−4.20
2100 0.0133 -4.31999
2400 0.0115 -4.46541 −4.35

−4.50

−4.65

0 𝑡 in sec
300 600 900 1200 1500 1800 2100 2400
 First-order reactions
1 Integrated rate law: ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0

𝑦= 𝑚 𝑥+ 𝑏 Equation of a straight line

2 Graph:

𝑙𝑛[𝐴]0 3 Half-life (𝑡1/2)

Slope (m) = -k 0.693

ln[𝐴]𝑡 (𝑡1/2 ) =
𝑘
The half life depends on the
rate constant only.
𝑡
 First-Order Reaction (Example)
What is concentration of substance A in first order reaction at 100 secs? If the initial
concentration is 1.50 M and the rate constant is 5.78 𝑥 10−3 /𝑠.

Given: [𝐴]𝑜 = 1.50 M ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0

t = 100 secs. ln[𝐴]𝑡 = −(5.78 𝑥 10−3 /𝑠)(100 𝑠) + ln (1.50 𝑀)
k = 5.78 𝑥 10−3 /𝑠
ln[𝐴]𝑡 = −0.578 + 0.4054651081 𝑀
Find:
ln[𝐴]𝑡 = −0.1725348919 𝑀
[𝐴]100 = concentration at 100 s
[𝐴]𝑡 = 𝑒 −0.1725348919
Formula:
ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0 [𝐴]𝑡 = 0.84 𝑀
 First-Order Reaction (Example)
Determine the rate constant of a first-order reaction if the initial concentration of
substance A is 1.5 M and after 120 seconds the concentration of substance A is 0.75 M.
[𝐴]
ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0 ln( 𝑡 )
Given: [𝐴]𝑜 = 1.50 M [𝐴]0
𝑘=
ln[𝐴]𝑡 − ln[𝐴]0 = −𝑘𝑡 −𝑡
[𝐴]𝑡 = 0.75 M
t = 120 secs. −𝑡 −𝑡 0.75 𝑀
ln( )
𝑘= 1.5 𝑀
Find: Rate constant (k) ln[𝐴]𝑡 − ln[𝐴]0 −120 𝑠
𝑘=
Formula: −𝑡
𝑘 = 5.78 𝑥 10−3 /𝑠
ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0 [𝐴]
ln( 𝑡 )
[𝐴]0 𝑘 = 5.78 𝑥 10−3 𝑠 −1
𝑘=
−𝑡
 First-Order Reaction (Example)
What is the half-life of the first-order reaction if the initial concentration is 1.50 M and
the rate constant is 5.78 𝑥 10−3 /𝑠?
Prove:
0.693
Given: [𝐴]𝑜 = 1.50 M 𝑡1/2 = ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0
𝑘
k = 5.78 𝑥 10−3 /𝑠
0.693 ln[𝐴]𝑡 = −(5.78 𝑥 10−3 /𝑠)(119.90 𝑠) + ln (1.50 𝑀)
𝑡1/2 =
5.78 𝑥 10−3 /𝑠 ln[𝐴]𝑡 = −0.693022 + 0.4054651081 𝑀
Find: Half-life (𝑡1/2 )
0.693 0.693 ln[𝐴]𝑡 = −0.2875568919 𝑀
Formula: 𝑡1/2 = 𝑡1/2 =
𝑘 5.78 𝑥 10−3 /𝑠
[𝐴]𝑡 = 𝑒 −0.2875568919
𝑡1/2 = 119.90 s
[𝐴]𝑡 = 0.75 𝑀
 Questions?
Clarifications?
 Second-order
reaction
The rate is proportional to the square of
the concentration of one reactant.
 Second-order reactions
1 1
1 Integrated rate law: [𝐴]𝑡
= 𝑘𝑡 +
[𝐴]0

𝑦= 𝑚 𝑥+ 𝑏 Equation of a straight line

2 Graph:
 Second-order reactions
[𝐴]𝑡 𝑖𝑛 𝑀
0.240
time concentration
0 0.240 0.220
700 0.206
0.200
1400 0.180
2100 0.160 0.180
2800 0.144
3500 0.131 0.160
4200 0.120
0.140
4900 0.111
5600 0.103 0.120
6300 0.096
7000 0.090 0.100

0.80

0.60

0 𝑡 in sec
700 1400 2100 2800 3500 4200 4900 5600 6300 7000
 Second-order reactions
𝑙𝑛[𝐴]𝑡 𝑖𝑛 𝑀
−1.43
time [A] ln [A]
0 0.240 -1.42712 −1.53
700 0.206 -1.57988
−1.62
1400 0.180 -1.7148
2100 0.160 -1.83258 −1.72
2800 0.144 -1.93794
3500 0.131 -2.03256 −1.82
4200 0.120 -2.12026
−1.92
4900 0.111 -2.19823
5600 0.103 -2.27303 −2.02
6300 0.096 -2.34341
7000 0.090 -2.40795 −2.11

−2.21

−2.31

0 𝑡 in sec
700 1400 2100 2800 3500 4200 4900 5600 6300 7000
 Second-order reactions
1
𝑖𝑛 𝑀
[𝐴]𝑡 1 1
15 Slope (m) = k = 𝑘𝑡 +
[𝐴]𝑡 [𝐴]0
time [A] ln [A] 1/[A] 13.5
0 0.240 -1.42712 4.167
700 0.206 -1.57988 4.854 12 𝑦= 𝑚 𝑥+ 𝑏
1400 0.180 -1.7148 5.556
10.5
2100 0.160 -1.83258 6.250
2800 0.144 -1.93794 6.944 9
3500 0.131 -2.03256 7.634
4200 0.120 -2.12026 8.333 7.5
4900 0.111 -2.19823 9.009
6
5600 0.103 -2.27303 9.709 [𝑨]𝒕
6300 0.096 -2.34341 10.417 4.5 ln[𝐴]𝑡
7000 0.090 -2.40795 11.111
3
1
1.5 [𝐴]0

0 𝑡 in sec
700 1400 2100 2800 3500 4200 4900 5600 6300 7000
 Second-order reactions
1 1
1 Integrated raw law: [𝐴]𝑡
= 𝑘𝑡 +
[𝐴]0

𝑦= 𝑚 𝑥+ 𝑏 Equation of a straight line

2 Graph:
3 Half-life (𝑡1/2)

Slope (m) = k 1 The half-life is inversely

1 (𝑡1/2 ) = proportional to the
𝑘[𝐴]0 concentration of the
[𝐴]𝑡 1
reactant.
[𝐴]0

𝑡
 Second-Order Reaction (Example)

Determine the rate constant of a second-order reaction if the initial concentration of

substance A is 1.5 M and after 120 seconds the concentration of substance A is 0.75 M.
1 1 1 1
= 𝑘𝑡 + −
Given: [𝐴]𝑜 = 1.50 M [𝐴]𝑡 [𝐴]0 𝑘 = 0.75 𝑀 1.5𝑀
120 𝑠
[𝐴]𝑡 = 0.75 M
1 1 1 1 1
t = 120 secs. − = 𝑘𝑡 𝑘 = (0.75 𝑀 − 1.5𝑀) (120 𝑠)
[𝐴]𝑡 [𝐴]0
Find: Rate constant (k) 𝑡 𝑡
Formula: 1 1 𝑘 = 5.56 𝑥 10−3 / M.s
= 𝑘𝑡 + 1 1
[𝐴]𝑡 [𝐴]0 −
[𝐴]𝑡 [𝐴]0
𝑘=
𝑡
 Second-Order Reaction (Example)
How long (in seconds) will it take for the concentration of substance A to decrease
from 1.20 M to 0.75 M? The reaction is in second order and the rate constant of the
reaction is 5.56 𝑥 10−3 / M.s
1 1 1 1
= 𝑘𝑡 + −
Given: [𝐴]𝑜 = 1.20 M [𝐴]𝑡 [𝐴]0 t = 0.75 𝑀 −31.2 𝑀
5.56 𝑥 10 / M.s
[𝐴]𝑡 = 0.75 M
1 1 1 1 1 Ms
k = 5.56 𝑥 10 −3
/ M.s − = 𝑘𝑡 t=( − ) (5.56 𝑥 10−3)
[𝐴]𝑡 [𝐴]0 0.75 𝑀 1.2𝑀
Find: Time (t) in seconds 𝑘 𝑘 t = (0.5 /𝑀) (179.8561151 𝑀𝑠)
Formula: 1 = 𝑘𝑡 + 1 1 1
[𝐴]𝑡 [𝐴]0 −
[𝐴]𝑡 [𝐴]0
t= t = 89.93 𝑠
𝑘
 Second-Order Reaction (Example)
What is the half-life of the second-order reaction if the initial concentration is 1.20 M
and the rate constant is 5.56 𝑥 10−3 / M.s?
𝑃𝑟𝑜𝑣𝑒: 1 1
1
= 𝑘𝑡 +
Given: [𝐴]𝑜 = 1.20 M 𝑡1/2 = [𝐴]𝑡 [𝐴]0
𝑘[𝐴]0
1 1
k = 5.56 𝑥 10 −3
/ M.s = (5.56 𝑥 10−3 / M.s )(149.88 𝑠) +
[𝐴]𝑡 1.20 𝑀
1
𝑡1/2 =
( 5.56 𝑥 10−3 / M.s ) (1.20 M) 1
= 0.8333328/𝑀 + 0.8333333333/𝑀
Find: Half-life (𝑡1/2 ) [𝐴]𝑡
1 1
1 𝑡1/2 = = 1.666666133 /𝑀
Formula: 𝑡1/2 = 6.672 𝑥 10−3 𝑠 [𝐴]𝑡
𝑘[𝐴]0
𝑡1/2 = 149.88 𝑠 [𝐴]𝑡 =
1𝑀
1.666666133 [𝐴]𝑡 = 0.60 𝑀
Summarize
Zero – Order First Order Second Order
1 1
Integrated Rate Law [𝐴]𝑡 = −𝑘𝑡 + [𝐴]0 ln[𝐴]𝑡 = −𝑘𝑡 + ln[𝐴]0 = 𝑘𝑡 +
[𝐴]𝑡 [𝐴]0

1
Linear-Relationship 𝐴 𝑣𝑠. 𝑡 𝑙𝑛 𝐴 𝑣𝑠. 𝑡 𝑣𝑠 𝑡
[𝐴]𝑡

Straight-line plot

[𝐴]0 0.693 1
Half-life 𝑡1/2 = 𝑡1/2 = 𝑡1/2 =
2𝑘 𝑘 𝑘[𝐴]0
Thank you and
God bless! 