Physical Chemistry II

(CHE21M5)

Lecture #8:
Rates of Reactions
Elements Of Physical Chemistry, Peter Atkins & Julio de Paula, 5th
Ed, Chapter 5, From page 219
Rate of Reaction
• Chemical kinetics is concerned with the rates of chemical
reactions. How rapidly reactants are consumed and
Products - B
products formed (change in concentration), how reaction
rates respond to changes in the conditions or the presence
of a catalyst, how quickly a reaction mixture approaches
equilibrium
• Instantaneous rate: is the change in the rate at a particular
instant. The slope of a graph of concentration vs time,
tangent to the graph at t. Average rate: overall. Reactants - A

• The rate of reaction is often found to be proportional to the

molar concentrations of the reactants raised to a simple
power
−𝑑[𝐴] 𝑑[𝐵]
• Reaction: A  B Rate α OR Rate α
𝑑𝑡 𝑑𝑡
−𝑘 𝑑 𝐴 𝑘𝑑 𝐵
• Rate = OR Rate = (k = rate constant)
𝑑𝑡 𝑑𝑡
• Rate must specify which specie we are referring to. Sign
refers to increase (+ve) or decrease (-ve) of concentration. Units: concentration (mol.dm-3), the time (s),
rate is reported in mol.dm-3 s -1
Rate of Reaction: Rate Law
• A rate law is an equation that expresses • Example:
the rate of reaction in terms of the molar
concentrations (or partial pressures) of
the species in the overall reaction
• If we have reaction: A + B  C • Rate of formation of NH4+ = 2 x rate of (NH2)2CO
consumption. 1 mole of (NH2)2CO is consumed while
The rate is directly proportional to the 2 moles of NH4+ is formed
concentrations of the reactants A and B,
Rate α [A] [B]
Example: The rate of formation of NH3 in the reaction
• Rate Law: Rate = k [A] [B] N2(g) + 3 H2(g) → 2 NH3(g) was reported as 1.2 mmol
• The rate constant (k) is dependent of the dm−3 s−1 under a certain set of conditions. What is the
concentrations of the species taking part rate of consumption of N2 and H2?
in the reaction 1
Rate N2 = x NH3 = 0,6 mmol dm−3 s−1
2
• If we have reaction: A  B 3
Rate H2 = x NH3 = 1,8 mmol dm−3 s−1
The rate of formation of B is equal to rate 2
of consumption of A
Rate of Reaction: Effects of concentration

• Stoichiometric coefficient is 1 for all, therefore all rates

are the same.
• These results indicate that the initial reaction rate is
proportional to the [NH4+] and [NO2-]

If we double [NH4+] and keep [NO2-]

constant (Exp 1 & 2), rate doubles

If we double [NO2-] and keep [NH4+]

constant (Exp 2 & 3), the rate doubles
 The rate of reaction is
often found to be
proportional
to the molar
concentrations of the
reactants raised to
a simple power

The exponents m and n are called reaction orders.

Note: If concentration of the reactants is the

same. Rate order for [NH4+] and [NO2-] is 1
each.

Overall reaction order is the sum of the orders

 1+ 1 = 2
Thus, for the reaction, the rate law has an
overall reaction order of 2
Overall order = a + b
Reaction Orders: Zero, 1st and 2nd Order
• The Order of Reaction refers to the power dependence of the rate on
the concentration of each reactant.
- For a zero-order reaction, the rate is independent on the concentration
of reactant
- For a first-order reaction, the rate is dependent on the concentration of a
single species.
- A second-order reaction refers to rate that is dependent on the square of
the concentration of a single reactant or the combined first-order
dependence on the concentrations of two different reactants (A + B → C)
0-order and Half Life
• Rate independent of the concentration of reactants, therefore the power is zero: A  B
• Rate α [A]o Rate = k[A]o Rate = k (a0 = 1)
Half-Life: The time required to reduce the
−𝑑 𝐴
• Integrated Rate Law: Rate = =k [A] by half (when t = t1/2)
𝑑𝑡 1
d[A] = -k dt [A]t = [A]0
2
[A]0−12 [A]0
න 𝑑 𝐴 = − න 𝑘𝑑𝑡 k=
t1/2

[A]t - [A]0 = -kt [A]0(1 −12 )

k=
t1/2
[A]t = -k t + [A]0 [A]0
1
[A]0
2
k=
t1/2
y = mx+C [A]t
1
[A]0− [A]t -k 2
[A]0
k= t1/2 =
𝑡 k
t
[A]0
t1/2 =
2k
This shows that if [A]t is plotted against t, then a zero-order reaction will give a straight line of slope −k
1st-order and Half Life
• Rate dependent on the concentration of one reactants, therefore the power is 1: A  B
• Rate α [A]1 Rate = k[A]1
−𝑑 𝐴
• Integrated Rate Law: Rate = = k [A] 1
Half-Life: [A]t = [A]0
𝑑𝑡
2
𝑑𝐴 kt = ln[A]0− ln[A]t
= -k dt
[𝐴] [A]0
𝑑𝐴 1 𝑑𝑥 k t1/2 = ln1
‫׬‬ = − ‫𝑡𝑑𝑘 ׬‬ (‫׬‬ = ln 𝑥) 2
[A]0
[𝐴] 𝑥 ln 2
t1/2 =
ln[A]t - ln[A]0 = -kt 𝑘

ln[A]t = -k t + ln[A]0
ln[A]0
y = mx+ C
ln[A]t
kt = ln[A]0− ln[A]t
-k

ln[A]0− ln[A]t t
k= 𝑡

This shows that if ln[A]t is plotted against t, then a first-order reaction will give a straight line of slope −k
2nd-order and Half Life
• Rate dependent on the square of the concentration of a single reactant (A + A B) or the combined first-
order dependence on the concentrations of two different reactants (A + B → C), therefore the power is 2:
• Rate α [A]2 Rate = k[A]2
−𝑑 𝐴 −𝑑 𝐵
• Integrated Rate Law: Rate = = = k [A]2 1
𝑑𝑡 𝑑𝑡 Half-Life: [A]t = [A]0
−𝑑 𝐴 2
= k [A]2 1 1
𝑑𝑡 − = kt
[A]t [A]0
𝑑𝐴
= -k 𝑑𝑡
[A]2 1 1
1 − = k t1/2
‫[ ׬‬A]−2 dA = − ‫𝑡𝑑𝑘 ׬‬ 2
[A]0 [A]0
2 1
−( [A]t−1 – [A]0−1) = -kt − = k t1/2
[A]0 [A]0
1 1 1
− + = -kt 𝟏 = k t1/2
[A]t [A]0 [A]0
[A]t
1 1
= kt + k 1
[A]t [A]0 t1/2 =
𝟏 [A]0𝑘
t
[A]0
y = mx+C 1
This shows that if is plotted against t, then a second-order reaction will give a straight line of slope k
[A]t
Rate Laws: Summary

ln
ln
Example 1: Plot your data to see which data
gives a straight line
• For 1st order: ln[A]t = -kt + ln[A]0
𝟏 𝟏
• For 2nd order: = kt +
[A]t [A]0 1st order
y = mx + C

Create New Table 2nd order

With additional columns 
Example 2: Is the reaction 0, 1st or 2nd order?

0th ln[HCl] 1st 1/[HCl] 2nd

2 0,8000 2,0000
0,6000
1,5 0,4000 1,5000
0,2000
[HCl] 1 1,0000
0,0000
-0,2000 0 100 200 300 400 500
0,5
-0,4000
time 0,5000

0
time -0,6000 time
0,0000
0 100 200 300 400 500 -0,8000 0 100 200 300 400 500
Exercises
1. For lecture examples 1 & 2, determine the rate constant k and the half-life.
2. -

3.-

c. Determine the half-life of the reaction.

 Physical Chemistry II
(CHE21M5)

Lecture #8(b):
Rates of Reactions (continuation)
Elements Of Physical Chemistry, Peter Atkins & Julio de Paula, 5th
Ed, Chapter 5, From page 232
The temperature dependence of reaction
rates: The Arrhenius parameters A and Ea
• The rates of most chemical reactions increase as the temperature is raised
• A graph of ln k, where kr is the rate constant for the reaction, against 1/T, where T is the
(absolute) temperature at which k is measured, gives a straight line with a slope that is
characteristic of the reaction
• Activation energy is the minimum amount of energy that must be provided to
compounds to result in a chemical reaction. The activation energy (Ea) of a reaction is
measured J/mol OR kJ/mol

k=rate constant,
Ea = activation energy,
R=universal gas constant
T = absolute temperature
𝑒 ln 𝐾𝑟 = 𝑒 ln 𝐴 𝑒 𝐸𝑎/𝑅𝑇
Collision Theory
• In this collision theory of reaction rates it is supposed
that reaction occurs only if two molecules collide with a
certain minimum kinetic energy along their line of
approach(Fig. 10.18).
• In collision theory, a reaction resembles the collision of
two defective billiard balls: the balls bounce apart if they
collide with only a small energy, but might smash each
other into fragments (products) if they collide with more
than a certain minimum kinetic energy.
• A reaction profile in collision theory is a graph showing
the variation in potential energy as one reactant
molecule approaches another and the products then
separate (Fig. 10.19).
• Reaction: A + B  C, then
Transition State Theory
• In the transition-state theory (also called the activated-complex theory) of
reactions, it is supposed that as two reactants approach, their potential energy
rises and reaches a maximum, as illustrated by the reaction profile in Fig. 10.23.
This maximum corresponds to the formation of an activated complex, a cluster of
atoms that is poised to pass on to products or to collapse back into the reactants
from which it was formed (Fig. 10.24).
 Examples
1. Make an appropriate Arrhenius plot of the
following data for the conversion of cyclo-
propane to propene and calculate the activation
energy for the reaction.
T/K 750 800 850 900

kr /s−1 1.8 × 10− 4 2.7 × 10−3 1 3.0 × 10−2 0.26

2. Estimate the activation energy for the

decomposition of urea in the reaction,
CO(NH2)(aq) + 2 H2O(l) →2 NH4+(aq) + CO32−(aq)
for which the first-order rate constant is 1.2 × 10−7 s−1
at 60°C and 4.6 × 10−7 s−1 at 70°C.