Chapter 4

Chemical Kinetics

 Studies the rate (vận tốc) of a

chemical process which the rate
of the reaction is very dependent
on the path of the process or
path between reactants and
products

 kinetics also points out

approaches to control reaction
and describes mechanism.
Factors affect reaction Rate
Concentration of Reactants: As the concentration of reactants
increases, so does the likelihood that reactant molecules will
collide.
 Temperature: At higher temperatures, reactant molecules have
move faster, and collide more often, therefore, increasing rate.

 Catalysts: increases rate of reaction

Reaction Rate
 Rate of reaction can be determined by monitoring the change in
concentration of either reactants or products as a function of
me. → C vs t

A → B

C4H9Cl(aq) + H2O(l) ↔ C4H9OH(aq) + HCl(aq)

The concentration of butyl chloride, C4H9Cl,

was measured at various times, t.
Average rate
 The average rate of the reaction over each interval is the change
in concentration divided by the change in time.

Va “+”: Calculate for products.

“-”: Calculate for reactants.
 Example:
C4H9Cl(aq) + H2O(l) ↔ C4H9OH(aq) + HCl(aq)

𝑪𝟒 𝑯𝟗 𝑪𝒍
Va =
Instantaneous rate (vận tốc tức thời)
Va V

 Example:
C4H9Cl(aq) + H2O(l) ↔ C4H9OH(aq) + HCl(aq)

 Step 1: A plot of concentration vs.

time for this reaction yields a curve
like this.

 Step 2: The slope of a line tangent

to the curve at any point is the
instantaneous rate at that time.
Reaction Rates and Stoichiometry
 The rate of reaction equals rate of disappearance of reactant or the
rate of appearance of product
 For a general reaction,
aA + bB cC + dD
 Average Rate:

Va= = = =

 Instantaneous Rate:

V= = = =
 Example: C4H9Cl(aq) + H2O(l) ↔ C4H9OH(aq) + HCl(aq)

-[C4H9Cl] [C4H9OH]
Va = =
t t
Rate Law
For a general reaction:
aA + bB cC + dD

V= = = =
 Rate law: Each reaction has its own equation that gives its rate
as a function of reactant concentrations
V = k [A]m [B]n
Where, For a reaction k has a specific value; k is rate constant;
k changes with temperature.

Note: m need not equal a; n need not equal b. Values m and n can
be obtained from experiment
Reaction Order (Bậc phản ứng)
The reaction order can be found by adding the exponents on the
reactants in the rate law
V= k [A]m [B]n
Order of the reaction = m + n

 The reaction order is determined by the experiments

 Example: N2O5(g) ↔N2O4(g) + 1/2 O2(g)

With V = k [N2O5] Reaction Order???

reaction is a first order reaction

Example
2HI(g) ↔ H2(g) + I2(g)
At 443oC the rate of the reaction increases with HI concentration as
follows:
Data point 1 2 3
[HI] mol L-1 0.0050 0.010 0.020
Rate mol L-1 s-1 7.5 x 10-4 3.0 x 10-3 1.2 x 10-2

 Questions:
a) Determine the order of the reaction and write the rate expression
b) Calculate the rate constant, and determine its units
c) Calculate the reaction rate for a concentration of HI = 0.0020M
Example
Solution
We have, V = k [HI]n

a) V1 = k ([HI]1)n V2 = k ([HI]2)n
V2 /V1 = ([HI]2)n/([HI]1)n 3.0 x 10-3 / 7.5 x 10-4 = (0.010/0.0050)n
4 = 2n
n=2 V = k [HI]2
b) Calculate the rate constant, and determine its units
We have, V1 = k [HI]12
7.5 x 10-4 mol L-1 s-1 = k (0.0050 mol L-1)2
k = 30 L mol-1 s-1
c) Calculate the reaction rate for a concentration of HI = 0.0020M
V = k [HI]2 = 1.2 x 10-4 mol L-1 s-1
Examples
2 NO(g) + O2(g) ↔ 2 NO2(g)
Determine the rate expression and the value of the rate constant
from the data below.
[NO] (mol L-1) [O2](mol L-1) rate (mol L-1 s-1)
1.0 x 10-4 1.0 x 10-4 2.8 x 10-6
1.0 x 10-4 3.0 x 10-4 8.4 x 10-6
2.0 x 10-4 3.0 x 10-4 3.4 x 10-5
Solution
We have, V = k [O2]m [NO]n
To determine the rate law from the data, first determine the
dependence of the rate on each reactant separately.
V2/V1 = k [O2]2m [NO]2n / k [O2]1m [NO]1n
8.4 x 10-6 / 2.8 x 10-6 = (3.0 x 10-4)m/ (1.0 x 10-4)m
3= 3m => m = 1; 1st order in O2
Example
We have, V3/V2 = k [O2]3m [NO]3n / k [O2]2m [NO]2n
3.4 x 10-5 / 8.4 x 10-6 = (2.0 x 10-4)n/ (1.0 x 10-4)n
4= 2n => n = 2; 2nd order in NO
V = k [O2][NO]2 Order of reaction = 3

2.8 x 10-6 mol L-1s-1 = k [1.0 x 10-4 mol L-1] [1.0 x 10-4 mol L-1]2

k = 2.8 x 106 L2 mol-2s-1

Zero-Order Reactions
 In a zero order reaction, the rate does not depend on the concentration
of reactant.
 For the general reaction: A → Products
V = k[A]0 = k
(The rate is independent on the concentration of A)

 Unit of rate constant (k) is unit of rate: mol.L-1.time-1

 For example, the decomposition of

HI (g) on a gold catalyst is a zero- slope = -k
order reaction
[A]
2 HI(g) → H2(g) + I2(g)

time
First Order Reactions
 For the general reaction: A → Products

We have, V = - d[A]/ dt

On the other hand, the experimental rate law for 1st order reaction is:
V = k [A]
V = - d[A]/ dt = k [A]
d[A]/ dt = - k [A]

ln [A] = - kt
[A]o
[A]o where is the initial concentration of A at time t = 0
 Units of k:
Example
ln[A] = ln [A]o - kt

N2O5(g) → N2O4(g) + 1/2 O2(g)

V= k [N2O5]
Half life (bán hủy) of 1st order reaction
Half life : time it takes for the concentration of the reactant A to fall
to half its initial value. t1/2 when [A] = [A]o/2

We have, ln[A] = ln [A]o - kt

ln ([A]o/2) = ln [A]o - k t1/2

ln ([A]o/2) - ln [A]o = - k t1/2

ln(1/2) = - k t1/2
t1/2 = ln(2) / k

0.693
t1/2 =
k
Examples
What is the rate constant k for the first order decomposition of
N2O5(g) at 25oC if the half life at this temperature is 4.03 x 104 s?
Under these conditions, what percent of the N2O5 molecules have
not reacted after one day?
N2O5(g) → N2O4(g) + 1/2 O2(g)
Solution
a) For 1st order reaction, t1/2 = 0.6931 / k
k = 1.72 x 10-5 s-1
[N2O5]
b) ln = - kt [N2O5]/[N2O5]o = e-kt
[N2O5 ]o
[N2O5]/[N2O5]o = 0.226
22.6% N2O5 molecules have not reacted after one day
Second order reactions
A+B Products
Or 2A Products
Rate Law, V = k [A] [B] or V = k [A]2

V=- d[A]/ dt = k [A]2 𝟐 = k.dt

1 1
  kt
[A] [A]o

1
Half life: t1/2 
k[A]o
 Units of k:
Examples
2C2F4 → C4F8

1 1
ln[C2F4] vs time is not linear   kt
[A] [A]o
V = k [C2F4]2 slope = k
Summary

Zero order First order Second order

Rate Laws V=k V = k [A] V = k [A]2

[A] 1 1
Integrated
- ln = - kt   kt
Rate Laws
[A]o [A] [A]o

0.693 1
Half-life - t1/2 = t1/2 
k k[A]o

Unit of rate
constant mol.L-1.time-1 time-1 L.mol-1.time-1
(k)
Relationship between temperature (T) and k
 In general, as temperature increases, so
does the increasing reaction rate because k
depends on temperature.

Arrhenius Equation:

Where,
k: Rate constant
A: frequency factor, with each reaction.
Ea: Activation Energy
R = 8.314 J.mol-1.K-1 = 1.987 cal.mol-1.K-1
 For a general reaction, we have, V = k[A]m.[B]n
When [A] = [B] = 1 → V = k
k is the private rate of reaction
Catalysts
 Catalyst: A compound which takes part in a chemical reaction,
speeds up the rate, but does not itself undergo a chemical
change.

 Catalyst lowers Ea

Ea ↓ → k ↑

Catalyst increases rate of

reaction
Chemical Equilibrium
In reversible reaction, both directions can occur at the same time
and when rate of forward reaction equal to one of reverse reaction
Chemical Equilibrium State

N2O4 (g) 2NO2 (g)

Colorless Brown

N2O4 → NO2 + NO2 NO2 + NO2  N2O4

Equilibrium Constant
 Consider the following equilibrium system:
aA + bB cC + dD
for forward reaction, V1= k1 [A]a [B]b
for reverse reaction, V2= k2 [C]c [D]d

At Equilibrium state, V1 = V2 k1 [A]a [B]b = k2 [C]c [D]d

Kc = Where, Kc is equilibrium constant of

concentration
The numerical value of Kc is calculated using the concentrations
of reactants and products that exist at equilibrium.
 Examples: [NH 3 ] 2
N2(g) + 3H2(g) ⇄ 2NH3(g); Kc =
[N 2 ][H 2 ]3
[PCl 3 ][Cl 2 ]
PCl5(g) ⇄ PCl3(g) + Cl2(g); Kc = [PCl ]
5
Equilibrium Constant of gas (Kp)
 Consider the following equilibrium system:
aA (g) bB (g)

P AV  n A RT
nA RT nB RT
PA   [ A]RT PB   [ B]RT
V V
P b [ B ]RT b [ B ]b RT b
K  B    K RT 

b  a 

p c
P a [ A]RT a [ A]a RT a
A

Or Kp = Kc (RT) ∆n
Le Châtelier’s Principle
when factors that influence an equilibrium are altered,
the equilibrium will shift to a new position that tends to
minimize those changes.

 Factors that influence equilibrium: Concentration,

temperature, and partial pressure (for gaseous)
The Effect of Changes in Concentration
Consider the reaction: N2(g) + 3H2(g) ⇄ 2 NH3(g);

[NH 3 ]2
Kc 
[N 2 ][H 2 ]3

If [N2] and/or [H2] is increased, K < Kc

 a net forward reaction will occur to reach new
equilibrium position with reducing [N2] and/or [H2].

If [NH3] is increased, K > Kc, and a net reverse reaction

will occur to come to new equilibrium position with
reducing [NH3].
Effects of Change in gas Pressure

 If the volume of a gas mixture is compressed, the overall gas

pressure will increase. The equilibrium will shift to either direction
which the reaction stoichiometry is smaller. If the volume of a gas
mixture is expended, the equilibrium will shift to either direction
which the reaction stoichiometry is greater.

2SO2(g) + O2(g) ⇄ 2SO3(g),

PCl5(g) ⇄ PCl3(g) + Cl2(g)

However, Reactions have same number of gas molecules in

reactants and products. Equilibrium is not affected by change in
pressure
CO(g) + H2O(g) ⇄ CO2(g) + H2(g);
H2(g) + Cl2(g) ⇄ 2HCl(g);
Examples

Determine whether the following reactions favor high or

low pressures?
1. 2SO2(g) + O2(g) ⇄ 2 SO3(g);
2. PCl5(g) ⇄ PCl3(g) + Cl2(g);
3. CO(g) + 2H2(g) ⇄ CH3OH(g);
4. N2O4(g) ⇄ 2 NO2(g);
5. H2(g) + F2(g) ⇄ 2 HF(g);
The Effect of changes in temperature
 Consider the following exothermic reaction:
N2(g) + 3H2(g) ⇄ 2NH3(g); Ho = -92 kJ,
 The forward reaction produces heat .
 When heat is added to increase temperature, reverse reaction will take place to
absorb the heat;
 If heat is removed to reduce temperature, a net forward reaction will occur to
produce heat..
 Exothermic reactions favor low temperature conditions
 Consider the following endothermic reaction:
CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g), Ho = 205 kJ
 Endothermic reaction absorbs heat
 If heat is added to increasing the temperature, it will cause a net forward
reaction.
 If heat is removed to reduce the temperature, it will cause a net reverse reaction.
 Endothermic reactions favor high temperature condition.
Examples
Determine whether the following reactions favors high
or low temperature?

1. 2SO2(g) + O2(g) ⇄ 2 SO3(g); Ho = -180 kJ

2. CO(g) + H2O(g) ⇄ CO2(g) + H2(g); Ho = -46 kJ
3. CO(g) + Cl2(g) ⇄ COCl2(g); Ho = -108 kJ
4. N2O4(g) ⇄ 2 NO2(g); Ho = +57 kJ
5. CO(g) + 2H2(g) ⇄ CH3OH(g); Ho = -270 kJ
Free energy and Equilibrium Constant
The following equation relates the standard-state free energy of
reaction with the free energy of reaction at any moment in time
during a reaction (not necessarily at standard-state conditions):

o
ΔG = Δ G + RT In Q
Where, G = free energy at any moment
Go = standard-state free energy
R = ideal gas constant = 8.314 J/mol-K
T = temperature (Kelvin)
lnQ = natural log of the reaction quotient

 At equilibrium state, ΔG = 0 and Q = Kc

𝒄 𝒅
o
Δ G = - RT In Kc = -RTln 𝒂 𝒃