CHEMICAL KINETICS

CHEMICAL KINETICS
area of chemistry that is concerned with the speeds,
or rates, at which reactions occur
CHEMICAL KINETICS
Reactions we want to go faster:
Sequestration of greenhouse gases

Reactions we want to go slower:

Spoilage of food
Rusting of iron
Destruction of the ozone layer
REACTION RATES
Consider a hypothetical reaction A → B, in which A molecules (red
spheres) are converted to B molecules (blue spheres)

Reaction rate
 A measure of how quickly A is consumed or how quickly B is produced
REACTION RATES
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝐵
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑖𝑚𝑒

∆(𝑚𝑜𝑙𝑒𝑠 𝐵)
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =
∆𝑡

∆(𝑚𝑜𝑙𝑒𝑠 𝐴)
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = −
∆𝑡
REACTION RATE
Rate in terms of concentrations

For the reaction C4H9Cl + H2O → C4H9OH + HCl

∆ 𝐶4𝐻9𝐶𝑙 ∆[𝐶4𝐻9𝑂𝐻]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = − =
∆𝑡 ∆𝑡
REACTION RATE
When the stoichiometric relationships are not one-to-one, the
coefficients in the balanced equation will be used in the reaction rate.

For the reaction 2HI → H2 + I2

2 moles HI disappears for every mole of H2 or I2 that forms
the rate of disappearance of HI is twice the rate of appearance
of H2 or I2

1 ∆ 𝐻𝐼 ∆ 𝐻2 ∆[𝐼2]
𝑅𝑎𝑡𝑒 = − = =
2 ∆𝑡 ∆𝑡 ∆𝑡
REACTION RATE
For the general reaction:
aA + bB → cC + dD

1 ∆A 1 ∆B
rate= – =–
a ∆t b ∆t

1 ∆C 1 ∆D
= =
c ∆t d ∆t
SAMPLE PROBLEM
If the rate of decomposition of N2O5 in the reaction:

2 N2O5(g) → 4 NO2(g) + O2(g)

at a particular instant is 4.2 × 10–7 M/s, what is the rate of

appearance of (a) NO2 and (b) O2 at that instant?
RATE LAW
an equation that shows the dependence of the reaction
rate on the concentration of the reactants

aA + bB ⟶ products
the Rate Law can be expressed as:
𝒎 𝒏
𝒓𝒂𝒕𝒆 = 𝒌 𝑨 𝑩 where k = rate constant (independent
of concentration but
temperature-dependent)
m, n = reaction order
REACTION ORDER
Reaction Order - the exponents in the rate law
 not based on stoichiometric coefficients
 can be determined experimentally
Consider the reaction,
2NO + O2 ⟶ 2NO2
rate = [NO]2[O2]

2nd order wrt NO and 1st order wrt O2

3rd order overall
SUMMARY OF REACTION ORDERS
Overall Reaction
Rate Law Units for k
Order
Rate = k Zeroth order M/s or Ms-1
Rate = k [A] First order 1/s or s-1
Rate = k [A]2 or Second order 1/(Ms) or M-1s-1
Rate = k [B]2 or
Rate = k [A] [B]
Rate = k [A]2 [B] or Third order 1/(M2s) or M-2s-1
Rate = k [A] [B]2
REACTION ORDER
May be determined through the following methods:

1. Method of Initial Rates

2. Integrated Rate Laws

METHOD OF INITIAL RATES
Initial rate
 instantaneous rate determined just after the reaction begins (after t = 0)
in which the initial concentration of the reactants have not yet changed
significantly

 For the reaction, A ⟶ products

 rate = k[A]m
 For the reaction, A + B ⟶ products
 rate = k[A]m[B]n
 SAMPLE PROBLEM
The initial rate of a reaction A + B → C was measured for several
different starting concentrations of A and B, with the results given:
Experiment Observed Initial
Initial [A], M Initial [B], M
no. Rate (M/s)
1 0.100 0.100 4.0 x 10-5
2 0.100 0.200 4.0 x 10-5
3 0.200 0.100 16.0 x 10-5

From the data collected, determine the rate law for the reaction and the
reaction order; and calculate the rate law constant.
Ans.: rate = k[A]2[B]0 = k[A]2; 2nd order wrt A, zeroth order wrt B, 2nd order overall;
k = 4.0 x 10-3 M-1s-1
SAMPLE PROBLEM
The reaction of nitric oxide with hydrogen at 1280°C is:

2NO(g) + 2H2(g) → N2(g) + 2H2O(g)

From the following data collected at this temperature, determine the rate law
and calculate the rate law constant.
Experiment Observed Initial
Initial [NO], M Initial [H2], M
no. Rate (M/s)
1 5.0 x 10-3 2.0 x 10-3 1.25 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

• Answer: rate = k[NO]2[H2] ; k = 250 /M2-s

INTEGRATED RATE LAW
 Rate laws that establish reactant concentration as a function
of time
 Zeroth Order Rate Law
𝒅𝑨
𝒓𝒂𝒕𝒆 = − =𝒌
𝒅𝒕
𝑨 𝒕− 𝑨 𝟎 = −𝒌𝒕
𝑨 𝒕 = −𝒌𝒕 + 𝑨 𝟎 Linear form (y = mx + b)
Plot [A]t vs t; m = -k; b = [A]o
INTEGRATED RATE LAW
 First Order Rate Law
𝒅𝑨
𝒓𝒂𝒕𝒆 = − =𝒌𝑨
𝒅𝒕
𝑨𝒕
𝒍𝒏 = −𝒌𝒕
𝑨𝟎
𝒍𝒏 𝑨 𝒕 = −𝒌𝒕 + 𝒍𝒏 𝑨 𝟎 Linear form (y = mx + b)
Plot ln[A]t vs t; m = -k; b = ln[A]o
INTEGRATED RATE LAW
To know the reaction order with respect to A, [A]t vs. t (zeroth order) or
ln[A]t vs. t (first order) maybe plotted.

In these illustrations, the reaction is first order wrt A since the ln[A]t vs. t
plot is more linear than the [A]t vs. t plot
INTEGRATED RATE LAW
 Second Order Rate Law
𝒅𝑨 𝟐
𝒓𝒂𝒕𝒆 = − =𝒌 𝑨
𝒅𝒕
𝟏 𝟏
= 𝒌𝒕 + Linear form (y = mx + b)
𝑨𝒕 𝑨𝟎

Plot 1/[A]t vs t; m = k; b = 1/[A]o

SAMPLE PROBLEM
The following data were obtained for
the gas-phase decomposition of NO2 Time, s [NO2], M
at 300°C: 0.0 0.01000
50.0 0.00787
NO2(g) → NO(g) + ½ O2(g)
100.0 0.00649
200.0 0.00481
A. Determine the order of the reaction.
B. What is the value of the rate Answers:
constant? 2nd order
k = 0.539 /M-s
SAMPLE PROBLEM Time, s
0.0
[N2O5], M
0.1000
Using the data for the reaction: 50.0 0.0707
100.0 0.0500
200.0 0.0250
2N2O5(g) → 4NO2(g) + O2(g)
300.0 0.0125
400.0 0.00625
A. Verify that the reaction is first
order wrt [N2O5].
Answers:
B. Calculate [N2O5] at 150s after
k = 6.93×10–3 /M-s
the start of the reaction. [N2O5]150s = 0.0354 M
HALF-LIFE, t1/2
 Time required for the
concentration of a reactant to
reach one-half of its initial value

 A convenient way to describe

how fast a reaction occurs:
faster reactions have short half-
lives
HALF-LIFE, t1/2
FIRST ORDER SECOND ORDER
1 1
ln 𝐴 𝑡 = −𝑘𝑡 + ln 𝐴 0 = 𝑘𝑡 +
𝐴𝑡 𝐴0
𝐴0 1 1
ln = −𝑘𝑡1 2 + ln 𝐴 0 = 𝑘𝑡1 2 +
2
0.5 𝐴 0 𝐴0
ln 𝐴 0 − ln 2 − ln 𝐴 0 = −𝑘𝑡1 2 2 1
− = 𝑘𝑡1 2
𝐴0 𝐴0
𝒍𝒏 𝟐 𝟏
= 𝒕𝟏 𝟐 = 𝒕𝟏 𝟐
𝒌 𝒌𝑨 𝟎
SAMPLE PROBLEM
The decomposition of ethane to methyl radicals is a 1st order
reaction with a rate constant of 5.36 × 10–4 s–1 at 700°C:

CH3CH3(g) → 2 •CH3(g)

Calculate the half life of the reaction in minutes.

Answer: 21.6 min

SAMPLE PROBLEM
The reaction 2A →B is 2nd order with a rate constant of
51 M–1min–1 at 24°C.

1. Starting with [A]0 = 0.0054 M, how long will it take

to have [A]t = 0.0016 M?
2. Calculate the half life of the reaction. Answers:
1. 8.6 min
2. 3.6 min
INTEGRATED RATE LAW
First Order Second Order
Rate law 𝑹𝒂𝒕𝒆 = 𝒌[𝑨] 𝑹𝒂𝒕𝒆 = 𝒌[𝑨]𝟐
Unit of k s–1 M–1s–1
Integrated 𝟏 𝟏
rate law in 𝐥𝐧 𝑨 𝒕 = −𝒌𝒕 + 𝐥𝐧 𝑨 𝟎 = 𝒌𝒕 +
𝑨𝒕 𝑨𝟎
linear form
Plot for 𝟏
𝐥𝐧[𝑨]𝒕 𝐯𝐬. 𝒕 𝐯𝐬. 𝒕
straight line 𝑨𝒕
COLLISION THEORY
Central idea:
For a chemical reaction to take place, the particles
(atoms or molecules) must collide
Rate of reaction is directly proportional to the frequency of
collision
Factors determining an effective collision:
Orientation of particles
Energy of colliding particles
COLLISION THEORY
Proper orientation of colliding particles
COLLISION THEORY
Colliding particles must have sufficient energy for an
effective collision to take place
ACTIVATION ENERGY, EA
The minimum amount of energy needed by colliding
particles for a chemical reaction to proceed
 TRANSITION STATE

High energy state of the

particles that is intermediate
between the reactants and
the products

Partial bond breaking and

partial bond formation
FACTORS AFFECTING RATE OF REACTION
1.Surface area of solid or liquid reactants
2.Concentration of the reactants
3.Pressure at which the reaction occurs
4.Temperature at which the reaction occurs
5.Presence of a catalyst
1. SURFACE AREA OF SOLID OR LIQUID REACTANTS
Applies to reactions involving a solid and a gas, or a solid
and a liquid

Example: CaCO3(s) + 2 HCl(aq)  CaCl2(s) + H2O(l) + CO2(g)

Observation: Faster reaction with powdered calcium
carbonate compared to lumps of marble.

The more finely divided the solid is, the faster the reaction.
The powdered solid has a greater surface area.
1. SURFACE AREA OF SOLID OR LIQUID REACTANTS
Increasing the surface area of the solid increases the chances of
collision taking place
2. CONCENTRATION OF THE REACTANTS
Given a reaction between zinc and hydrochloric acid:
Zn(s) + 2 HCl(aq) → ZnCl2(s) + H2(g)

Observation: Zinc granules react fairly slow with dilute hydrochloric

acid, but much faster if the acid is concentrated

For many reactions involving liquids or gases, increasing the

concentration of the reactants increases the rate of reaction.
 2. CONCENTRATION OF THE REACTANTS
If the concentration is higher, the chances of collision are greater due
increase amount reactants.

Zn(s) + 2 HCl(aq)  ZnCl2(s) + H2(g)

+
zinc in dilute HCl Zinc in
Zinc HCl solution solution concentrated
HCl solution
3. PRESSURE AT WHICH THE REACTION OCCURS
Applies to reactions involving gaseous reactants:
N2(g) + H2(g) → NH3(g)

Observation: The rate of reaction is increased by the use of

very high pressures.

Changing the pressure on a reaction which involves only

solids or liquids has no effect on the rate.
3. PRESSURE AT WHICH THE REACTION OCCURS
Increasing the pressure of a gas is exactly the same as
increasing its concentration

Increasing the pressure decreases the volume

Molecules have space to move and increases the concentration. Molecules have
around, there is little chance of less space to move in and more likely to collide
a collision
4. TEMPERATURE
Applies to almost all kinds of reaction:
food + heat → spoiled food

Observation: Foods spoil faster during the summer and on hot

days.
As a rough estimate for many reactions happening at around room
temperature, the rate of reaction doubles for every 10 °C rise in
temperature.
4. TEMPERATURE
At higher temperature particles move faster and so
collide more frequently. Also large increase in the
number of the energetic particles which can collide with
enough energy to react.
4. TEMPERATURE
The Arrhenius Equation
describes the dependence of the rate constant k with temperature
𝑬𝒂
𝒌= 𝑨𝒆−𝑹𝑻
Where:
A = collision frequency factor
Ea = activation energy (J)
R = universal gas constant (8.314 J/mol-K)
4. TEMPERATURE
The Arrhenius Equation
Linear form (by taking the ln of both sides):
𝑬𝒂
𝐥𝐧 𝒌 = − + 𝐥𝐧 𝑨 𝑬𝒂 𝟏
𝑹𝑻 𝐥𝐧 𝒌 = − ∙ + 𝐥𝐧 𝑨
𝑹 𝑻
Linear plot: ln k vs. 1/T
Slope: –Ea/R
𝒚 = 𝒎 ∙ 𝒙 + 𝒃
y-intercept: ln A
 T (K) k (1/M1/2-s)
4. TEMPERATURE 700 0.011
The rate constants for the decomposition of 730 0.035
acetaldehyde: 760 0.105
790 0.343
CH3CHO(g) → CH4(g) + CO(g)
810 0.789
was measured at different temperatures as
shown.

Determine the Ea (in kJ/mol) for the reaction.

Ans.: Ea = 1.8 × 102 kJ/mol

4. TEMPERATURE
The table shows the rate constants for the T (K) k (s-1)
rearrangement of methyl isonitrile at 462.9 2.52 x 10-5
various temp.
472.1 5.25 x 10-5
a. Determine the Ea (in kJ/mol) for the
reaction. 503.5 6.30 x 10-4

b. What is the value of the rate constant 524.4 3.16 x 10-3

at 430.0 K?

Ans.: Ea = 1.6 × 102 kJ/mol;

k = 1.0 x 10-6 s-1
5. PRESENCE OF A CATALYST
Catalysts
Substances that affect the
rates of chemical reactions
without being consumed in the
reaction

Catalysts increase the rate of

reactions by providing an
alternative reaction path with
a lower Ea
5. PRESENCE OF A CATALYST
Enzymes
Catalysts in biological systems