Chemical Kinetics

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Chemical Kinetics
• area of chemistry that is concerned with the speeds,
or rates, at which reactions occur

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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

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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 4
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
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Reaction Rate
• Rate in terms of concentrations

For the reaction C4H9Cl + H2O → C4H9OH + HCl

∆ 𝐶4𝐻9𝐶𝑙 ∆[𝐶4𝐻9𝑂𝐻]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = − =
∆𝑡 ∆𝑡

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Rate Law
• An equation that shows the dependence of the reaction rate
on the concentration of the reactants
• For a general reaction:
aA + bB → products
rate Law is expressed as:
𝒓𝒂𝒕𝒆 = 𝒌[𝑨]𝒎[𝑩]𝒏
where k = rate law constant (independent of
concentration but temperature-dependent)
m, n, p = reaction order
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Rate Law and Reaction Rate
• For a reaction of the sort A → products,

∆𝐴
𝑅𝑎𝑡𝑒 = − = 𝑘[𝐴]
∆𝑡

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Reaction Order
• The exponents in the rate law
• Experimentally determined and cannot be based on
the stoichiometry
𝑚
𝑅𝑎𝑡𝑒 = 𝑘 𝐴 𝐵 𝑛…
• If m = 1 and [A] is doubled, the rate doubles
• If m=2 and [A] is doubled, [A]2 quadruples and the
rate increases by a factor of 4.
• In general, the rate is proportional to [A]m.
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Reaction Order
• The exponents m and n are reaction orders and their sum
is the overall reaction order

• Example:
Rate = k [A]2 [B]
Interpretation: The reaction is second order with
respect to A, first order with respect to B and third order
overall.

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Determination of Reaction Order
NH4 +(aq) + NO2-(aq)  N2(g)+ 2 H2O(g)
Observed Initial Rate
Experiment no. Initial NH4+ conc, M Initial NO2- conc, M
(M/s)
1 0.0100 0.200 5.4 x 10-7
2 0.0200 0.200 10.8 x 10-7
3 0.0400 0.200 21.5 x 10-7
4 0.200 0.0202 10.8 x 10-7
5 0.200 0.0404 21.6 x 10-7
6 0.200 0.0606 32.4 x 10-7

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Determination of Reaction Order
• If 𝑁𝐻4+ is doubled while holding [𝑁𝑂2− ] constant, the rate
doubles (compare experiments 1 and 2)
• If 𝑁𝐻4+ is increased by a factor of 4 (compare experiments 1
and 2), the rate changes by a factor of 4

• The results indicate that the rate is proportional to 𝑵𝑯+

𝟒 raised
to the first power

• When [𝑁𝑂2− ] is similarly varied while 𝑁𝐻4+ is held constant,

the rate is affected in the same manner, thus rate is proportional
to [𝑵𝑶−𝟐 ] raised to the first power 12
Determination of Reaction Order
• Thus for the reaction,
NH4 +(aq) + NO2-(aq)  N2(g)+ 2 H2O(g)

the rate law is: 𝑅𝑎𝑡𝑒 = 𝑘 𝑁𝐻+ [𝑁𝑂− ]

4 2

and the reaction is first order wrt [NH4+], first order wrt
[NO2-] and second order overall.

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Zeroth Order
• Very rare
• A → product/s

0
𝑅𝑎𝑡𝑒 = 𝑘 𝐴

𝑅𝑎𝑡𝑒 = 𝑘
• Rate has no dependence on the concentration of A

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First Order
• Depends on the concentration of only one reactant

1
𝑅𝑎𝑡𝑒 = 𝑘 𝐴

𝑅𝑎𝑡𝑒 = 𝑘[𝐴]

• Rate has dependence on the concentration of A

• Initial rate of the reaction doubles when the reactant is
doubled 15
Second Order
• Depends on the concentrations of one second-order reactant, or
two first-order reactants

2
𝑅𝑎𝑡𝑒 = 𝑘 𝐴
2
𝑅𝑎𝑡𝑒 = 𝑘[𝐵]
𝑅𝑎𝑡𝑒 = 𝑘 𝐴 [𝐵]
• The initial rate of the reaction quadruples when the reactant is
doubled 16
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

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Reaction Order
Determine the overall reaction order for the following
reactions.

1.2N2O5(g) → 4NO2(g) + O2(g) Rate = k[N2O5]

2.CHCl3(g) + Cl2(g) → CCl4(g) + HCl(g) Rate = k[CHCl3][Cl2]1/2

3.H2(g) + I2(g) → 2HI(g) Rate = k[H2][I2]

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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 Initial A conc, Initial B conc, Observed Initial Rate

no. M M (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 19
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.

• Answer: rate = k[NO]2[H2] ; k = 250 /M2-s 20

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

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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

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Collision Theory
• Proper orientation of colliding particles

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Collision Theory
• Colliding particles must have sufficient energy for an
effective collision to take place

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Activation Energy, Ea
• The minimum amount of energy needed by colliding
particles for a chemical reaction to proceed

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Transition State

• High energy state of the

particles that is
intermediate between
the reactants and the
products

• Partial bond breaking

and partial bond
formation
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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

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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. 28
1. Surface area of solid or liquid reactants
• Increasing the surface area of the solid increases the
chances of collision taking place

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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.
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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 Zinc in
Zinc HCl solution HCl solution concentrated
HCl solution
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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. 32
3. Pressure at which the reaction occurs
• Increasing the pressure of a gas is exactly the same as
increasing its concentration

Molecules have space to Increasing the pressure decreases the volume and
move around, there is little increases the concentration. Molecules have less
chance of a collision space to move in and more likely to collide
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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.

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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.

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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)
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4. Temperature
The Arrhenius Equation
• Linear form (by taking the ln of both sides):

𝑬𝒂 𝑬𝒂 𝟏
𝐥𝐧 𝒌 = − + 𝐥𝐧 𝑨 𝐥𝐧 𝒌 = − ∙ + 𝐥𝐧 𝑨
𝑹𝑻 𝑹 𝑻

Linear plot: ln k vs. 1/T

Slope: –Ea/R 𝒚 = 𝒎 ∙ 𝒙 + 𝒃

y-intercept: ln A
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4. Temperature
• The rate constants for the T (K) k (1/M1/2-s)
decomposition of acetaldehyde: 700 0.011
CH3CHO(g) → CH4(g) + CO(g) was
730 0.035
measured at different temperatures
as shown. 760 0.105
790 0.343
810 0.789
• Determine the Ea (in kJ/mol) for the
reaction.
Plot 1/T vs ln k
Ans.: Ea = 1.8 × 102 kJ/mol
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4. Temperature
• The table shows the rate constants for
the rearrangement of methyl isonitrile
at various temp. T (K) k (s-1)
462.9 2.52 x 10-5
• a. Determine the Ea (in kJ/mol) for the 472.1 5.25 x 10-5
reaction. 503.5 6.30 x 10-4
• b. What is the value of the rate 524.4 3.16 x 10-3
constant at 430.0 K?
Ans.: Ea = 1.6 × 102 kJ/mol;
k=1.0 x 10-6 s-1
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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

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5. Presence of a catalyst
Enzymes
• Catalysts in biological systems

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