Chemical Kinetics

Chemical Kinetics

• The study of the

rate of chemical
reactions, including
the mechanism by
which a reaction
occurs and the
different factors that
affect it.

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Rate of a Reaction

• Rate of reaction is critical in all

areas of chemistry
• The rate of reaction can be
defined as the change in the
Imagine cold a lizard slows down
concentration of a reactant or
product per change in time.
• The concentration of the
reactants decreases as the
reaction proceeds

Imagine a rocket launch

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The Rate of a Chemical Reaction

Rate
• The rate of a chemical
reaction is a measure of how
fast the reaction occurs

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The Rate of a Chemical Reaction
Rate
aA + bB cC + dD

1 [A] 1 [B]
Rate= - 1 [C]
a t =- b t =
c t

1 [D]
= d t

By convention, a negative sign is attached on the change in the

concentration of the reactants, which underscores the fact that the
concentration of the reactants decreases as the reaction proceeds. This
convention maintains the positive sign for the rate

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 Sample Problem
Hydrogen peroxide (agua oxygenada, H2O2) is a colorless
liquid used as disinfectant and bleach. At high
temperatures, it decomposes easily into water and oxygen.
2H2O2(aq) 2H2O(l) + O2(g)
Write the equation for the rate of reaction based on the
concentration of the reactants and products

Answer: 1 [H2O] [O2]

1 [H2O2]
Rate= - = t =
2 t 2 t

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 Sample Problem
Express the rate of the chemical reactions in terms of the
change in concentration of the reactants or products
2N2O(aq) 2N2(g) + O2(g)
Answer:

1 [N2] [O2]
- 1
[N2O]
Rate= = t =
2 t 2 t

Copyright © Cengage Learning. All rights reserved 7

 Assignment
Express the rate of the following chemical reactions in
terms of the change in concentration of the reactants or
products

1. N2(g) + 3H2(g) 2NH3(g)

2. 2C4H10(g) + 13O2(g) 8CO2(g) + 10 H2O(g)

Copyright © Cengage Learning. All rights reserved 8

 The Rate of a Chemical Reaction

Rate
• Speed of chemical reaction is measured as a
change in the amount of some reactant or
product per unit time.
H2 (g) + I2 (g) → 2 HI (g)
• The rate expression shows the relative speed at
which the concentration of one species changes
with respect to that of another species.

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 The Rate of a Chemical Reaction

Rate
• H2 (g) + I2 (g) → 2 HI (g)

• Disappearance of reactant

• Appearance of product

– The concentration of HI increases at 2x the rate of that I2 or H2

decreases
• For the overall rate to have the same value when defined
with respect to any reactant the change in HI must be
multiplied by 1/2
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 The Rate of a Chemical Reaction
Change in Reactant and Product Concentrations

• H2 (g) + I2 (g) → 2 HI (g) Fig 13-2

• 2 mole HI produced for

every mole of H2
consumed

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 The Rate of a Chemical Reaction

The Average Rate of the Reaction

• If we look at 10 sec time intervals the rate of

reaction gets slower over time.

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 The Rate of a Chemical Reaction

The Instantaneous Rate of the Reaction

• Rate at any single
point.
• Determined by
calculating the slope of
the tangent to the
curve

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 The Rate of a Chemical Reaction

The Instantaneous Rate of the Reaction

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 The Rate of a Chemical Reaction

General Definition of Rate and Rate of Reaction

• aA + bB → cC + dD

• We can predict the rate of change of one

reactant or product based on the rate of change
of another
– We cannot predict rate based on the balanced
equation alone.
• Must be done experimentally
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 The Rate of a Chemical Reaction

Learning Check
• For 2N2O (g) → 2 N2 (g) + O2 (g)

1. Express the rate in terms of change in

concentration of reactants and products.
2. In the first 15 sec., 0.015 mol of O2 is produced
in a 0.500 L reaction vessel. Determine the
average rate of reaction?

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 The Rate of a Chemical Reaction

Solution
• For 2N2O (g) → 2 N2 (g) + O2 (g)

1.

2.

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 The Rate of a Chemical Reaction

Measuring Reaction Rates

• Chemical Polarimetry
– By measuring the degree of
polarization of light passing
thru a solution of reactants
and products can determine
the relative amounts of
each.

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 The Rate of a Chemical Reaction

Measuring Reaction Rates

• Spectroscopy
– Light is passed thru a sample
– Absorption of light is proportional to concentration.
– More light absorbed = higher concentration.

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 The Rate of a Chemical Reaction

Measuring Reaction Rates

• Pressure Measurement
– Concentrations of gaseous reactants can be
monitored by measuring changes in pressure

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 The Rate Law: The Effect of Concentration on Reaction Rate

Reaction Rate vs Rate Expression vs Rate Law

• Rate (0.0070 M/s)
– Production of product or loss of reactant over time
• Rate expression
– From balanced equation
– How loss of reactants and production of products
relate to each other
• Rate Law
– Experimentally determined
– Describes how rate depends on concentration of
reactants

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 The Rate Law: The Effect of Concentration on Reaction Rate

The Rate Law

• Rates of reaction often depend on the
concentration of one or more reactants
• Consider a simple reaction A → products
• We can express this relationship in a Rate Law

• Rate = k [A]n
– Where k is a proportionality constant called a rate
constant and n is the reaction order

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 The Rate Law: The Effect of Concentration on Reaction Rate

The Rate Law

• Rate = k [A]n
• The value of n determines how the rate depends
on the concentration of the reactant

Value Reaction rate

of n order
0 zero Independent of the [A]
1 first Directly proportional to [A]
2 second Proportional to [A]2

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The Rate Law: The Effect of Concentration on Reaction Rate

Zero, First and Second-Order Reactions

• We can examine reaction order by
looking at:

• Fig 13-5 [reactant] vs time

– The slope of this line = rate
• Δ [R] / Δt

• Fig 13-6 Rate vs [reactant]

– How does [R] affect rate

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 The Rate Law: The Effect of Concentration on Reaction Rate

Zero-Order Reaction
• Rate = k[A]0 = k
– Independent of reactant concentration

• [Reactant] decreases linearly with

time
– Constant reaction rate
– Reaction does not slow down as
reaction progresses

• Rate is the same at any [reactant]

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 The Rate Law: The Effect of Concentration on Reaction Rate

Zero-Order Reaction
• Example of a zero-order reaction is decomposition of
NH3 in presence of molybdenum or tungsten catalyst
[Mo]

• 2NH3 (g) → N2 (g) + 3H2 (g)

• The surface of the catalyst is almost completely covered

by NH3 molecules. The adsorption of gas on the surface
cannot change by increasing the pressure or
concentration of NH3. Thus, the concentration of gas
phase remains constant although the product is formed.

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 The Rate Law: The Effect of Concentration on Reaction Rate

First-Order Reaction
• Rate = k[A]1 = k
– Directly proportional to [reactant]
• [Reactant] decreases with time
– Not linear – slope becomes less steep
– Reaction slows down as reaction
progresses
– Rate decreases
• Rate is directly proportional to
[reactant]
– linear

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 The Rate Law: The Effect of Concentration on Reaction Rate

Second-Order Reaction
• Rate = k[A]2
– Proportional to square of [reactant]
• [Reactant] decreases with time
– Not linear – slope becomes less steep
– Reaction slows down as reaction
progresses
– Rate decreases
• Rate is proportional to square
[reactant]

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The Rate Law: The Effect of Concentration on Reaction Rate

Determining Reaction Order (method of initial rates)

• Measure the (initial) rate of reaction at several
different [reactant].
• In this set of data when [A] doubles the rate
doubles
• Rate is directly
proportional to [A]
• First order
• Rate = k [A]

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The Rate Law: The Effect of Concentration on Reaction Rate

Determining Reaction Order (method of initial rates)

• This set of data shows no effect on rate with
increasing [A].
• Rate is independent of [A].
• Zero order
• Rate = k

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The Rate Law: The Effect of Concentration on Reaction Rate

Determining Reaction Order (method of initial rates)

• In this set of data when [A] doubles the rate
quadruples.
• Rate is directly
proportional to [A]2
• Second order
• Rate = k [A]2

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The Rate Law: The Effect of Concentration on Reaction Rate

Determining Reaction Order: Method of Initial Rates

The rate law for the reaction can be experimentally
determined through the method of initial rates.
A+B C
Mathematically, the order can be determined using
two rate laws:
Rate2 K[A]2x [B]2y
=
Rate1 K[A]2x [B]2y

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The Rate Law: The Effect of Concentration on Reaction Rate

Concept Check
• The initial rate of reaction is measured for the
reaction NO2 (g) + CO (g) → NO (g) + CO2 (g)
• Determine the rate law and rate constant for the
reaction.

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The Rate Law: The Effect of Concentration on Reaction Rate

Solution
• The initial rate of reaction is measured for the
reaction NO2 (g) + CO (g) → NO (g) + CO2 (g)
• Determine the rate law and rate constant for the
reaction.
• Rate = k [NO2]2[CO]0
• Rate = k [NO2]2
k= rate 0.0021 M/s
=
[NO2] 2 [0.10 M] 2

= 0.21 M - s -

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 The Rate Law: The Effect of Concentration on Reaction Rate

Reaction Rate vs Rate Expression vs Rate Law

• Rate (0.0070 M/s)
– Production of product or loss of reactant over time
• Rate expression
– From balanced equation
– How loss of reactants and production of products
relate to each other
• Rate Law Rate = k [H2]1[I2]1
– Experimentally determined
– Describes how rate depends on concentration of
reactants

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