Chapter 12

Chemical Kinetics

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 Chemical Kinetics
• Studies the rate(Speed) at which a chemical process
occurs.

• Speed of a reaction is measured by the change in

concentration over time.

• Different from Thermodynamics: which determines if

a reaction take place.

• Our goal is to understand chemical reactions at the

molecular level.(mechanics of the reaction)
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 Outline: Kinetics
Reaction Rates How we measure rates.

How the rate depends on concentration

Rate Laws of reactants.
How to calc amount left or time to reach
Integrated Rate Laws a given amount.
How long it takes to react 50% of
Half-life reactants.

Arrhenius Equation How rate constant changes with T.

Link between rate and molecular scale

Mechanisms processes.

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 Reaction Rates

• We define the reaction rate as the change in

concentration of a reactant or product per unit time.

•For the reaction “A B” there are two ways of

measuring rate:
(1) the speed at which the reactants disappear
(2) the speed at which the products appear

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 Reaction Rates

Rates of reactions can be determined by

monitoring the change in concentration of
either reactants or products as a function of
time.
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Factors That Affect Reaction Rates
• 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 more kinetic energy,
move faster, and collide more often and with greater energy.
• Catalysts
Speed rxn by changing mechanism.
• Surface area
More area for reactants to be in contact with each other.
• Pressure of gaseous reactants or Products.
Increased number of collisions

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Chemica
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 Chemical Kinetics
Most Common Units… Rate = M/s
(Remember…Molarity (M) = moles/Liter)

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B

Δ[A] Δ[A] = change in concentration of A over

rate =
Δt time period Δt
-
Δ[B] Δ[B] = change in concentration of B
rate =
Δt over time period Δt
Because [A] decreases with time, Δ[A] is negative.
AVERAGE Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
[C4H9Cl] M
In this reaction, the
concentration of
butyl chloride,
C4H9Cl, was
measured at various
times, t.

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AVERAGE Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)
Average Rate, M/s
The average rate of
the reaction over
each interval is the
change in
concentration divided
by the change in time:

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 Reaction Rates
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

• Note that the average

rate decreases as the
reaction proceeds.
• This is because as the
reaction goes forward,
there are fewer
collisions between
reactant molecules.

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Reaction Rates and Stoichiometry
C4H9Cl(aq) + H2O(l) ⎯⎯→ C4H9OH(aq) + HCl(aq)

• In this reaction, the ratio

of C4H9Cl to C4H9OH is
1:1.
• Thus, the rate of
disappearance of
C4H9Cl is the same as
the rate of appearance
of C4H9OH.

-Δ[C4H9Cl] Δ[C4H9OH]
Rate = = Chemica
Δt Δt l
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Reaction Rates and Stoichiometry

• What if the ratio is not 1:1?

H2(g) + I2(g) ⎯⎯→ 2 HI(g)
• Only 1/2 HI is made for each H2 used.

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Reaction Rates and Stoichiometry

• To generalize, for the reaction

aA + bB cC + dD

Reactants Products
(decrease) (increase)

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 THE RATE LAW USING
INITIAL CONCENTRATIONS
Each reaction has its own
equation that gives its rate as a
function of reactant
concentrations. Chemica
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 Calculating The Initial Rate Law
The rate law expresses the mathematical relationship of the rate
of a reaction to the concentrations of the reactants. The products
play no role in the calculations.
aA + bB products

Rate = k [A] x [B] y

Rate = Molarity /sec

k= rate constant and it varies with each reaction, temperature
dependent.
[A] [B] = Concentrations of reactants in M (moles/liter)
x and y = Values for the reaction order. They tell us how
important each of the reactants is in regard to [Link]
higher the number the more value it has to overall speed.
x does not equal a and y does not equal b
 aA + bB products

Trial [A] M/S [B] M/S Rate M/S

1 0.100 .100 2.00 x10-3
2 0.200 .100 4.00 x 10 -3
3 0.200 .200 16.00 x 10 -3
 Concentration and Rate
Homework

Compare Experiments 1 and 2:

when [NH4+] doubles, the initial rate doubles.
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 ZERO ORDER
The rate of change is independent of the
concentration of the reactant.
A products

Rate = k [A] 0
Rate = k

Ex: Decomposition of ammonia over tungsten

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 Concentration and Rate
Homework

Likewise, compare Experiments 5 and 6:

-
when [NO2 ] doubles, the initial rate doubles.
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INTEGRATED RATE LAWS

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Zero Order Integrated Rate Law
The rate of change is independent of the
concentration of the reactant.

[A]t = - kt + [A]0

Y = mx + b
This means that we can graph the concentration as a
function of time and it should create a straight line that
will give a slope and then you can find the value of -k! Chemica
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 First Order Integrated Rate Law
The rate is proportional to the concentration of a single
reactant raised to the first power

Using calculus you get the following equation:

ln[A]t = - kt + ln [A]0
Y = mx + b

If a reaction is first-order, a plot of ln[A]t vs t

will give a straight line with a slope of -k.
So, use graphs to determine rxn order. Chemica
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Second Order Integrated Rate Law
The rate is proportional to a either the
concentration of a single reactant raised to the
second power or two reactants each raised to the
first power.

also in the form y = mx +

b Chemica
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How are these equations helpful?
• You now have a technique for determining the order of a
reaction by observing graphs created from experimental
data of concentration vs time.

• If a simple graph of concentration vs time is a straight line

then you know that it is a zero order reaction.

• If the natural log of concentration vs time is a straight line

then you know that it is a first order reaction.

• If the reciprocal concentration vs time is a straight line then

you know that it is a second order.
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The conclusion:
In all cases, once you get a straight line
fit , you can then get the rate constant
from calculating the slope of the line.

Slope (m) = ΔY
ΔX

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Chemica
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 Zero Order Integration
2NH3(g) N2 + 3 H2 (g) [A]t = - kt + [A]0

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 First-Order Integration

• When lnCH3NC is plotted as a function of time, a straight line

results.
• The reaction is first-order, a plot of ln [A]t vs. t will yield a
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straight line with a slope of -k. l
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.
 Second-Order Integration

So if a reaction is second-order in A, a plot of

vs. t will yield a straight line with a slope of k.

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 Determining rxn order
The decomposition of NO2 at 300°C is described by
the equation
2NO2 (g) 2NO (g) + O2 (g)
and yields these
data:
Time (s) [NO2], M ln [NO]2 1/ [NO2]
0.0 0.01000
50.0 0.00787
100.0 0.00649
200.0 0.00481
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300.0 0.00380 l
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 [NO2] vs Time

• The plot is not a straight line, so the

process is not zero-order. Chemica
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 Determining rxn order
Graphing ln [NO2] vs. t yields:

• The plot is not a straight

line, so the process is not
first-order in [A].
Time (s) [NO2], M ln [NO2]
0.0 0.01000 -4.610
50.0 0.00787 -4.845 Does not fit:
100.0 0.00649 -5.038
200.0 0.00481 -5.337
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300.0 0.00380 -5.573 l
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 Second-Order Processes
A graph of 1/[NO2] vs. t
gives this plot.

Time (s) [NO2], M 1/[NO2] • This is a straight line.

0.0 0.01000 100 Therefore, the
50.0 0.00787 127 process is second-
100.0 0.00649 154 order in [NO2].
200.0 0.00481 208
300.0 0.00380 263 k= 0.543 Chemica
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Chemica
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 Half-Life
• Half-life is defined as the time required for
one-half of a reactant to react.

• Half-Life is also defined as the rate of decay

of a radioactive substance. A radioactive
substance is one that will slowly decay into
a more stable form as time goes on.

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 Determining a Half Life
To determine a half life, t½, the time required for the initial
concentration of a reactant to be reduced to one-half its initial
value, we need to know:

● The order of the reaction or enough information to determine

it.
● The rate constant, k, for the reaction or enough information to
determine it.
● In some cases, we need to know the initial concentration, [Ao]
● Substitute this information into the equation for the half life of
a reaction with this order and solve for t½.

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 Half-Life
For a first-order reaction the formula is as follows and
it is also found on the AP Reference sheet in the
Kinetics section. A Products

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1st Order reactions Half-life is constant

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Half-Life for a Second- Order Reaction

A products
A+B products

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 2nd order reaction half-life is variable.
It increases with decreasing concentration.

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Chemica
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Finding the Overall Rate Law
by Utilizing Reaction
Mechanisms

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 Reaction Mechanisms
• Not all reactions occur in one step.

• The step by step sequence of 2 or more

simple reactions that combine to form the
overall reaction.

• A chemical mechanism describes in detail

exactly what takes place at each stage of an
overall chemical reaction.
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 Reaction Mechanism Terms
Complex reaction- overall reaction
elementary steps- series of simpler reactions
that combine to form the complex reaction.

Intermediate-a substance produced in one

elementary step and consumed in another.

Catalyst-increases the rate but not consumed

by the [Link] remains unchanged.
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 Multistep Mechanisms
• In a multistep process, one of the steps will
be slower than all others.

• The slowest step is called the rate-

determining [Link] will be the one used to
find the rate law for the overall reaction.

• The overall reaction cannot occur faster

than this slowest, rate-determining step Chemica
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 Hypothetical Reactions #1
1)P + Q B (SLOW)

2) B + Q 2R (FAST)

What is the overall rate law for this reaction?

What is the complex equation for this reaction? Chemica
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 Hypothetical Reactions # 2

1)P + Q B (SLOW)

2) B + Q P + 2R(FAST)

What is the overall rate law for this reaction?

What is the complex equation for this reaction? Chemica
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 Practice Reactions
1. 2NO N2O2 (slow)
2.N2O2 + H2 N2O + H2O (fast)
3.N2O + H2 H2O +N2(fast)

a.)Which is the rate determining step?

b.)Does this reaction have a catalyst?
c.)What is the complex equation for this
reaction?
d.) What is the rate law?
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Answers to practice problem

A.) Step one is the rate determining step

B.) No catalyst
C.) 2NO + 2H2 N2 + 2H2O
D.) rate = k [NO]2

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 Please Remember!!!!

• YOU CAN ONLY USE THE COEFFICIENT

METHOD TO DETERMINE THE RATE LAW
OF ELEMENTARY STEPS.

• YOU CANNOT USE THE COEFFICIENTS

FROM THE COMPLEX EQUATION AND
DO THE SAME THING.
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