Unit 4

Chemical Kinetics and

Chemical Equilibrium
 Reaction Rates
 Rate Laws
 First and Second Order Reactions
 Chemical Equilibrium
 Equilibrium Constants
 LeChatelier’s Principle
 Reaction Rates
 Questions to consider:
 What makes “superglue” bond instantly
while Elmer’s glue does not?
 What factors determine how quickly food
spoils?
 Why do “glow sticks” last longer when
stored in the freezer?
 How do catalytic converters remove
various pollutants from car exhaust?
 Reaction Rates
 These types of questions can be answered
using chemical kinetics.
 The study of the speed or rate at which
chemical reactions occur
 Reaction Rates
 The rate of a chemical reaction is affected
by many factors, including:

 concentration of reactants
 as concentration of reactants

increases the rate of reaction generally

increases
 Reaction Rates
 The rate of a chemical reaction is affected
by many factors (cont):

 reaction temperature
 food spoils more quickly at room

temperature than in a refrigerator

 bacteria grow faster at RT than at

lower temperatures
 Reaction Rates
 The rate of a chemical reaction is affected
by many factors (cont):
 presence of a catalyst
 a substance that increases the rate of

a reaction without being consumed in

the reaction
 Enzymes
 biological catalysts

 proteins that increase the rate of

biochemical reactions
 Reaction Rates
 The rate of a chemical reaction is affected
by many factors (cont):

 surface area of solid or liquid reactants

or catalysts
 as surface area increases the rate of

reaction generally increases

 Reaction Rates
 The speed of an object or event is the
change that occurs in a given time interval.

 Speed of a car = change in distance

time interval
= d
t

Remember, the term change always refers to

final value minus initial value.
 Reaction Rates
 Similarly, the rate (or speed) of a reaction can
be determined:

Rate = change in concentration (or moles) of product

time interval

Rate =  (conc. or moles)

t
 Reaction Rates
Consider the chemical reaction:
A B

Time = 0. t = 20. min t = 40. min

10. mol A 5.0 mol A 2.0 mol A
5.0 mol B 8.0 mol B
 Reaction Rates
If the number of moles of A and B are
measured and plotted, a graph such as this
one can be obtained
12
10
This data
moles A or B

8
moles A can be
6
4 moles B used to
2 find the
0
0 20 40 60 80 reaction
time (min) rate.
 Reaction Rates
 The reaction rate for a chemical reaction
can be expressed as either:

the increase in concentration (or number


of moles) of a product as a function of
OR time.
 the decrease in concentration (or number
of moles) of a reactant as a function of
time
 Reaction Rates
In this reaction:

Average rate of
appearance of B = change in # of moles of B
change in time

=  (mol B)
t

 We can calculate the average rate for any

time interval involved in the reaction.
 Reaction Rates
If we consider the rate of appearance of B over
the first 20 minutes of reaction:

Average rate of
appearance of B =  (mol B)
t

= 5.0 mol B – 0.0 mol B

20. min – 0. min

= 0.25 mol/min
 Reaction Rates
 The average rate of appearance of B during
the second 20 minutes of the reaction:

Avg. rate = 8.0 mol B – 5.0 mol B

40. min – 20. min

= 0.15 mol/min

Notice that the average rate of reaction

decreases over the course of the reaction.
 Reaction Rates
 The rate of a reaction can also be
expressed as the disappearance of A as a
function of time.

 For this particular reaction, when 1 mole of

B is formed, 1 mole of A must disappear.

A B
 Reaction Rates
Time B A
Interval t t

0 – 20.0 min 0.25 mol

min

20.0 – 40.0 min 0.15 mol

min

Notice: B/t = - A/t

 Reaction Rates
 We don’t want to report two different values
for the rate of the reaction.

For reactions with 1:1 stoichiometry:

 Avg. rate =  (moles product)

t

= -  (moles reactant)
t
 Reaction Rates
 For most reactions, the reaction rate is expressed
as a change in concentration of a particular
reactant or product

Average Rate =  [Product] = -  [Reactant]

t t

where [Product] = concentration of product

[Reactant] = concentration of reactant

 units: M / sec or M / min

 M = molarity = moles/liter
 Reaction Rates
 On the exam, you will be expected to find
the average rate of reaction for a specific
time interval when given the concentration
or number of moles of either reactants or
products as a function of time.
 Reaction Rates
Example: Given the following data, what is
the average rate of the following reaction over
the time interval from 54.0 min to 215.0 min?

CH3OH (aq) + HCl (aq) CH3Cl (aq) + H2O (l)

Time (min) [HCl] (M)

0.0 1.85
54.0 1.58
107.0 1.36
215.0 1.02
 Reaction Rates
Given: [HCl]54 min = 1.58 M
[HCl]215 min = 1.02 M

Find: avg. rate of disappearance of HCl

Avg. rate = -  [HCl]

t
= - (1.02 M - 1.58 M)
215 min - 54 min

= 0.0035 M / min
 Reaction Rates
Example: Calculate the average reaction rate
for the reaction A  B during the first 60.0
minutes using the following data:

Time [A]

0.0 min 1.50 M

20.0 min 1.00 M
40.0 min 0.80 M
60.0 min 0.75 M
80.0 min 0.70 M
 Reaction Rates
 So far, all reactions have had a one-to-one
stoichiometry.

 What happens when the coefficients are not

all 1?

2A 3B
 Reaction Rates
Consider the following reaction:

2 HI (g) H2 (g) + I2 (g)

Time mol mol mol

(min) HI H2 I2

0.0 2.00 0.0 0.0

10.0 1.50
20.0 1.00
30.0 0.75
 Reaction Rates
Calculate the change in HI and H2 as a function
of time for the first 20.0 minutes of reaction:

2 HI (g) H2 (g) + I2 (g)

HI H2
Time mol mol mol t t
(min) HI H2 I2 (mol/min)

0.0 2.00 0.0 0.0

10.0 1.50 0.25 0.25
20.0 1.00 0.50 0.50
30.0 0.75 0.75 0.75
 Reaction Rates
 The average reaction rate must be numerically
the same, regardless of whether you express
it as the rate of appearance of product or the
rate of disappearance of reactant.

 HI disappears twice as fast as H2 appears. To

make the rates equal:

Rate = - 1  [HI] =  [H2]

2 t  t
 Reaction Rates
 In general, for a reaction:

aA + bB cC +dD

the rate of the reaction can be found by:

Rate = - 1 [A] = - 1 [B] = 1 [C] = 1[D]

a t b t c t d t
 Reaction Rates
Rate = - 1 [A] = - 1 [B] = 1 [C] = 1[D]
a t b t c t d t

This equation can be used to establish the

relationship between rate of change of one
reactant or product to another reactant or
product.
 You have to be able to do this on the
test, too!
 Reaction Rates
Example: How is the rate of disappearance of
N2O5 related to the rate of appearance of NO2
in the following reaction?

2 N2O5 (g) 4 NO2 (g) + O2 (g)

 Reaction Rates
Example: If the rate of decomposition of N2O5
in the previous example at a particular instant
is 4.2 x 10-7M /s, what is the rate of
appearance of NO2?

2 N2O5 (g) 4 NO2 (g) + O2 (g)

Given: - [N2O5] = 4.2 x 10-7 M /s

t
 Reaction Rates
2 N2O5 (g) 4 NO2 (g) + O2 (g)

Rate = - 1 [N2O5] = 1 [NO2]

2 t 4 t
So:

[NO2] = - 4 [N2O5]
 t 2 t

= 2 x 4.2 x 10-7 M /s = 8.4 x 10-7 M/s

 Reaction Rates
 Recall that the average reaction rate
changes during the course of the reaction.

 Until now, we have calculated average

reaction rates.

 The reaction rate at a particular time (not

time interval) is called the instantaneous
reaction rate.
 Reaction Rate
 The instantaneous reaction rate is found by
determining the slope of a line tangent to
the curve at the particular time of interest.

 Fortunately (for you), you won’t have to do

this on the exam or HW!
 Rate Laws
 Consider the data presented earlier for the
disappearance of HCl as a function of time
for the following reaction.

CH3OH (aq) + HCl (aq) CH3Cl (aq) + H2O (l)

Time (min) [HCl] (M)

0.0 1.85
54.0 1.58
107.0 1.36
215.0 1.02
 Rate Laws
 The average reaction rate decreases with time.
 The reaction slows down as the
concentration of reactants decreases.

CH3OH (aq) + HCl (aq) CH3Cl (aq) + H2O (l)

Time (min) [HCl] (M) Avg. Rate (M /min)

0.0 1.85
54.0 1.58 0.0050
107.0 1.36 0.0042
215.0 1.02 0.0031
 Rate Laws
 In general, the rate of any reaction depends
on the concentration of reactants.

 The way in which the reaction rate varies

with the concentration of the reactants can
be expressed mathematically using a rate
law.
 An equation that shows how the reaction
rate depends on the concentration of the
reactants
 Rate Laws
 For a generalized chemical reaction:

wA+xB yC+zD

the general form of the rate law is:

Rate = k[A]m [B]n

where k = rate constant

m, n = reaction order
 Rate Laws
 Rate Constant (k)
 a proportionality constant that relates the
concentration of reactants to the reaction
rate

 Reaction Order
 the power to which the concentration of a
reactant is raised in a rate law

 Overall reaction order

 The sum of all individual reaction orders
 Rate Laws
 Rate laws must be determined
experimentally.
 Measure the instantaneous reaction rate
at the start of the reaction (i.e. at t = 0) for
various concentrations of reactants.

 You CANNOT determine the rate law by

looking at the coefficients in the balanced
chemical equation!
 Rate Laws
 First Order Reaction
 Overall reaction order = 1
 Rate = k[A]

Expt [A] (M) Rate (M/s)

1 0.50 1.00

2 1.00 2.00

3 2.00 4.00
 Rate Laws
 Second Order Reaction
 Overall reaction order = 2
 Rate = k[A]2

Expt [A] (M) Rate (M/s)

1 0.50 0.50

2 1.00 2.00

3 1.50 4.50
 Rate Laws
 Third Order Reaction
 Overall reaction order = 3
 Rate = k[A]3

Expt [A] (M) Rate (M/s)

1 0.50 0.25

2 1.00 2.00

3 1.50 6.75
 Rate Laws
 Zero Order Reaction
 Overall reaction order = 0
 Rate = k[A]0 = k

Expt [A] (M) Rate (M/s)

1 0.50 2.00

2 1.00 2.00

3 1.50 2.00
 Rate Laws
REMEMBER

 Rate laws must be determined experimentally.

 Determine the instantaneous reaction rate
at the start of the reaction (i.e. at t = 0) for
various concentrations of reactants.

 You CANNOT determine the rate law by

looking at the coefficients in the balanced
chemical equation!
 Rate Laws
 To determine the rate law from
experimental data,
 identify two experiments in which the
concentration of one reactant has been
changed while the concentration of the
other reactant(s) has been held constant

 determine how the reaction rate changed

in response to the change in the
concentration of that reactant.
 Rate Laws
 To determine the rate law from
experimental data (cont)
 Repeat this process using another set of
data in which the concentration of the
first reactant is held constant while the
concentration of the other one is
changed.
 Rate Laws
Example: The initial reaction rate of the
reaction A + B C was measured for
several different starting concentration of A
and B. The following results were obtained.
Determine the rate law for the reaction.

Expt # [A] (M) [B] (M) Initial rate (M /s)

1 0.100 0.100 4.0 x 10-5
2 0.100 0.200 8.0 x 10-5
3 0.200 0.100 16.0 x 10-5
 Rate Laws
Expt # [A] (M) [B] (M) Initial rate (M /s)
1 0.100 0.100 4.0 x 10-5
x2 x2
2 0.100 0.200 8.0 x 10 -5

3 0.200 0.100 16.0 x 10-5

Rate = k [A]m [B]n

Compare experiments 1 and 2 to find n:

[A] = constant Rate doubles: [2]n = 2.0
[B] = doubles 8.0 x 10-5 = 2.0 n=1
4.0 x 10-5
Rate = k[A]m[B]1
 Rate Laws
Expt # [A] (M) [B] (M) Initial rate (M /s)
1 0.100 0.100 4.0 x 10-5
x4
2 0.100 x 2 0.200 8.0 x 10-5
3 0.200 0.100 16.0 x 10-5

Rate = k [A]m [B]n

Compare experiments 1 and 3 to find m:
[A] = doubles Rate quadruples: [2]m = 4.0
[B] = constant 16.0 x 10-5 = 4.0 n=2
4.0 x 10-5
Rate = k[A]2[B]
 Rate Laws
You can also solve this using algebra:
Rate = k [A]m [B]n

Compare experiments 1 and 3 to find m:

Rate 2 = k [0.200 M]m [0.100 M]n = 16.0 x 10-5 =4.0

Rate 1 k [0.100 M]m [0.100 M]n 4.0 x 10-5

[0.200 M]m = 4.0

[0.100 M]m [2.00]m = 2.0
2m = 4.0 only if m = 2
Rate = k[A]2[B]n
 Rate Laws
You can also solve this using algebra:
Rate = k [A]m [B]n

Compare experiments 1 and 2 to find n:

Rate 2 = k [0.100 M]m [0.200 M]n = 8.0 x 10-5 = 2.0

Rate 1 k [0.100 M]m [0.100 M]n 4.0 x 10-5

[0.200 M]n = 2.0

[0.100 M]n [2.00]n = 2.0
2n = 2.0 only if n = 1
Rate = k[A]2[B]