Chemical

Kinetics
Chapter 14

1
RATE is a measurement of how quickly something happens
PER UNIT OF TIME.

The rate at which you might drive down the road is

determined by these signs:

60 miles per hour

30 kilometers per hour

30 kilometers = 30 kilometers/h= 30 km h-1

1 hour

2
The previous speeds have one thing in common.

They both represent how much something happens

(a variable) in a specific amount of time; that is, what
distance we travel per unit of time.

Rates can be expressed in different units.

3
Chemical Kinetics
Some reactions are spectacular,

and others take a longer time.

What is governing these chemical reactions?

In this unit we will look at the quantitative calculation

involving the species involved in a chemical reaction,
followed by a qualitative look at what happens at the
molecular level.
4
 Knowledge of reaction rates is useful in drug design,
food processing, industrial chemistry, to name a few.

This enables chemists to alter the rate to suit a specific purpose.

For example:
• slow down food spoilage
• slow down corrosion
• speed up the action of a medication
• speed up a step in an otherwise long, expensive process.

5
 Reaction Rates
Definitions:

Chemical Kinetics: the rates and mechanisms of

chemical reactions.
A mechanism is the series of simple steps a reaction
follows.
Reaction Rate:
The measure of the number of moles of
reactant used up (consumed) during a unit of
time (or the number of moles of product
produced).
6
Reaction Rate:

The rate of change of the concentration of reactants and

products.

For example: if A → 2 B,
◦ how quickly does A get used up?
◦ how fast does B get produced?

7
Reaction Rate:
Some quantity per unit of time:
If A → 2 B

∆X Rate = ∆[A] 0r ∆PB

Rate =
∆t ∆t ∆t

concentration pressure
M/s atm/s

This “quantity” measured depends on the type of

reaction.
8
What changes (in a reaction) could you easily follow
and measure?
energy pH
H+ or OH-
(kJ) pH meter
calorimeter

mass
gas product
conductivity scale
(presence of ions)
conductivity probe

9
 volume
pressure (mL)
(g) eudiometer
manometer

10
 absorbance
colorimeter
absorbance
(shade of colour given)
colorimeter

11
For example: ∆ conductivity
ions
∆ pressure
a) Pb2+(aq) + 2I-(aq) → PbI2(s) gas

b) Li(s) + H2O → H2(g) + Li+ + OH-

ions Mass of system

measure ∆ in conductivity. a base

∆ pH

12
 c) 3H2(g) + N2 (g) → 2NH3(g) + 92 kJ

heat produced
measure ∆ t
4 mol of gas →2 mol of gas
measure ∆ pressure

d) CuSO4(aq) + Zn(s) → ZnSO4 + Cu(s)

blue colourless

Absorbance
(wavelength)
Try Edvantage practice 1.1.1

13
 Quantifying Reaction Rates
The average rate of a chemical change is defined as:

R = ∆ quantity
∆ time

Often the quantity chosen is a:

change in concentration or a change in pressure

R=∆[ ] Of any reactant R= ∆P

∆ time or product ∆ time
species.
Not solids or liquids – Gases only.
can’t ∆ [ ] .
14
Consider NO(g) + O3(g) → NO2(g) + O2(g)

Looking at the reactants, the average rate can be expressed as:

R = ∆ [NO ] = [NO2 ]f – [NO2]i R = ∆ (PNO)

∆ time tf - ti ∆ time

∆ = “change in” = final – initial

(remember – aqueous or gases only)

BUT, rate can be the change in concentration of

any reactant or product.

15
 Therefore, for the previous example:
NO(g) + O3(g) → NO2(g) + O2(g)

R = - ∆ [NO ] = - ∆ [O3 ] = ∆ [NO2 ] = ∆ [O2 ]

∆ time ∆ time ∆ time ∆ time

Note: if we measure rate in terms of ∆ in a reactant,

reactants are assigned a negative value because their
concentration decreases with time.

RATE IS ALWAYS A POSITIVE VALUE.

16
 For a reaction involving different molar coefficients, we
must be careful to specify the species that is being used to
measure the rate.

e.g. 1 N2(g) + 3 H2(g) → 2 NH3(g)

For this reaction, the rate at which ammonia is produced

is twice (2X) the rate at which N2 is used. (Look at the
molar coefficients)
Or, the rate of hydrogen is 3X the rate of nitrogen.

Or, the rate of hydrogen is 3/2 X the rate of ammonia.

Or, the rate of ammonia is 2/3 X the rate of hydrogen.

17
 Example: write the rate of the following reaction
in terms of oxygen:

e.g. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H20(g)

5 mols of O2 react in the same time period as 4 mol of NH3

Therefore, Rate O2 = 5/4 Rate of NH3 = -5 ∆ [NH3]

4∆t
reactant

18
But we can also compare O2 to any product:
e.g. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H20(g)

5 mol of O2 react in the same time period as 4 mol of NO

Therefore, Rate O2 = 5/4 Rate of NO = 5 ∆ [NO]

4∆t

Positive : NO is product

19
 How would the rate of O2 compare to water?

e.g. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H20(g)

5 mols of O2 react in the same time period as 6 mol of H2O

Therefore, Rate O2 = 5/6 Rate of H2O = 5 ∆ [H2O]

6∆t

Positive : H2O is product

20
Remember, we don’t have to measure concentration.
If we have gases, we could measure gas pressure.
Rate = ∆ p / ∆ t

e.g. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H20(g)

In this case we could say rate of O2 consumption =

Rate O2 = - 5∆PNH3 = 5∆PNO = 5∆PH2O

4 ∆t 4 ∆t 6 ∆t

21
 The stoichiometric rate(relative rate) is written in terms
of one mole of each substance. To determine this,
divide each substance by its own molar coefficient:

1 N2(g) + 3 H2(g) → 2 NH3(g)

Rate = -∆[N2(g)] = -∆[H2(g)] = ∆[NH3(g)]

1∆t 3∆t 2∆t

22
What would be the relative stoichiometric
rate for the each of the substances in the
following reaction?

4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g)

23
 Putting it all together:
A + 3 B → 2 C + 2 D Initially the concentration of A is
0.9986 M and 13.20 min. later it is found to be 0.9746 M.
time final [ ]
Initial [ ]

a. What is the average rate of reaction of A during this time

period, expressed in M/s?

R = - ∆ [A ] = -( [A ]f – [A]i) = -(0.9746 – 0.9986)

∆ time ∆ time (13.20 min)(60s/min)

R = 3.03 x 10-5 M/s

24
 From question: A + 3 B → 2 C + 2 D
b. What is the average rate of production of D?

Looking at the equation: Rate of D = 2X Rate of A

RD = 2RA

From part a: Rate of A = 3.03 x 10-5 M/s

Rate of D = 2(3.03 x 10-5 M/s) = 6.06 x 10-5 M/s

25
From question: A + 3 B → 2 C + 2 D
c. What is the average rate of consumption of B?

Looking at the equation: rate of B = 3 rate of A

RB = 3RA

Rate of B = 3(3.03 x 10-5 M/s) = 9.09 x 10-5 M/s

26
Calculating Reaction Rates
Converting Reaction Rates in terms of concentration
to Reaction Rates in terms of pressure.

In terms of concentration: RC = R[ ] = ∆ [ ] / ∆ t

In terms of pressure: RP = ∆ P / ∆ t

How are these two related to one another?

Ideal gas law: PV = nRT or, rearranged: P = nRT
V
Since n, P = [ ] RT R = 0.0821 atm L / mol K
V T = Kelvin
27
 RP = ∆ P / ∆ t and P = [ ]RT
If T is constant, then ∆P = ∆[ ]

∆P = ∆[ ]RT
∆t ∆t
R = 0.0821 atm L / mol K
T = Kelvin
RP = R[ ]RT

OR R[ ] = RP
RT

28
Example:

Consider the reaction: 4PH3(g) → P4(g) + 6H2(g)

Suppose that, at a particular moment during the
reaction, molecular hydrogen is being formed at the
rate of 0.078 M/s at a temperature of 200oC?
a) At what rate is P4 being formed?
RP4 = 1/6 RH2 = 1/6 (0.078) = 0.013 Ms-1

b) At what rate is PH3 reacting?

RPH3 = 4/6 RH2 = 4/6 (0.078) = 0.0052 Ms-1

c) What would be the rate (in terms of pressure) for H2?

RP = R[ ]RT
RP = (0.078 M/s)(0.0821 Latm/molK)(200 + 273)
= 3 atms-1

29
Measuring Reaction Rates

To determine a rate of reaction we need to

measure changes in concentration over time of
any of the reactants or products. This could be
directly or indirectly, for example, if [H+] changes
we can measure pH, whereas some reactions
might have a colour change to indicate changes
in concentration.

30
 Volume of
To determine the rate of H2O2 O2
decomposition (2H2O2→ 2H2O + O2)
the set-up shown is used.

Oxygen is given off and is trapped,

and the volume is measured. This
can be related to decreases in
[H2O2].

Another, more difficult option, is to remove

small samples of the reaction mixture from H2O2
time to time and analyze these samples for
concentration.
31
Decomposition of H2O2
Rate= - ∆ [H2O2]
∆t
Time [H2O2] Rate (M/s)
(s) (M) R= - ([final] – [initial])
0 2.32 (0s – 200s) ∆t
R= - (2.01 – 2.32) = 1.56 x 10-3 M/s Overall Rate:
(200 – 0) = - (0.25 – 2.32)
200 2.01 (200 – 400) R= - (1.72 – 2.01) (3000 – 0)
(400 – 200) = 1.45 x 10-3 M/s
400 1.72 (400 – 600) R= - (1.49 – 1.72) = 1.15 x 10-3 M/s = 6.9 x 10-4 M/s
(600 – 400)
R= - (0.98 – 1.49) Is the rate the same
600 1.49 (600 – 1200) (1200 – 600) = 8.5 x 10-4 M/s
for the duration of
1200 0.98 (1200-1800) R= -(1800
(0.62 –0.98)
– 1200) = 6.0 x 10 M/s
-4 the reaction?

1800 0.62 (1800 – 3000) R= -(3000

(0.25 –0.62)
– 1800)
= 3.1 x 10-4 M/s Calculate the
average rate for
each interval given.
3000 0.25 What do you notice?
32
 This data shows that the rate of a reaction is not
constant.

The reaction is usually fastest at the beginning, and

slows over time due to the decrease in the amount
of available reactants for the reaction.

To obtain a better value for rate, we can graph

concentration of H2O2 vs. time.

33
 [H2O2] versus time

[H2O2]
(M)

Time (s)
34
 1. What does the shape of the graph tell
you about the rate of the reaction?

A curved line – rate is not constant.

fastest – 2. How can you tell if the graph represents

[H2O2] (M)

greatest slope a reactant or a product species?

If concentration decreases, it is a reactant
(gets used up during the reaction).
If concentration increases, it is a
product (gets produced)
slowest 3. When is the reaction the fastest? slowest ?
shallow slope Can you suggest why this might be?
time (s)

35
If we graph concentration (or pressure) for the duration
of a reaction, most graphs will have the following
shape.

This shape shows us:

36
 We already know that Rate = ∆ quantity
∆ time
On a graph this works out to be:

∆ [ ] or ∆ p = ∆Y (vertical axis) = rise = Slope of

∆t ∆t ∆X (horizontal axis) run the line

Rate = slope
[H2O2] (M) ∆[ ] = ∆Y = rise

∆ t = ∆ X = run
time (s)
37
 Average rate
To find an average rate, calculate the slope of a
straight line that is drawn by connecting the two points
(initial and final) of the time interval in question.

1st: put two dots on the curve at the

[ ] two times in question (time A and
or
B). (if it just asks for average rate
p
– assume it means from the very
beginning to the very end.)

A B 2nd: connect them with a straight line.

time

38
 3rd: Using any two points on the line you have drawn
(further apart is better), find [ ]f, [ ]i, tf and ti
[ ] You may use points A and B,
[]f but often other points are
f easier to read.

4th: calculate slope

[]i i
Rave= ( [ ]f – [ ]i )
tf – ti

time
ti tf

initial final
39
Instantaneous Rate:
Find the slope of a tangent line drawn the point in
time given in the question. The tangent line can only
touch the curve at one point.

1. Draw a point on your curve at the time given.

2. Draw a tangent line at that point.

(you are trying to figure out the slope
of the line at that instant in time)

A
40
 3. Find any two points on your tangent and use them
to calculate the slope.

[]f Rate = slope = ∆ rise

∆ run

Rate = ∆ ([ ]f – [ ] i)
[]i
∆ (tf – ti)

ti A tf

41
42
LAB #1
Graphical
Determination
of the Rate of a
Chemical
Reaction

43
Factors Affecting Rates
There are four main factors that affect the rate of
a reaction. They are:

•concentration of the reactants

•the nature of the reactants (surface area, phase)

•the temperature of the reacting system

•the use of a catalyst

44
Generally:
- slight rearrangements of electrons will be fast reactions

e.g. precipitate reactions

Ag+(aq) + Cl-(aq) → AgCl(s)

- if many covalent bonds must be broken, the reaction

will tend to be slow at room temperature.

e.g. decomposition
H2CO3(s)→ H2O(l) + CO2(s)

45
More Specifically:
States of Matter:
Gases tend to react faster than aqueous solutions, liquids or
solids.
Simple aqueous ions react almost instantaneously
Also - When we look at a reaction it can be either:

Homogeneous: all the reactants are in the same phase.

2H2(g) + O2(g) → 2H2O(l)

C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)

Heterogeneous: reactants are in more than one phase.

4Fe(s) + 3O2(g) → 2Fe2O3(s)

Cu(NO3)2(aq) + Zn(s) → Cu(s) + Zn(NO3)2(aq)
Homogeneous reactions will tend to be faster than
heterogeneous reactions because the reactants can
more easily collide and mix.

Reaction occurs
throughout.

Heterogeneous reactions will be slower because the

reactants only collide where the 2 phases come in
contact.
Reaction occurs only
on solid surface.
Bond Type:
Reactions involving ionic species tend to be faster than those involving
molecular compounds.

Bond Strength:
Reactions involving the breaking of weaker bonds proceed faster than
those that weaker breaking stronger bonds.
Number of bonds

Reactivity of Metal

50
Try these: Which of the following reactions would be faster?
Why?

1. H2(g) + I2(g) → 2 HI(g) versus

Pb(NO3)2 (aq) + 2 NaI(aq)→ PbI2(s) + 2 NaNO3(aq)

2. 2 NO(g) + O2(g) → 2 NO2(g) versus

2 C8H18 (g) + 25 O2(g) → 16 CO2(g) + 18 H2O(g)

51
 14.5: Temperature and Rate

Collision Theory
Recall: Particle Theory:
• All matter is made of particles

• All particles are in constant (random) motion.

This means:
• Particles are continually bumping into one
another.

• Their collisions are “elastic” (no loss of

energy).

53
 Before any reactants can undergo a chemical change,
the reacting particles must have an effective collision.
A collision that results in a reaction is called an
effective collision.

Rate α number of collisions

second
Remember the Kinetic
Molecular Theory?

Particles are always in

motion.
 An effective collision requires:
1. A minimum energy called the threshold energy
(activation energy). This energy is required to
break the old bonds in the reactants and comes
from the kinetic energy of the colliding
molecules. H O
H H O O H O
H

H H H

4 covalent bonds to break 4 covalent bonds to make

Breaking a bond requires energy, and forming a bond releases energy.
2. Proper Collision Geometry. The colliding
molecules need to be oriented properly
otherwise they won’t necessarily react.
Therefore: NO2(g) + CO(g) → NO(g) + CO2(g)

This reaction will only occur when a molecule of NO2

collides with a molecule of CO with enough energy
(activation energy), and at the proper angle.
Activated Complex :
(transition state)

This is an unstable transition product consisting of

the atoms supplied by the colliding molecules.
Often the nature of an activated complex is
unknown because it is short-lived.
The transition state (activated complex) for the
reaction between H2O and HCl probably looks like
this.

In the transition state, the new O-H bond is partially

formed and the H-Cl bond is partially broken.
The atoms in the activated complex can regroup
to form products or can separate to reform the
reactants.
No reaction.

New products.
H2 + I2
activated
+
complex
The rate of a reaction will be changed by any
factor which changes the:

• collision rate (# of collisions/time)

• forcefulness of the collisions

• required activation energy

• required orientation
 Looking at a reaction:
e.g. 2C8H18(g) + 25 O2(g) → 16 CO2(g) + 18 H2O(g)

This balanced equation is the overall or net

equation.

It shows the relationship between the reactants and

products, but does NOT represent what really
happens as octane burns.
e.g. 2C8H18(g) + 25 O2(g) → 16 CO2(g) + 18H2O(g)

This net reaction shows that 27 molecules are

involved.

We now know that all 27 molecules won’t collide

at the same time, so the reaction must occur in a
series of simpler steps.
Usually collisions involve only 2 particles at a time.

*3-particle collisions do occur, but are rare.

A series of elementary steps (simple 2 – 3 particle

collisions) that represent the progress of the overall
reaction at the molecular level is referred to as a
reaction mechanism.
A reaction intermediate in a reaction
mechanism, is a product of an early step,
which becomes a reactant in a later step.

65
A catalyst can also be identified in a reaction
mechanism. It will appear first as a reactant,
but will be found as a product, un-altered, in
a later step.

66
The sum of all the steps in a reaction mechanism will equal
the net reaction.
Example 1: 2 NO(g) + O2(g) → 2NO2(g)
(3 reacting molecules) – this is not a single step reaction.
It needs to be broken down into 2-particle collisions.
A possible mechanism is:
Step 1: NO + NO → N2O2
N2O2
Step 2: N2O2 + O2 → 2NO2 (intermediate)

NO + NO + O2 → 2NO2

Each step has only 2 particles reacting (colliding).

If you add the steps together, you should get the
overall reaction.
 Example 2: 2 A + 2 B → 2 AB

Since this shows 4 particles as reactants we know this

will take a few steps to occur.
A possible reaction mechanism (using only 2 particles at
a time, of the 4 possible reactants):
A, A, B, B A2 B2 Note – intermediates appear as
a product then a reactant.
Step 1: A + A → A2 (not 2A) A2 + B2 are intermediates –
they are not products in the
Step 2: B + B → B2
final reaction.
Step 3: A2 + B2 → 2AB
Adding together we should get the
2 A + 2 B → 2 AB
overall.
Same Example: 2 A + 2 B → 2 AB
There exists another possible mechanism for the same
reaction:

Available reactants: A, A, B, B

Step 1: A + B → AB
Step 2: A + B → AB

Overall: 2 A + 2 B → 2 AB
H2(g) + 2ICl(g) → I2(g) + 2HCl(g)

(1) slow H2 + ICl → HI + HCl

(2) fast HI + ICl → I2 + HCl

70
 Example 4: 4HBr + O2 → 2 H2O + 2 Br2 slow

5 particles
This reaction mechanism is known and is as follows:
Step 1: HBr + O2 → HOOBr (a slow step) rate determining
Step 2: HOOBr + HBr → 2 HOBr (fast) step
Step 3: HOBr + HBr → H2O + Br2 (fast)
Step 4: HOBr + HBr → H2O + Br2 (fast)

This overall reaction would be slow even though there are 3

fast steps. The slowest step in a reaction mechanism is called
the rate determining step. (You can’t go faster than the
slowest step).
 What would be the rate-determining step in each of
the following?

clearing the table of dishes, washing them, drying them and

putting them away

raking vs. collecting the leaves

writing addresses on envelopes, folding letters, stuffing

letters sealing them, and stamping them
 The molecularity of a reaction is the number of
molecules reacting in an elementary step.
These molecules may be of the same or different
types.

Bimolecular (most common):

two molecules involved
A + B →…. 2A →….
Unimolecular: only one reacting molecule (C → )
Examples of Unimolecular Reactions:

The gas phase decomposition of ozone:

The gas phase decomposition of cyclobutane to ethylene:

74
Termolecular: very unlikely (3) (2A + B →)

• These are uncommon because the probability of three

particles colliding simultaneously is less than one one-
thousandth of the probability of two particles colliding.

Examples of Termolecular Reactions:

75
Which of the following reactions would be faster? Why?

H2(g) + I2(g) → 2 HI(g)

versus
Pb(NO3)2 (aq) + 2 NaI(aq)→ PbI2(s) + 2 NaNO3(aq)

2 NO(g) + O2(g) → 2 NO2(g)

versus
2 C8H18 (g) + 25 O2(g) → 16 CO2(g) + 18 H2O(g)
Recall the four main factors that affect the rate of a
reaction:

•concentration of the reactants

•the nature of the reactants (surface area, phase)

•the temperature of the reacting system

•the use of a catalyst

Let’s look at each of the factors and see why each of

these affect the rate of a reaction.
The Effect of Concentration:
In most cases, an increase in concentration will cause
an increase in reaction rate (a decrease in the required
time) by causing an increase in the chance for collisions
(less distance between particles).

78
Calculations based on the kinetic molecular theory
show that (at 1 atm and 298 K) there are 1 x 1027
binary collisions in 1.0 mL of volume every second in
the gas phase – even more occur in liquids.

Therefore, not all collisions are effective – if they were,

all reactions would be instantaneous.
The Effect of Pressure:
(similar to changing concentration of gases)
Changing the pressure on a reaction system
usually only affects the reaction rates of gas
phase reactions.

There are a few ways to change pressure:

• Add or remove some of the reactants/products

• Increase or decrease the size of the container

As particles get closer together (by pushing them into

a smaller space, or adding more particles), the
chance for an effective collision increase, so reaction
rate will increase.
Rank the diagrams below in order of expected reaction rate
for this reaction: G(g) + B(g)  GB(g)

Explain your ranking. Assume the same temperature in all

three reacting systems.
 The Effect of Temperature:
An increase in temperature increases the rate of almost
all chemical reactions.
*Approximately a 10oC rise in temperature doubles the
rate of the reaction (halves the time).

If a rate at 30oC takes 15 minutes, how long would it

take at 40oC ? Temperature increased, so rate gets faster. 10
degree change – time halves to 7.5 minutes.
How long would it take at 10oC ?
Temperature decreased (30 to 10), so rate gets slower. For the
first 10oC change time doubles to 30 minutes. It then doubles
again for the 2nd 10oC change, making it take 60 minutes.
83
Temperature is a measure of the average kinetic
energy (motion) of molecules in a sample (at constant
temperature).

As temperature increases the kinetic energy of the

molecules also increases. This causes the
molecules to move faster and collide more often.

The greater K.E. also increases the forcefulness of the

collisions, increasing their effectiveness (more
molecules achieve the required activation energy).

84
 The Effect of a Catalyst:
A catalyst is any substance that speeds up the rate of a
chemical reaction without itself being permanently altered.
e.g. platinum, manganese dioxide, copper (II) oxide

A catalyst speeds up a reaction by either:

• changing the reaction mechanism
to include steps with lower activation
energies. This allows more molecules
to effectively collide.
Or
•by improving the collision geometry.
85
86
Estimates are that 90% of all commercially produced
chemical products involve catalysts at some stage in
the process of their manufacture.

87
Catalysts may be
classified as
heterogeneous or
homogeneous.

Heterogeneous catalysts are those in which reactions are

limited to their surface area only.

Most heterogeneous catalysts are solids.

The most common are transition metals such as platinum or nickel.

Catalysts of this type undergo adsorption of reactants onto their

surface.

The catalyst energizes the reactants and holds them in a position

that allows easy interaction between them and other reacting
species.
Heterogeneous catalysis also occurs inside the exhaust system of
our automobiles. A device called a catalytic converter activates
several oxidation and/or reduction reactions.

Harmful pollutants such as carbon monoxide, a variety of

hydrocarbons, and nitrogen oxides are transformed into carbon
dioxide, water, and nitrogen gas.

The converter contains a series of honeycomb-patterned channels

lined with the catalyst, platinum. A number of other transition
metals may function as catalysts in a catalytic converter.
Catalysts which exist in the same phase as the rest of the
reaction system, are sometimes called homogeneous catalysts.

One of the most important catalysts in the world is

the enzyme, nitrogenase. Nitrogenase catalyzes the
life-sustaining process of nitrogen fixation.
 Look at the following mechanism: Identify the:

X + C → XC (1) Intermediate(s)?
Y + XC → XYC (2) Catalyst?
XYC → CZ (3) Overall reaction?
CZ → C + Z (4)

Indicate whether each of the following reactions involves heterogeneous or

homogeneous catalysis:

a) H2(g) + CH2CH2(g) Pt(s) CH3CH3(g) hydrogenation of ethylene

b) Chlorofluorocarbons (CFC(g)) catalyze the conversion of ozone (O3(g))

to oxygen O2(g).

c) 2H2O2(aq) MnO2(s) 2H2O (l) + O2(g)

The Effect of Surface Area: (nature of the reactant)
The more surface area available for the reaction,
the faster the reaction. (chance for more collisions)
For example, kindling ignites and burns faster than
a regular sized log.

Fires have occurred explosively in grain elevators and

coal mines where a fine dust has been suspended
throughout the air and ignited accidentally.
93
Look at the reaction between magnesium metal and dilute
hydrochloric acid: Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)

Hydrogen ions can hit

the outer layer of
atoms...

With the same number of

atoms now split into lots of
smaller bits, there are hardly
any magnesium atoms
which the hydrogen ions
can’t get at.
94
 14.3: The Differential Rate Law:
The effect of Concentration on Rate

One of the goals in kinetics is to derive an

equation that can be used to predict how a rate
of a reaction depends on the concentrations of
reactants.

This equation is called the RATE LAW or RATE

EQUATION.

95
 Consider: aA + bB → cC + dD
The x and y are exponents
Differential R = k[A]x[B]y: (Generally small
Rate Law: whole #’s)

proportionality
constant Reactants only.
Square brackets – concentration of….

Generally there is no relationship between the

exponents (x and y) and the molar coefficients (a and b)
in the balanced equation.

96
 The term order is used to describe a rate of reaction.

R = k[A]x[B]y:
If x =1, we say the reaction is first order with respect
to (w.r.t.) [A]. (R∝ A 1) (don’t need to write the one)
This means that if the concentration (of A) doubles
(e.g. from 1 M to 2 M) the rate also doubles. (21 = 2)

If the concentration (of A)triples (e.g. 2 M to 6M)

the rate triples (31 =3).
∆[ ]order = ∆ rate

97
 R= k[A]x[B]y: R = k[A]x[B]y

If y = 2, we say the reaction is second order w.r.t. [B].

This means that if the concentration (of B) is

doubled, the rate quadruples . [ ]y = R so 22 = 4.

If the concentration (of B) triples, the rate goes up

by 32 = 9.

The overall ORDER of the reaction is the sum of

all the exponents (x + y).

98
 Rate law = R = k[A]x[B]y:
k = proportionality constant or rate constant

• value depends on the reaction , the presence of

a catalyst, and temperature.
• its units depend on the order of the reaction.

• The larger the k, the faster the reaction

99
 e.g. R = k [ NO ] 1 [ O3 ] 1

Rate is first order w.r.t [NO]

Rate is also first order w.r.t [O3]

Reaction is (1 + 1) second order overall.

If concentration of one is doubled, reaction will

double. ∆[ ]1[ ]1 = ∆R, so [2]1[1] 1 = 2

But if the concentration of both are doubled, the

rate will quadruple. ∆[ ]1[ ]1 = ∆R, so [2]1[2] 1 = 4
100
**In one-step reactions, the coefficient(s) in the balanced
equation become the exponent.** In single step reactions
both reactants are involved in the rate determining step.

To recognize a single step reaction, count the # of reacting

particles – there should be only 2. If it is a termolecular
reaction occurring in a single step, it will say so.

For example: 2H2O2 → 2H2O + O2 R = k[H2O2]2

SO2Cl2 → SO2 + Cl2 R = k[SO2Cl2]1

H2O2 + 2HI → 2H2O (one-step) R = k [H2O2] [HI]2

101
If we know the reaction mechanism for a multi-step
reaction, the rate law is related to the reactants in
the slowest (rate determining step).

2 NO2 → NO3 + NO (slow)

NO3 + CO → NO2 + CO2 (fast)

R = k[NO2]2

102
Example : 4HBr + O2 → 2 H2O + 2 Br2

Known reaction mechanism:

Step 1: HBr + O2 → HOOBr (a slow step) **
Step 2: HOOBr + HBr → 2 HOBr (fast)
Step 3: HOBr + HBr → H2O + Br2 (fast)
Step 4: HOBr + HBr → H2O + Br2 (fast)

For this overall reaction, the rate law =

R = k[HBr][O2]

103
SUMMARY:

a. If the reaction is one step, the rate law is directly

related to the molar coefficients of the reactants
involved.
2A + B → C rate law = k[A]2[B]1

b. If the reaction mechanism for a multi-step

reaction is known, the rate law is determined by
the rate determining step (slowest step).

104
 Four Types of Rate Law Questions
•Write the rate law given a single step reaction or the
rate determining step.
e.g. 2 NO → N2O2

•Find the value of k.

e.g. What is the value of k if [NO] decreases at
0.50 M/min if it starts at 2.02 M?

k = R = = 0.50 M/min = 0.123 M-1min-1

[NO]2 [2.02 M]2 = 0.12 M-1min-1

105
 •Find R.
e.g. What is the rate if [NO] is 1.0 x 10-2 M?

R= k[NO]2 =

•Proportionality Questions
e.g. How does R vary if the [NO] is doubled?
Cut in half?
R α [NO]2

If [NO] is doubled: If [NO] is cut in half:

106
 Method of Initial Rates:
Determining Rate Order by Experiment

For most reactions there is more than one reactant.

Unless we know either the rate determining step, or
that the reaction is single-step, determination of the
rate order is a little more involved.

In these cases, the rate of the reaction is measured

at the beginning of the reaction (before the
concentrations have had time to change
significantly).
The initial concentration of only one reactant is then
changed, while all other initial concentrations are kept
constant, and the rate is measured again.

This procedure is repeated for each reactant, and

the initial rate is measured each time.

To determine the rate order, the change in

concentration for a reactant is compared to the
related change in reaction rate, during a trial where
all other reactant’s concentrations are unchanged.
 3 particles – not a single step reaction &
Example: mechanism isn’t given.

For the reaction: 2 NO(g) + Cl2(g) → 2 NOCl(g) the

following data was obtained at 300 K:
Experiment [NO] [Cl2] Rate (M/s)
1 0.010 0.010 1.2 x 10-4
2 0.010 0.020 2.3 x 10-4
3 0.020 0.020 9.6 x 10-4

The same experiment was started 3 different times, each time

keeping one reactant [ ] the same and changing the other.
We know that the rate law can be written as:
R =k [NO]x [Cl]y
 Experiment [NO] [Cl2] Rate (M/s)

1 0.010 0.010 1.2 x 10-4

2 0.010 0.020 2.3 x 10-4
∆[] ∆R
3 0.020 0.020 9.6 x 10-4

NO: When [Cl2] is kept constant (trials 2 and 3):

Looking at the ∆ [ ] of NO: Looking at the ∆ R of NO:
Trial 3 = 0.020 M = 2 Trial 3 = 9.6 x 10 -4 = 4.2 ≈ 4
Trial 2 0.010 M Trial 2 2.3 x 10-4
concentration doubled rate quadrupled
Recall: ∆ [ ]x = ∆ R Or – set up one equation:
2x = 4
X=2 0.020 X= 9.6 x 10 -4
X = order = log ∆ R = log 4 second 0.010 2.3 x 10-4
log ∆ [ ] log 2 order
This means that R α [NO]2
 Experiment [NO] [Cl2] Rate (M/s)
1 0.010 0.010 1.2 x 10-4
2 0.010 0.020
∆[ ]2.3 x 10-4 ∆R
3 0.020 0.020 9.6 x 10-4

Cl2 : When [NO] is kept constant (trials 1 and 2):

Looking at the ∆ [ ] of Cl2 : Looking at the ∆ R of Cl2 :
Trial 2 = 0.020 M = 2 Trial 2 = 2.3 x 10 -4 = 2
Trial 1 0.010 M Trial 1 1.2 x 10-4
concentration doubled
rate doubled
Recall: ∆ [ ]y = ∆ R Or – set up one equation:
2y = 2
Y = 1 (first order) 0.020 X= 2.3 x 10 -4
0.010 1.2 x 10-4
This means that R α [Cl2]1
 Putting them together:
R α [NO]2 R α [Cl2]1

R α [NO]2[Cl2]1

R = k [NO]2[Cl2]1

Overall order = Add the exponents = 2 + 1 = 3rd order

Knowing the rate law, we can now solve some other

questions:
1. What is the value of the rate constant at 300 K for the
following reaction?
2 NO(g) + Cl2(g) → 2 NOCl(g)
Rearranging:
We already know: R = k [NO] [Cl2]
2 1
k= R
[NO]2[Cl2]1

Experiment [NO] [Cl2] Rate (M/s)

1 0.010 0.010 1.2 x 10-4
2 0.010 0.020 2.3 x 10-4
3 0.020 0.020 9.6 x 10-4
Obtain values for your calculation using any experiment in your
data table (all values must come from the same row).
k= 1.2 x 10-4 M/s k = 120 M/s = 120 M-2s-1
(0.010 M)2(0.010 M)1 M3
2. At 300 K, what is the rate of the reaction when [NO] =
0.030 M and [Cl2] = 0.040 M ?

We already know: R = k [NO]2[Cl2]1

and k = 120 M-2s-1

Putting them together with the new information from

the question: R = (120 M-2s-1 )[0.030]2[0.040]1

R =0.0043 M/s
3. What happens to rate when [NO] is tripled and [Cl2] is
doubled?

R = k [NO]2[Cl2]1
Change this to a proportionality statement:
R α [NO]2[Cl2]1

Instead of putting in actual concentrations, put

in the change:
R α [3]2[2]1

R is 18 X the original rate

Note :
• if you change the concentration, but there is no
change in the rate (it stays the same), then the
reaction order is zero! (Very uncommon)

• you may have more than 2 trials from which to

choose your data for your calculations. Make sure
you choose the trials where only one substance
changes.
Differential and integral rate laws

Measuring instantaneous rates as we did for our colorimeter

lab is the most direct way of determining the rate law of a
reaction, but is not always convenient, and it may not even
be possible to do so with any precision.

• If the reaction is very fast, its rate may change more rapidly
than the time required to measure it; the reaction may be
finished before even an initial rate can be observed.

• In the case of very slow reactions, observable changes in

concentrations occur so slowly that the observation of a truly
"instantaneous" rate becomes impractical.

117
The differential rate law tells us how the rate of a reaction
depends on the concentrations of the reactants.

But for many practical purposes, it is more important to

know how the concentrations of reactants (and of products)
change with time.

For example, if you are carrying out a reaction on an

industrial scale, you would want to know how long it will
take for, say, 95% of the reactants to be converted into
products.

This is the purpose of an integrated rate law.

118
 14.4: The change of Concentration with Time
- Graphing and Integrated Rate Laws -
Recall: a zero order reaction (very rare):

A → products , R = -∆[A] / t = k rate =k

(units of k = M/s)
Graphing: rate is independent of any changes to concentration:
Rate vs. [ ] [ ] vs. t

119
There are two general conditions that can give
rise to zero-order rates:

Only a small fraction of the reactant molecules are in a location or

state in which they are able to react, and this fraction is
continually replenished from the larger pool.

When two or more reactants are involved, the concentrations of

some are much greater than those of others

120
Example: Decomposition of Nitrous Oxide

2N2O →2N2(g)+ O2(g)

This reaction, in the presence of a hot platinum wire (which acts as a catalyst),
is zero-order.

The N2O molecules that react are limited to those

that have attached themselves to the surface of the
catalyst. Once the sites are occupied, additional
molecules must wait until a site is free.

121
 We can transform the equation into a form that
relates the concentration of A at the start to its
concentration at any time in the reaction.

-∆[A] / t = k
-([A]t – [A]o) = kt
[A]t – [A]o = -kt
[A]t = -kt + [A]o
y = mx+b
*Graph of [A] vs t will give a straight line with slope -k
122
Half-life: the time needed for half of the reactant to be
depleted in a reaction.

For a zero-order reaction the half-life is given by:

[A]o = -kt1/2 + [A]o [A]o = -2kt1/2 + 2[A]o
2

t ½ = [A]o
2k

Or if a graph is drawn,
read the half-life from it.

123
Recall: a first order reaction (A → products) :
R = k[A]1 and rate = -∆[A]/t k = s-1

Graphing: rate depends on the reactant concentration (raised to a

power of one). Doubling the concentration, doubles the rate.

Rate vs. [ ] [ ] vs. time

124
125
Decay rate is dependent upon the number of
radioactive atoms, in terms of chemical kinetics, one
can say that radioactive decay is a first order reaction
process.

However, it is not affected by factors that alter a typical

chemical reactions. In other words, the reaction rate
does not depend upon the temperature, pressure, and
other physical determinants.

126
Using calculus and rearranging, the integrated rate
law becomes: y = mx + b
ln[A]t = -kt + ln[A]o

concentration concentration at
Watch units. start of reaction
at time t

*Graph of ln [A] vs t gives a straight line with a

slope of –k.
127
slope = -k

128
Example: The conversion of cyclopropane to propene in the
gas phase is a first-order reaction with a rate constant of 6.7 x
10-4 s-1 at 500oC.
a) If the initial concentration of cyclopropane was 0.25 M,
what is the concentration after 8.8 min.?
ln[A]t = -kt + ln[A]o = -(6.7 x 10-4)(528 s) + ln[0.25]
= 0.18 M
b) How long (in min.) will it take for the concentration of
cyclopropane to decreased from 0.25 M to 0.15 M?
ln[A]t = -kt + ln[A]o ln[.15] = -6.7x10-4t + ln[.25]
t = 13 min
c) How long would it take to convert 74% of the starting
material?
ln[.26] = -6.7x10-4t + ln[1]
ln[A]t = -kt + ln[A]o
t = 33 min
129
 Half Life for a first order reaction:

ln[0.5] = -kt + ln[1.0]

0.693 = -kt1/2 + 0
rearranging:
t1/2 = 0.693/k

*Notice that t1/2 does not depend on initial [reactant].

It takes the same time for 100g to go to 50g as for 0.1g

to go to 0.05g.
130
Example: The decomposition of ethane to methyl radicals is a
first order reaction with a rate constant of 5.36 x 10-4 s-1 at
700oC: C2H6(g) → 2CH3(g). Calculate the half life of the reaction
in minutes.

First order reaction: t1/2 = 0.693/k

t1/2 = 0.693/(5.36 x 10-4 s-1)

t1/2 =1.29 x 103 s (1 min/60 s)

t1/2 = 21.5 min

131
Recall: A second order reaction:
2A → products or A + B → products
R = k[A]2
Graphing: rate depends on the reactant concentration (raised to a
power of two). Doubling the concentration, quadruples the rate.
Rate vs. [ ] [ ] vs. time

132
 The integrated rate law is:

1_ = kt + 1_
[A]t [A]o
y = mx + b

*Graph of 1/ [A] vs t gives a straight line with a slope of +k.

133
 slope = k

Then you graph ln[ ] vs t…..

And still get a curve

134
Half-Life Expression for Second Order Reactions:

t1/2 = 1/k[A]0

*Note that half-life does depend

on initial concentration,
unlike first order reactions.

Each successive half-life is twice as long as the preceding

one. This type of half life problem is quite rare.

135
Examples: Iodine atoms combine to form molecular iodine in
the gas phase: I(g) + I(g)→ I2(g) This reaction follows second
order kinetics and has the high rate constant 7.0 x 109 M∙s at
23oC.
a) If the initial concentration of I was 0.086 M, calculate the
concentration after 2.0 min.
b) Calculate the half-life of the reaction if the initial concentration of I
is 0.60 M and if it is 0.42 M
a) 1_ = kt + 1_ 1_ = (7.0 x 109)(2 min)(60 s/min) + 1_
[A]t [A]o [A]t 0.086 M
[A]t = 1.2 x 10-12 M
b) t1/2 = 1/k[A]0 t1/2 = 1/(7.0 x 109)(0.60) =2.4 x 10-10 s
t1/2 = 1/(7.0 x 109)(0.42) = = 3.4 x 10-10 s
136
 To use graphing to determine reaction order, begin with a
[ ] vs. time graph, and proceed with other graphs (ln[ ] vs. t
then 1/[ ] vs t) until the points can be connected with a
straight-line.

137
One to try:
Ethyl iodide (C2H3I) decomposes at a certain temperature
in the gas phase as follows: C2H5I(g) → C2H2(g) + HI(g)

From the following data, determine the order of the reaction

and the rate constant:

Time (min) [C2H5I] M

0 0.36
15 0.30
30 0.25
48 0.19
75 0.13

138
 Not zero order
Time (min) [C2H5I] M ln [ ] 1/ [ ]
0 0.36 -1.02 2.78
15 0.30 -1.20 3.33
ln [ ] vs. time
30 0.25 -1.39 4
48 0.19 -1.66 5.26
75 0.13 -2.04 7.69
First order ?

First order

Not second order!

139
140
Time to work on Text Book practice
exercises and Rate Law questions.

141
Potential Energy Diagrams (P.E.D.s)

Potential energy diagrams can show the activation

energy (the energy needed to form the activated
complex) and the energy absorbed or released during a
reaction.

142
 An Exothermic Reaction:

required
activation Ea(r) -
P.E. of energy activation
reactants energy of the
start of forward reverse
reaction → reaction
← start of
reverse reaction end of
P.E. of forward
products reaction

∆H: Heat of reaction =

Ea(f) - activation
PEproducts – PE reactants
energy of the
∆H is negative for an forward reaction
exothermic reaction. 143
144
Another Example:

Eaf

Ear Exothermic
– products
∆H are lower.
(-)

The activation energy of a reaction dictates the

relative rate of a reaction. The higher the activation
energy the slower the reaction rate and vice versa.
145
An analogy for activation energy:

No
Ea reaction

reaction

The higher the hill (activation energy) the slower the

reaction.
146
Endothermic Reactions require energy because the
products have lower KE's (and higher PE's) than the
reactants:

Ear
Eaf

∆H
(+)

Larger activation energy (bigger hill) so this would be a

slower reaction.
147
 A potential energy diagram can be drawn for multi-
step reactions too. This is a P.E.D. for a three step
reaction.

Highest energy
– the last step is
the RDS.

The rate determining step is not the one with the highest
activation energy for the step. The rate determining step
is the step whose transition state has the highest energy.
148
Catalysis : recall, a catalyst speeds up a reaction
without being present in the overall balanced
equation.

It does this by providing an alternate mechanism for

the reaction that has a lower activation barrier than
does the uncatalyzed pathway.

149
No change

150
151
Compare the catalytic and regular mechanisms for the
hydrogenation of ethylene to ethane and their
associated reaction coordinate diagrams in :

152
 One step -
uncatalyzed

Ea

Two steps -
catalyzed

Eac
Same heat of
reaction.
catalyst

153
154
155
Draw an energy diagram for a two-step reaction
that is exothermic overall, and consists of a fast but
endothermic first step, and a slow but exothermic
second step.

156
Kinetic Energy (Maxwell Boltzman) Distribution Curves:
Every particle of a gas is in motion, and therefore possesses
kinetic energy.

The Maxwell-Boltzmann distribution shows how many

particles in a gas have the different speeds.

i.e. Kinetic Energy 157

For a reaction to take place, molecules must collide with
sufficient energy to create a transition state.

This usually only happens for the fastest molecules, so if the

Maxwell-Boltzmann distribution tells us how many molecules
have energies or speeds above a certain level, that will be
useful to us.
At a given temperature, only
these molecules with a
minimum energy will react.

Ea Kinetic 158
The Effect of Temperature:

Value for Ea does

not change, but
the distribution
curve will shift left
or right depending
on temp. changes.

Ea
At a higher temperature, more molecules have higher
kinetic energies. Thus, a larger fraction will have the
required activation energy to undergo a reaction.
159
This is a more accurate representation of how the
kinetic energy changes with temperature.

As temperature increases, the curve will spread to the

right and the value of the most probable kinetic energy
will decrease.
160
When a catalyst is added, the required Ea is
lowered, increasing the number of particles with
enough energy to react.

Eac Ea

161
In 1899, the Swedish chemist Svante Arrhenius
(1859-1927) combined the concepts of activation
energy and the Boltzmann distribution law into one of
the most important relationships in physical chemistry:

The Arrhenius Equation

Arrhenius noted that, for most reactions, the increase in

rate with increasing temperature was nonlinear.

162
He found that most reaction rate data obeyed an equation
based on 3 factors:

a) the fraction of molecules having enough activation energy

b) the number of collisions per second

c) the fraction of collisions that have the appropriate

orientation.

163
 Base of the
natural Temperature
logarithm (K)
(Euler’s No.)

The Arrhenius Equation: k = Ae –Ea/RT

rate constant
frequency
# of collisions factor universal gas
activation
that result (constant) constant
energy (J)
8.314 J/mol-K
# of collisions
with proper
orientation

The probability that any given

collision will result in a reaction.

164
Using the Arrhenius equation:

You can use the Arrhenius equation to show the effect of a change
of temperature on the rate constant - and therefore on the rate of
the reaction.

What happens if you increase the temperature by 10°C from, say, 20°C
to 30°C (293 K to 303 K)?

The frequency factor, A, in the equation is approximately constant for

such a small temperature change.

We need to look at how e (EA /RT) changes - the fraction of molecules with
energies equal to or in excess of the activation energy.

165
 Let’s assume an activation energy of 50 kJ/mol.

At 20oC (293 K) the value of the fraction is:

e - EA / RT = e - 50 000Jmol-1/ (8.31 JK-1mol-1)(293 K)

= 1.21 x 10-9

By raising the temperature just a little bit (to 303 K), this increases:

e - EA / RT = e - 50 000Jmol-1/ (8.31 JK-1mol-1)(303 K)

= 2.38 x 10-9
You can see that the fraction of the molecules able to react has almost
doubled by increasing the temperature by 10°C. That causes the rate of
reaction to almost double.
166
The Arrhenius Equation: k = Ae –Ea/RT

Taking natural logs of both sides and rearranging:

ln k = ln Ae –Ea/RT
ln k = ln A –Ea/RT

This can be rearranged into a

linear equation:

ln k = - Ea 1 + ln A
R T
y = m x +b
This means that a plot of ln k vs 1/T gives a straight
line whose slope m is equal to -Ea/R. Graphically we
can determine the activation energy of a reaction.
167
Example: Use the following data to determine the activation
energy for the decomposition of HI:
Temperature Rate Constant
(K) 1 / T (M/s) ln k
573 0.00175 2.91 x 10-6 -12.7
673 0.00149 8.38 x 10-4 -7.08
773 0.00129 7.65 x 10-2 -2.57

Graph ln k vs 1/T:

168
Determine slope (= -Ea/R)

Slope: ∆y / ∆x
-4 /1.8 x 10-4
= - 2.2x104

- 2.2x104 = -Ea/R
- Ea = (8.314 J/K mol)(-2.2x104 K) = -1.83 x105
Ea = 183 kJ/mol
169
170
Using Arrhenius’ Equation, we can derive an equation
that relates two different rate constants (k1 and k2) at
two different temperatures (T1 and T2), in order to find k
at another temperature or to find activation energy.

ln k1 - ln A = -Ea/RT1 ln k2 - ln A = -Ea/RT2

Subtracting ln k2 from ln k1:

ln k1 - ln k2 = Ea 1 - 1
R T 2 T1

ln k1 = Ea 1 - 1
k2 R T2 T1

171
Using our previous questions, calculate the rate
constant for the decomposition of HI at 600°C.
Temperature Rate Constant (k)
ln k1 = Ea 1 - 1 (K) (M/s)
573 2.91 x 10-6
k2 R T2 T1 673 8.38 x 10-4
773 7.65 x 10-2

Choose any line for k and T T1 = 573 k1 = 2.91 x 10-6

From the question, T2 = 600 + 273 = 873 K

ln 2.91 x 10-6 = 183 000 J/mol 1 - 1_

k2 (8.314 J/K mol) 873 573

k2 = 1.57 M/s
172
 That’s it for Chapter 14.

Work on Textbook practise exercises,

review questions, and then go and
try the AP Classroom assignments.

173