Chemical Dynamics

CHEM 1001

Chapter 13
Chemical Kinetics

Winter 2025
1
In this chapter you will learn…
• How to calculate concentrations of reactants and products at
different times during a reaction

• How to use the information on reaction kinetics to understand the

molecular steps involved in a reaction (reaction mechanism)

• How temperature affects the rate of chemical reactions

• How chemical reactions can be accelerated by special substances

called catalysts

2
The rate of a chemical reaction
• Rate (speed) of a process is a change in some quantity with
respect to time
• Example: speed of a car:

Δt

3
Δx
iClicker Question
If the initial value of something is larger than the final value of
something, will its Δ be:

A) POSITIVE

B) NEGATIVE

4
The rate of a chemical reaction

5
The rate of a chemical reaction
Let’s consider the following reaction: H2 (𝑔) + I2 (𝑔) 2 HI(𝑔)

In terms of the reaction itself,

Δ[H2 ] [H2 ]t2 – [H2 ]t1

𝑟𝑎𝑡𝑒 = − = –
Δ𝑡 t 2 – t1
Why is there a negative sign?

What are the units for reaction rate?

6
The rate of a chemical reaction
Let’s consider the following reaction: H2 (𝑔) + I2 (𝑔) 2 HI(𝑔)

Reaction rate can be expressed using any reactant or product:

Δ I2 1 Δ[HI]
𝑟𝑎𝑡𝑒 = − =
Δ𝑡 2 Δ𝑡
Why is there no “-” sign on the right hand side?

Why is there a “1/2” term for the HI?

7
The rate of a chemical reaction
A graphical representation
of this reaction:

8
The rate of a chemical reaction
Summary so far:
• Reaction rate can be expressed using any reactant or product
• Reaction rate is always positive
• The value of reaction rate is independent of which reactant or
product was used in the calculation
• Rates of change of concentration of individual components can be
calculated from the reaction rate value

• Reaction rates can change over the course of a reaction

9
The rate of a chemical reaction
In other words…

𝑎A + 𝑏B 𝑐C + 𝑑D

1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[D]

𝑟𝑎𝑡𝑒 = − =− = + = +
𝑎 Δ𝑡 𝑏 Δ𝑡 𝑐 Δ𝑡 𝑑 Δ𝑡

10
Let’s work a problem
Consider the following reaction:

In the first 10 seconds of the reaction, [I-] drops 1.000 mol L-1 to 0.868 mol L-1.
a) Calculate the average rate of reaction over this time interval
b) Determine the rate of change in concentration of [H+] over the same time
interval

11
Let’s work a problem
(additional space)

12
Instantaneous vs. average reaction rate
• So far, all reaction rates calculated have been averages over a
finite time interval

• Average rate, slope

of secant line (red)

• Instantaneous rate,
slope of tangent line (blue)

• Instantaneous rate is related

to the rate law of the reaction
13
Measuring reaction rates
• To measure reaction rates, accurate measurements of
concentration over time must be made
• Various experimental methods exist to measure concentrations of
compounds depending on molecular structure
• Some methods based on the absorption of light

14
iClicker Question
Some methods of measuring reaction rates are less technical. If the
following reaction proceeds in a sealed container…

2 N2O(g) → 2 N2(g) + O2(g)

will the pressure

A) Increase
B) Decrease
C) Stay the same

15
The rate law
• In the H2 + I2 → 2 HI example, we saw the reaction rate decreased
as the reaction progressed (this is quite common)

• Relationship between reaction rate and

reactant concentrations is the rate law

• Rate law has the form

rate = k[H2]m[I2]n

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The rate law
• Any general reaction has a rate law of the form rate = k[A]m[B]n….
where concentrations of all reactants are raised to a power

• Powers m, n, etc. are the reaction orders with respect to that

reagent and can be 0, a positive number or a negative number

• Reaction orders generally DO NOT correspond to reaction

stoichiometry and must be determined by experiment

• k is the rate constant and units will vary depending on the reaction
orders
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iClicker Question
If rate = k[A]2 , what are proper units of k?

A) mol L-1
B) mol L-1 s-1
C) mol-1 L s-1
D) mol-1 L-1 s

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Common rate laws
For the simple reaction A → products

• Zero-Order Reaction:

• First-Order Reaction:

• Second-Order Reaction:

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Common rate laws

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Determining rate laws
• Rate laws can be determined experimentally using method of initial rates
Example: Consider A → products
• Rate of reaction is measured at the very start of the reaction at a particular
initial concentration of A
[A] (mol L−1) Initial Rate (mol L−1 s−1)

0.10 0.015

0.20 0.030

0.40 0.060

• What is the reaction order with respect to [A]? What is k?

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Determining rate laws
• IF the reaction was [A] (mol L−1) Initial Rate (mol L−1 s−1)
zero-order with respect to [A] 0.10 0.015
0.20

0.40

[A] (mol L−1) Initial Rate (mol L−1 s−1)

• IF the reaction was 0.10 0.015
First-order with respect to [A] 0.20

0.40

[A] (mol L−1) Initial Rate (mol L−1 s−1)

• IF the reaction was 0.10 0.015
Second order with respect to [A] 0.20

0.40
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Determining rate laws
What if you have trouble derive the reaction order by simple inspection?
[A] (mol L−1) Initial Rate (mol L−1 s−1)
A more mathematical approach, 0.10 0.015
take any two experiments and go 0.15 0.034
through the following steps: 0.40 0.240

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Determining rate laws
If a reaction has multiple reactants, reaction order must be determined
experimentally for all reactants

𝑎A + 𝑏B 𝑐C + 𝑑D
rate = k[A]m[B]n

• Remember, m and n do not generally relate to “a” and “b”

• m + n is called the overall reaction order
Example:
H 2 (g ) + 2 NO (g ) ⎯⎯
→ N 2 (g ) + 2 H 2O(g ) Rate = k[H 2 ][NO ]2

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Determining rate laws
For the following reaction:
𝑁𝑂2 + 𝐶𝑂 → 𝑁𝑂 + 𝐶𝑂2
the following initial rate data was observed:

What is the rate law for the reaction? What is k?

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Determining rate laws
(additional space)

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iClicker Question
(additional space)

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Integrated rate laws
Consider A → products

• So far, rate laws have been in differential form,

𝑚
∆𝐴
𝑟𝑎𝑡𝑒 = 𝑘 𝐴 =−
∆𝑡

• Now consider the integrated rate law

𝐴 =𝑓 𝑡
− Allows us to find [A] at any timepoint t
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Integrated rate laws
• Removal of
harmful CFCs from the
atmosphere is a first
order kinetic process

• CFC concentrations
in the future can be
predicted by integrated
rate laws

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First order integrated rate law
A ⎯⎯
→ products rat e = k[A]
The integrated raw law is:

ln[A]𝑡 =– 𝑘𝑡 + ln[A]0

or can be written as:

[A]𝑡
ln =– 𝑘𝑡
[A]0

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First order integrated rate law
Plotting ln [A] vs. t will give a straight
line if the reaction is first order

ln[A]𝑡 =– 𝑘𝑡 + ln[A]0
(why would you do this???)

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iClicker Question
For a first order reaction, what is the nature of the slope of a plot of
ln[A]t vs. t?

A) Always a positive slope

B) Always a negative slope
C) Could be a positive slope or a negative slope

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First order integrated rate law
Plotting ln [A] vs. t will give a straight
line if the reaction is first order

ln[A]𝑡 =– 𝑘𝑡 + ln[A]0
(why would you do this???)

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First order integrated rate law
Here’s some real data for the decomposition of SO2Cl2:
𝑆𝑂2 𝐶𝑙2 → 𝑆𝑂2 + 𝐶𝑙2

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First order integrated rate law
Trying a plot of ln [SO2Cl2] vs. t gives a straight line, confirming the reaction is
first order with respect to SO2Cl2

What is k?

35
Let’s work a problem
In the previous example, we know rate = k[SO2Cl2] and k = 2.90 x 10-4 s-1

If the initial concentration of SO2Cl2 was 0.0225 mol L-1 , what is [SO2Cl2] after
14.42 minutes?

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iClicker Question
Sometimes you may be given percentages of a reactant instead of absolute
concentrations.

In the first order reaction A ⎯⎯

→ products rat e = k[A]
If 75% of reactant A has been consumed at time t, what is the value
𝐴𝑡
of ln ?
𝐴0

A) ln (0.50) C) ln (0.25)
B) ln (4.00) D) ln (0.75)

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Second order integrated rate law

A products rat𝑒 = 𝑘[A]2

The integrated raw law is:

1 1
= 𝑘𝑡 +
[A]𝑡 [A]0

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Second order integrated rate law
Plotting 1/[A]t vs. t will give a straight
line if the reaction is second order
1 1
= 𝑘𝑡 +
[A]𝑡 [A]0
(why would you do this???)

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Second order integrated rate law
Here’s some real data for the decomposition of NO2:
𝑁𝑂2 → 𝑁𝑂 + 𝑂

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Second order integrated rate law
Trying a plot of 1/[NO2] vs. t gives a straight line, confirming the reaction is
second order with respect to NO2

What is k?

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Zero order integrated rate law
A ⎯⎯
→ products r ate = k[A] = k
0

The integrated rate law is:

[A]t = −kt + [A]0

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Zero order integrated rate law
Plotting [A] vs. t will give a straight
line if the reaction is zero order

[A]t = −kt + [A]0

(why would you do this???)

43
Half life of a reaction
• t1/2 is the time taken for the concentration of a reactant to decrease
to half its original value

• Seen often in nuclear science (ex: half life of 235U = 704 million
years) but also applies to chemical reactions as well

• For the simple reaction A products , what is the half life

exactly?

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Half life of a reaction
• If A products has a first order rate law, how do we calculate
t1/2?

Start with ln[A]𝑡 =– 𝑘𝑡 + ln[A]0

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Half life of a reaction

46
iClicker Question
If the first order reaction A products has [A]0 = 0.300 mol L-1 and
has a half life of 25 minutes, what is the concentration of A (in mol L-1) after 50
minutes?

47
Quick note about lifetime
• Related to half life is the lifetime of a compound (τ)
• In a first order reaction, lifetime is time needed to decrease to 1/e
(~37%) of the original amount

• Our textbook mentions it, it won’t be tested in this course but be aware of
it

48
Half life of a reaction
• If A products has a second order rate law, how do we
calculate t1/2?
1 1
Start with = 𝑘𝑡 +
[A]𝑡 [A]0

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Half life of a reaction
• If A products has a zero order rate law, how do we calculate
t1/2?

Start with [A]t = −kt + [A]0

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iClicker Question
• In a zero order reaction, do you expect the half life to increase or
decrease over time as the reaction proceeds?

A) Increase

B) Decrease

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Summary of rate laws

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iClicker Question
A decomposition reaction, with a rate that is observed to slow down as the
reaction proceeds, is found to have a half-life that depends on the initial
concentration of the reactant. Which of the following is most likely to be true of this
reaction?

A) A plot of the natural log of the concentration of the reactant as

a function of time will be linear

B) The half-life of the reaction increases as the initial as the initial

concentration increases

C) A doubling of the initial concentration of the reactant results in

a quadrupling of the rate
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Effect of Temperature on Reaction Rate
• The rate of most chemical reactions increases at higher temperature
• The rate law does not have an explicit temperature term
• The value of the rate constant is temperature-dependent

• Arrhenius equation relates temperature to rate constant

ALWAYS positive!

ALWAYS positive!
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iClicker Question
What is the relationship between rate constant and activation energy?

𝐸𝑎
−
𝑘= 𝐴𝑒 𝑅𝑇

A) As Ea increases, k increases
B) As Ea increases, k decreases
C) There is no relationship between the two terms

55
Reaction Coordinate Diagrams
Ex: 2 H2 + O2 → 2 H2O
The reacting species
(e.g. molecules) must
cumulatively possess
at least the amount of
energy equal to Ea for
the reaction to take place.

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Reaction Coordinate Diagrams
Consider the isomerization reaction from methyl isocyanide
to produce acetonitrile

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The Activated Complex

• CANNOT be isolated
• Is not a stable chemical
species

58
iClicker Question
What is the sign of ΔH in this reaction overall?

A) ΔH < 0
B) ΔH = 0
C) ΔH > 0

59
Frequency factor vs. exponential factor
𝐸𝑎
−
𝑘= 𝐴𝑒 𝑅𝑇

• The frequency factor (A) is the number of times the activated

complex configuration is approached per unit time

• The exponential factor is always between 0 and 1 (no units),

represents the fraction of atoms/molecules that have energy equal
to or greater than Ea

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Exponential Factor
• Atoms/molecules have energy distributions that are dependent on
temperature

• If Ea is low and/or T is high

• If Ea is high and/or T is low

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Arrhenius Plots
• How can Ea be determined from experimental data?

• First, transform the Arrhenius equation into a more workable form

𝐸𝑎
−𝑅𝑇
𝑘 = 𝐴𝑒

𝐸𝑎
ln 𝑘 = ln 𝐴 −
𝑅𝑇

𝐸𝑎 1
ln 𝑘 = − + ln 𝐴
𝑅 𝑇
62
Arrhenius Plots

63
Arrhenius Plots
Plotting ln k vs. 1/T gives
the graph on the right
How to find Ea?

How to find A?

64
Two-Point Form of Arrhenius Equation
• Another way to find Ea – measure k at just two temperatures and
use the following method:
𝐸𝑎 1 𝐸𝑎 1
ln 𝑘1 = − + ln 𝐴 ln 𝑘2 = − + ln 𝐴
𝑅 𝑇1 𝑅 𝑇2

𝐸𝑎 1 𝐸𝑎 1
ln 𝑘2 − ln 𝑘1 = − + ln 𝐴 − (− ( ) + ln 𝐴 )
𝑅 𝑇1 𝑅 𝑇2

𝑘2 𝐸𝑎 1 1
ln =− ( − )
𝑘1 𝑅 𝑇2 𝑇1

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Let’s work a problem
For a reaction, the rate constant at 701 K is 2.57 M-1 s-1 and at 895 K the rate
constant is 567 M-1 s-1. What is the activation energy in kJ/mol?

66
The Collision Model
• If most chemical reactions result from molecular collisions, we can
examine frequency factor “A” more closely

• Composed of two terms: orientation factor and collision frequency

𝐸𝑎
𝑘= 𝐴𝑒 −𝑅𝑇

𝐸𝑎
−
𝑘= 𝑝𝑧𝑒 𝑅𝑇

• Collision frequency (z) tends to be very high

67
Orientation Factor
• Consider the reaction between 2 NOCl to produce 2 NO and Cl2:

• p = 0.16 but why?

68
Orientation Factor
• Only 16% of all collisions occur in the proper orientation for the
reaction to produce products

69
iClicker Question
• What is p for the following reaction?

𝐼 𝑔 + 𝐶𝑙 𝑔 → 𝐼𝐶𝑙 (𝑔)

A) ~ 0
B) ~ 0.5
C) ~ 1

70
Orientation Factor
• Some reactions of larger organic molecules have much smaller
values of p:

H 2 ( g ) + H 2 C=CH 2 ( g ) ⎯⎯
→ CH 3 –CH 3 ( g ) p = 1.7 10 −6

• Some reactions can have p > 1 by a “harpoon” mechanism

K ( g ) + Br2 ( g ) ⎯⎯
→ KBr ( g ) + Br ( g ) p = 4.8

71
Reaction Mechanisms
• Most of the time, balanced chemical equations simply describe
reactants and products but no intermediate steps are evident:

H 2 (g ) + 2 ICl (g ) ⎯⎯
→ 2 HCl ( g ) + I 2 ( g )

• Overall reaction may not correspond to the individual steps on the

molecular scale by which the reaction occurs (the mechanism)

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Reaction Mechanisms
• This is a possible reaction mechanism for the reaction between H2
and 2 ICl:

Step 1 H 2 (g ) + ICl (g ) ⎯⎯ → HCl ( g ) + HI ( g )

Step 2 HI (g ) + ICl (g ) ⎯⎯ → HCl ( g ) + I 2 ( g )
Overall Rxn H 2 (g ) + 2 IC l (g ) ⎯⎯→ 2 HCl ( g ) + I 2 ( g )

• Each step describes an elementary reaction/step

• What is the role of HI?

73
Rate Laws for Elementary Steps
• Elementary steps are characterized by their molecularity (number
of molecules that come together)
• By far the most common are unimolecular and bimolecular steps:

A ⎯⎯
→ products unimol ec ular
Common
A + A ⎯⎯
→ products bimo lecular
molecularities
A + B ⎯⎯
→ products bimo lecular

Termolecular reaction.
A + B + B → products Very uncommon. WHY?
74
Rate Laws for Elementary Steps
• If a reaction is known to be elementary, then its rate law follows the
reaction stoichiometry:
Elementary Step Molecularity Rate Law
A → products 1 Rate = k[A]

A + A → products 2 Rate = k[A]2

A + B → products 2 Rate = k[A][B]

75
Rate Determining Step
• In a multi-step chemical reaction, the slowest step is known as the
rate determining (or limiting) step

• Sometimes called the “reaction bottleneck”

76
Rate Determining Step
• The rate of the rate-determining step is generally proportional to the
rate of the entire overall reaction

• Consider the following reaction:

NO 2 (g ) + CO (g ) ⎯⎯
→ NO(g ) + CO 2 ( g )

observed rate law: rate = k[NO 2 ] 2

• How do we know the overall reaction doesn’t proceed in one step?

77
Rate Determining Step
• Here’s a proposed mechanism for this reaction:

Step 1 ⎯⎯
NO 2 ( g ) + NO 2 ( g ) ⎯
k1
→
⎯ NO3 ( g ) + NO( g )
k −1

Step 2 NO3 ( g ) + CO( g ) ⎯⎯

k2
→ NO 2 ( g ) + CO 2 ( g )
Overall Rxn N O 2 ( g ) + CO( g ) ⎯⎯
→ NO( g ) + CO 2 ( g )

• If we are provided with a reaction coordinate diagram of the

reaction, we can determine which step is rate determining

78
A Possible Reaction Mechanism
So which step is likely to be
rate determining?

79
A Possible Reaction Mechanism

Step 1 ⎯⎯
NO 2 ( g ) + NO 2 ( g ) ⎯
k1
→
⎯ NO3 ( g ) + NO( g )
k −1

Step 2 NO3 ( g ) + CO( g ) ⎯⎯

k
→
2
NO 2 ( g ) + CO 2 ( g )
Overall Rxn N O 2 ( g ) + CO( g ) ⎯⎯
→ NO( g ) + CO 2 ( g )

• If step 1 is the slow rate determining step, then

𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 = 𝑘 𝑁𝑂2 2

… which matches experimental data!

80
iClicker Question
If a proposed reaction mechanism gives the overall reaction
stoichiometry when all the steps are added

AND

If the rate law arising from the proposed mechanism matches the
experimental rate law then…

A) The reaction mechanism is completely proven

B) The reaction mechanism is not completely proven

81
Steady State Approximation
• If we are not given a reaction coordinate diagram, or told which step is the
slowest, then the SSA is a way to solve for a very general rate law from a
proposed mechanism

Step 1 ⎯⎯
NO 2 ( g ) + NO 2 ( g ) ⎯
k
→
⎯
1
NO3 ( g ) + NO( g )
k −1

Step 2 NO3 ( g ) + CO( g ) ⎯⎯

k
→ 2
NO 2 ( g ) + CO 2 ( g )
Overall Rxn N O 2 ( g ) + CO( g ) ⎯⎯
→ NO( g ) + CO 2 ( g )

• Trick: express rate in terms of an irreversible product formation (CO2)

Δ[CO2 ]
𝑟𝑎𝑡𝑒 = = 𝑘2 [NO3 ][CO]
Δ𝑡
82
Steady State Approximation
• We need to eliminate NO3 from our rate law expression since it’s not a reactant
we can easily measure
• Steady state approximation: throughout most of the reaction, the concentration
of NO3 should remain constant

83
Steady State Approximation
• rate of production of NO3 = rate of loss of NO3

Step 1 ⎯⎯
NO 2 (g ) + NO 2 ( g ) ⎯ → NO3 ( g ) + NO( g )
⎯
k −1

Step 2 NO3 (g ) + CO (g ) ⎯⎯
k
→ NO 2 ( g ) + CO 2 ( g )
2

• rate of production of NO3:

• rate of loss of NO3

84
Steady State Approximation
• Hence, using SSA:

k1[NO 2 ]2 = k−1[NO3 ][NO] + k2 [NO 3 ][CO]

• Isolate and solve for [NO3]

2
k1[NO 2 ]
[N O3 ] =
k−1[NO] + k2 [CO]

85
Steady State Approximation
• Substitute for [NO3] in the general rate law expression:

Δ[CO2 ]
𝑟𝑎𝑡𝑒 = = 𝑘2 [NO3 ][CO]
Δ𝑡

𝑘1 𝑘2 [NO2 ]2 [CO]
𝑟𝑎𝑡𝑒 =
𝑘−1 [NO] + 𝑘2 [CO]

• This is the “general-case” rate law, complicated but may be simplified under
certain “limiting cases”

86
Steady State Approximation
Step 1 ⎯⎯
NO 2 ( g ) + NO 2 ( g ) ⎯
k1
→
⎯ NO3 ( g ) + NO( g )
k −1

Step 2 NO3 ( g ) + CO( g ) ⎯⎯

k
→
2
NO 2 ( g ) + CO 2 ( g )
Overall Rxn N O 2 ( g ) + CO( g ) ⎯⎯
→ NO( g ) + CO 2 ( g )
• What if step 2 is MUCH faster than step 1?
• That would imply k2 is very large and/or [CO] is very high

𝑘1 𝑘2 [NO2 ]2 [CO]
𝑟𝑎𝑡𝑒 =
𝑘−1 [NO] + 𝑘2 [CO]

87
Steady State Approximation
Step 1 ⎯⎯
NO 2 ( g ) + NO 2 ( g ) ⎯
k1
→
⎯ NO3 ( g ) + NO( g )
k −1

Step 2 NO3 ( g ) + CO( g ) ⎯⎯

k
→
2
NO 2 ( g ) + CO 2 ( g )
Overall Rxn N O 2 ( g ) + CO( g ) ⎯⎯
→ NO( g ) + CO 2 ( g )
• What if step 2 is MUCH slower than step 1?
• That would imply k2 is very small and/or [CO] is very low

𝑘1 𝑘2 [NO2 ]2 [CO]
𝑟𝑎𝑡𝑒 =
𝑘−1 [NO] + 𝑘2 [CO]

88
When to use SSA

89
Catalysis
POPULAR DEFINITION #1

“A catalyst is a substance that speeds up a chemical reaction without

taking part in it”

POPULAR DEFINITION #2

“A catalyst lowers the activation energy barrier for the chemical

reaction”

90
Catalysis

91
Catalysis
• Ozone depletion is catalyzed by chlorine atoms

Step 1 Cl ( g ) + O3 ( g ) ⎯⎯
→ C lO ( g ) + O 2 ( g )
Step 2 ClO ( g ) + O( g ) ⎯⎯
→ Cl ( g ) + O2 ( g )
Overall Rxn O3 ( g ) + O( g ) ⎯⎯
→ 2 O2 ( g )

• Cl is needed at the start of the reaction but is regenerated at the

end

• Where do the chlorine atoms come from?

92
Catalysis
• Catalytic converter in automobile exhaust systems
2 NO( g ) + 2 CO( g ) ⎯⎯⎯
catalyst → N 2 ( g ) + 2 CO 2 ( g )

CH 3CH 2 CH 3 ( g ) + 5 O 2 ( g ) ⎯⎯⎯
catalyst → 3 CO 2 ( g ) + 4 H 2 O(g)

93
Catalysis
• Homogeneous vs. heterogeneous catalysts

94
iClicker Question
Catalytic converters are examples of what type of catalyst?

A) Homogeneous catalyst
B) Heterogeneous catalyst

95
Heterogenous Catalysts
Example: Hydrogenation of Olefins

96
Enzymes: Biological Catalysts
• The majority of the tens of thousands of chemical reactions that occur in living
cells are too slow at normal temperatures

• Enzymes are large molecules (proteins or RNA) that act as homogeneous

catalysts

• Enzymes have complex three-dimensional structures optimized for a particular

reaction

• Enzymes provide an alternative mechanism for the biological reaction that is

rate-enhanced

• Some enzymes can speed up the reactions by a factor of 109!

97
Enzymes: Biological Catalysts
• Most enzymes require binding of substrate to the active site for
catalysis to occur
E +S ⎯⎯
⎯ →
k1
⎯ ES ⎯⎯
k
→
2
E+P
k −1

98
Enzymes: Biological Catalysts
• Example: sucrose binds to active site of sucrase to facilitate
hydrolysis into glucose and fructose

99
Enzyme Kinetics
• Consider the following plots of initial reaction rate vs. [sucrose]

100
Enzyme Kinetics
• Michaelis-Menten enzyme kinetics can be used to explain the
dependence on reaction rate vs. [S]

E +S ⎯⎯
⎯ →k1
⎯⎯
→ E+P
k ⎯
k2
ES
−1

E +S ⎯⎯
⎯ →k1
⎯⎯
→ E+P
k ⎯
k2
ES
−1

𝑟𝑎𝑡𝑒 = 𝑘2 [𝐸𝑆]
101
Enzyme Kinetics
Using steady state approximation for ES

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐸𝑆 = 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑙𝑜𝑠𝑠 𝑜𝑓 𝐸𝑆

𝑘1 𝐸 𝑆 = 𝑘−1 𝐸𝑆 + 𝑘2 [𝐸𝑆]

We know total enzyme concentration [E]0

𝐸 0 = 𝐸 + 𝐸𝑆

𝐸 = 𝐸 0 − [𝐸𝑆]
102
Enzyme Kinetics
Substitute in for [E] to obtain

𝑘1 ( 𝐸 0 − 𝐸𝑆 ) 𝑆 = 𝑘−1 𝐸𝑆 + 𝑘2 [𝐸𝑆]

𝑘1 𝐸 0 𝑆
𝐸𝑆 =
𝑘1 𝑆 + 𝑘2 + 𝑘−1

Divide numerator and denominator by k1

𝐸0𝑆
𝐸𝑆 =
𝑘2 + 𝑘−1
𝑆 +
𝑘1
103
Enzyme Kinetics
Define a new term, the Michaelis constant (KM)

𝑘2 + 𝑘−1
𝐾𝑀 =
𝑘1

𝐸0𝑆
𝐸𝑆 =
𝑆 + 𝐾𝑀

Now, substitute in for rate = k2[ES]

𝑘2 𝐸 0 𝑆
𝑟𝑎𝑡𝑒 =
104 𝑆 + 𝐾𝑀
iClicker Question
The Michaelis-Menten equation is a complex and general rate law but
can simplify in extreme cases…
If [S] is very high, then what does the reaction order become with
respect to [S]?

𝑘2 𝐸 0 𝑆
𝑟𝑎𝑡𝑒 =
𝑆 + 𝐾𝑀

A) Zero order
B) First order
C) Second order
105
iClicker Question
The Michaelis-Menten equation is a complex and general rate law but
can simplify in extreme cases…
If [S] is very low, then what does the reaction order become with
respect to [S]?

𝑘2 𝐸 0 𝑆
𝑟𝑎𝑡𝑒 =
𝑆 + 𝐾𝑀

A) Zero order
B) First order
C) Second order
106
Let’s work a problem

107
Let’s work a problem

108
Let’s work a problem

109