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Outline
PART 1: RATES OF REACTIONS
• 14-1 Rate of a Chemical Reaction
• 14-2 Measuring Reaction Rates
CHEMICAL KINETICS • 14-3 Effect of Concentration on Reaction Rates: The
Chem 17 Lecture 3 Rate Law
Midyear 2018 • 14-4 Zero-Order Reactions
Moises Jerome Garrero • 14-5 First-Order Reactions
• 14-6 Second-Order Reactions
• 14-7 Reaction Kinetics: A Summary

Introduction: Chemical Kinetics Introduction: Chemical Kinetics

• Chemical kinetics deals with the following: • Rates of reaction can widely vary!
• Rates of chemical reactions
• Theoretical predictions of reaction rates
• Studies of reaction mechanisms

3 4

Rate of a Chemical Reaction Rate of a Chemical Reaction

• Consider the following hypothetical reaction: • For a general reaction
A+3B⟶2C+D 𝑎A + 𝑏B → 𝑐C + 𝑑D
• Initially, [A] = 0.1 M and [B] = 0.3 M. After 4 minutes, the rate of reaction is defined as
[A] becomes 0.05 M.
1∆ A 1∆ B 1∆ C 1∆ D
• Question 1: What is the rate of disappearance (or rate rate = − =− =+ =+
of consumption) of A? Of B? 𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡
• Question 2: What is the rate of appearance (or rate of
production or of formation) of C? • By this definition, it is ensured that the reaction rate is
always positive

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Average vs. Instantaneous Rate Rate of a Chemical Reaction

• The average rate of reaction (in terms of A) is: • EXAMPLE 3.1: Consider the following unbalanced
reaction:
1∆ A 1 A − A N2O5(g) ⟶ NO2(g) + O2(g)
average rate = − =−
𝑎 ∆𝑡 𝑎 𝑡−𝑡 Initially, in a 2.00-L vessel, 3.54 mol of N2O5 is present.
After 800.0 seconds, 1.07 mol of O2 is produced.
Calculate the following average rates:
• If we take the time interval to be very small
(infinitesimal), then the average rate becomes the (a) rate of production of O2
instantaneous rate of reaction: (b) rate of consumption of N2O5
(c) rate of appearance of NO2
1∆ A 1𝑑 A
instantaneous rate = lim − =− (d) rate of reaction
∆ → 𝑎 ∆𝑡 𝑎 𝑑𝑡
7 8

Measuring Reaction Rates Measuring Reaction Rates

• Measuring time is easy, but • Plot of [H2O2] vs. time
measuring a constantly changing • Slope of tangent line = instantaneous rate
concentration is difficult
• Initial rate = instantaneous rate at start of reaction
• Example: decomposition of H2O2
• Two methods:
• Measure volume of O2
• Determine [H2O2] by titration
with KMnO4

9 10

Factors that Affect Reaction Factors that Affect Reaction

Rates Rates
• Physical state of reactants • Reaction temperature
• Solid, liquid, or gas • Reactions are generally faster at higher
• Homogeneous or heterogeneous temperatures
• Reactant concentration • Arrhenius equation
• Relationship is given by the rate law or rate • Presence of a catalyst
equation • Catalyst = a substance that increases the rate of a
reaction but is not used up in the reaction

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Effect of Concentration on
Rate Law: Order of Reaction
Reaction Rates
• Rate law: a relationship between the concentrations of rate = 𝑘 A 𝒎 B 𝒏
reactants and the rate of reaction • Order: value of each exponent m and n
• For a general reaction • We say that the order of reaction with respect to A is
aA + bB ⟶ cC + dD m, or that the reaction is mth order in A
the rate law is (usually) expressed as • ILLUSTRATION: If m = 1, then the reaction is first order
in A; if n = 2, then the reaction is second order in B; etc.
rate = 𝑘 A B • Reaction orders are generally NOT related to
stoichiometric coefficients
• Overall order of reaction: sum of individual reaction
orders (exponents in the rate law)

13 14

Rate Law: Rate Constant Determination of the Rate Law

rate = 𝒌 A B
• Rate constant, k: proportionality constant in a rate law
• Value depends on several factors, including: the nature
of the reaction itself, presence of catalyst, temperature
• The larger the value of k, the faster the reaction
• The units of the rate constant depend on the overall
order of reaction
• You can tell the overall order from the units of the
rate constant
• We usually use the method of initial rates:
1. Several runs are done, in which one reactant
concentration is varied and the others are kept
constant
2. The effect of changing one concentration on the
initial rate of reaction is noted
3. The exponent (order) is deduced from the ratio of
initial rates
4. This is repeated for other reactants

15 16

Method of Initial Rates Method of Initial Rates

• EXAMPLE 3.2: Consider the hypothetical reaction • EXAMPLE 3.3: Initial rate data are given for the
A+B⟶C+D reaction:
Initial rate data are given below: A+2B+C⟶2D+E

Run [A], M [B], M Initial rate, M/s Run [A], M [B], M [C], M Initial rate, M/min
1 0.100 0.100 3.50 × 10–3 1 1.40 1.40 1.00 1.00 × 10–3
2 0.200 0.100 1.40 × 10–2 2 0.70 1.40 1.00 5.00 × 10–4
3 0.200 0.200 2.80 × 10–2 3 0.70 0.70 1.00 1.25 × 10–4
4 1.40 1.40 0.50 2.00 × 10–3
Determine the rate law and the rate constant. 5 0.70 0.70 0.50 ?

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Method of Initial Rates Zero-Order Reactions

• EXAMPLE 3.3 (continued): A ⟶ products
(a) Determine the rate law, including the value of the • Rate law: rate = k[A]0 = k
rate constant. • The graph of [A] vs. time
(b) Determine the initial rate for run 5. is a straight line with
slope equal to –k
• Units of rate constant?
• Integrated rate law
(relationship of [A] and
time):
A = A − 𝑘𝑡

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First-Order Reactions First-Order Reactions

A ⟶ products • Half-life, t1/2: time required for one-half of a reactant
• Rate law: rate = k[A] to be consumed
• Rate is directly proportional to remaining amount of • For first-order reactions, the half-life is independent of
the reactant the reactant concentration:
• Units of rate constant? ln 2
• Integrated rate law: ln A = ln A − 𝑘𝑡 OR 𝑡 / =
𝑘
A
ln = −𝑘𝑡
A
• The rate constant can be determined by measuring the
• The plot of ln [A] vs. time is a straight line with slope half-life
equal to –k
• Common example: nuclear decay
21 22

First-Order Reactions First-Order Reactions

• EXAMPLE 3.4: The decomposition of H2O2(aq) into • For gases, rates are often
H2O(l) and O2(g) follows first-order kinetics. If the initial measured in terms of gas
concentration of H2O2 is 0.819 M, and the half-life of pressures
the reaction is 2.19 hours, calculate: • For first-order
(a) the rate constant; and decompositions of gases,
(b) the concentration of remaining H2O2 after 3659 s. partial pressure can replace
concentration in the
integrated rate law (why?)
• Shown is the plot of PDTBP vs.
time for the decomposition
of di-t-butyl peroxide (DTBP)
at 147 °C
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First-Order Reactions First-Order Reactions

• EXAMPLE 3.5: The decomposition of N2O5 has a rate
constant of 6.21 × 10–4 s–1.
N2O5(g) ⟶ N2O4(g) + ½ O2(g)
If the initial partial pressure of N2O5 is 750.0 torr,
calculate the following:
(a) partial pressure of N2O5 after 5.00 min
(b) partial pressures of N2O4 and O2 after 5.00 min
(c) total pressure of the reaction vessel
• Challenge: Derive a general expression for Ptotal, in
terms of N2O5 partial pressure

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Second-Order Reactions Second-Order Reactions

A ⟶ products • For second-order reactions, the half-life is inversely
• Rate law: rate = k[A]2 proportional to the initial reactant concentration:
1
• The graph of 1/[A] vs. 𝑡/ =
𝑘A
time is a straight line with
slope equal to k • The half-life is not constant; it actually increases as the
reaction proceeds (why?)
• Units of rate constant?
• The rate constant can be determined by measuring the
• Integrated rate law: half-life, if the initial concentration is known
1 1
= + 𝑘𝑡
A A

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Second-Order Reactions Pseudo-First-Order Reactions

• EXAMPLE 3.6: The decomposition of NO2 has a rate
constant of 0.543 M–1 s–1.
NO2(g) ⟶ NO(g) + ½ O2(g)
The initial concentration of NO2 in a closed vessel is
0.0500 M.
(a) What will be the concentration of NO2 after 400 s?
(b) What is the half-life of the NO2 sample (at the
start)?
• Follow-up question: Is it possible to replace
concentrations with partial pressures?
• Consider the hydrolysis of 0.01 M ethyl acetate:
CH3COOCH2CH3 + H2O ⟶ CH3COOH + CH3CH2OH
• It is first order in ethyl acetate and in water:
rate = k[CH3COOCH2CH3][H2O]
• But since the “molarity” of H2O is very large (≈ 55.5 M)
compared to that of ethyl acetate, it essentially remains
constant throughout the reaction

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Pseudo-First-Order Reactions Summary

• Thus, we can introduce an apparent rate constant k’ =
k[H2O]
Units of
• The rate law becomes Order Rate Law
Integrated Straight
k= k (time Half-Life
Rate Law Line
rate = k’ [CH3COOCH2CH3] in s)
• We say that the reaction is pseudo-first-order overall A
0 rate = k A = A − 𝑘𝑡 [A] vs. t –slope M s–1
• This is commonly done to simplify the kinetic study of 2𝑘
a complex and/or high-order reaction 1 rate = k[A] ln
A
= −𝑘𝑡 ln [A] vs. t –slope s–1
ln 2
A 𝑘
rate = 1 1 1
2 = + 𝑘𝑡 1/[A] vs. t slope M–1 s–1
k[A]2 A A 𝑘A

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Determining Order of Reaction Determining Order of Reaction

• To determine the order of a reaction from • EXAMPLE 3.7: The data below are obtained for the
concentration vs. time data, we need to generate acid hydrolysis of sucrose into glucose and fructose.
three plots: Sucrose + H2O ⟶ Glucose + Fructose
• [A] vs. t (zero order)
• ln [A] vs. t (first order) Time, min [Sucrose], M
• 1/[A] vs. t (second order) 0 0.316
• The most linear plot (i.e. r2 is closest to 1) will give the 39 0.274
order of the reaction 80 0.238
• Rate constant is obtained from the slope 140 0.190
• Limitation: This only applies to decomposition 210 0.146
reactions (A ⟶ products)
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Determining Order of Reaction Zero-Order Plot (Ex. 3.7)

• EXAMPLE 3.7 (continued): 0.35
Water is present in a large excess, so its amount is 0.3
considered to be essentially constant. 0.25
[Sucrose], M

(a) Determine the pseudo-order of the reaction with 0.2

respect to sucrose.
0.15
(b) Determine the pseudo- (or apparent) rate constant. y = -8.0341E-04x + 3.0816E-01
0.1
R² = 0.99004
(c) Calculate the concentration of sucrose at 500 min
0.05
after the start of the reaction.
0
(d) If the reaction is sixth order in water, determine the
0 50 100 150 200 250
true rate constant.
Time, min

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First-Order Plot (Ex. 3.7) Second-Order Plot (Ex. 3.7)

0 8
y = 0.0175x + 2.9817
0 50 100 150 200 250 7
R² = 0.9847
-0.5 Time, min 6

1/[Sucrose], M-1
5
ln [Sucrose]

-1 4
3
-1.5
2
y = -3.6736E-03x - 1.1488E+00 1
-2
R² = 0.99976 0
0 50 100 150 200 250
-2.5
Time, min

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Theoretical Models for

Outline
Chemical Kinetics
PART 2: THEORIES AND REACTION MECHANISMS • Recall: Decomposition of N2O5(g) is first order,
• 14-8 Theoretical Models for Chemical Kinetics according to experiments
• 14-9 The Effect of Temperature on Reaction Rates • But why? Is there a theoretical explanation?
• 14-10 Reaction Mechanisms • Two theories are discussed in relation to chemical
kinetics:
• 14-11 Catalysis • Collision theory
• Transition state theory (TST)

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When Does a Collision Lead to a

Collision Theory
• RECALL: Kinetic-molecular theory of gases
• Collision density: number of collisions per unit volume
per unit time
• About 1032/L/s for gas-phase reactions
• If each collision of reactant molecules yielded products,
then the reaction rate will be ~106 M/s
• But why are gas-phase reactions actually much slower?
• Only a fraction of collisions will actually result to a
chemical reaction!
Reaction?
First factor: Molecular kinetic energies
• The kinetic energies of the colliding molecules must be
sufficient in order to break existing bonds and form
new bonds
• Activation energy, Ea: the minimum energy needed to
be surpassed by the molecules
• The number of energetic collisions is determined by
the distribution of molecular KEs

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When Does a Collision Lead to a

Molecular Kinetic Energies
Reaction?
Second factor: Orientation
• If two identical atoms combine to form a homonuclear
molecule, orientation is not important

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When Does a Collision Lead to a

Collision Theory
Reaction?
Second factor: Orientation • In summary, for a reaction to proceed:
• But for colliding molecules, orientation is very crucial 1. Reactant molecules must collide
2. The molecules must be energetic enough to
overcome the activation energy
3. The colliding molecules must have the correct
orientation relative to each other

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Transition State Theory Reaction Profile

• It is believed that a reaction proceeds as follows: • Reaction profile: a diagram showing the energies
reactant/s ⟶ transition state ⟶ product/s involved as a reaction progresses
• Transition state: a high-energy state that reactant
molecules undergo before being converted to products
• Activated complex: the species that exists during the
transition state (very unstable and non-isolable)
• Example: The reaction between N2O and NO (described
earlier)

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Transition State Theory Transition State Theory

• ILLUSTRATION: Rearrangement of methyl isonitrile to • ILLUSTRATION: Rearrangement of methyl isonitrile to
acetonitrile acetonitrile

• How is the transition state or activated complex

formed?

49 50

Effect of Temperature on
Transition State Theory
Reaction Rates
• EXAMPLE 3.8: For the following gas-phase reaction at • Reaction rates generally
298 K: increase when the temperature
2 N2O ⟶ 2 N2 + O2 is increased
(a) Draw a possible structure of the activated complex. • This is shown by the Arrhenius
equation (1889):
(b) Sketch the reaction profile, given that the average
bond energies of N≡N, N–O and O=O are 945 /
kJ/mol, 201 kJ/mol and 498 kJ/mol, respectively; 𝑘 = 𝐴𝑒
and that the activation energy for the reaction is
200 kJ/mol. Label the important parts of the profile. 𝐸
ln 𝑘 = ln 𝐴 −
𝑅𝑇

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Arrhenius Equation Arrhenius Equation

/ /
𝑘 = 𝐴𝑒 𝑘 = 𝐴𝑒
𝐸 𝐸
ln 𝑘 = ln 𝐴 − ln 𝑘 = ln 𝐴 −
𝑅𝑇 𝑅𝑇
• k = rate constant (units depending on reaction order) • Note that a plot of ln k vs. 1/T yields a straight line
• A = pre-exponential factor or frequency factor • What is the slope and y-intercept of this plot?
(same units as rate constant) • The Arrhenius equation can be rearranged to become:
• Ea = activation energy (in J mol–1)
• R = gas constant (8.3145 J mol–1 K–1) 𝑘 𝐸 1 1
ln = −
• T = absolute temperature (in K) 𝑘 𝑅 𝑇 𝑇

• Do you recall an equation that looks similar?

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Arrhenius Equation Steric Factor

• Recall the requirements for a reaction to proceed:

1. Collision of reactant molecules ⟶ collision

frequency, 𝒁𝟎

2. Sufficient kinetic energy ⟶ given by the

Boltzmann distribution:

/
𝑓=𝑒

3. Proper orientation ⟶ steric factor, 𝒑

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Arrhenius Equation Arrhenius Equation

• The rate constant is a product of these three factors: • EXAMPLE 3.9: For the following reaction,
N2O5 ⟶ NO2 + NO3
/ /
𝑘 = 𝑍 𝑝𝑓 = 𝑍 𝑝𝑒 = 𝐴𝑒 the value of the rate constant at 0.0 °C is 0.00916 s–1,
and the activation energy is 88.0 kJ/mol.
where 𝐴 = 𝑍 𝑝 (a) Determine the value of the rate constant at 2.0 °C.
• Thus, the pre-exponential factor shows the number of (b) Determine the pre-exponential factor.
possible collisions with the proper orientation in order
for the reaction to proceed

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Arrhenius Equation Arrhenius Plot for Ex. 3.10

• EXAMPLE 3.10: The table below shows the rate 0
constants for the rearrangement of methyl isonitrile at 0.00185 0.0019 0.00195 0.002 0.00205 0.0021 0.00215 0.0022
various temperatures. -2
Temp, °C k, s–1 -4
189.7 2.52 × 10–5
ln k

-6
198.9 5.25 × 10–5 y = -19050x + 30.529
-8 R² = 0.9995
230.3 6.30 × 10–4
251.2 3.16 × 10–3 -10
(a) Calculate the activation energy.
-12
(b) Calculate the pre-exponential factor. 1/T
(c) Determine the rate constant at 430.0 K.
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Reaction Mechanisms
• A balanced chemical equation does not show what
exactly happens to the reactants during the reaction
• Reaction mechanism: step-by-step detailed
description of a chemical reaction
• Elementary reaction/process: each step in a reaction
mechanism; describes any significant molecular event
• A plausible mechanism must:
1. have elementary steps that add up to the overall
reaction
2. account for the experimentally determined rate
law
Characteristics of Elementary
Processes
1. They are usually either unimolecular or bimolecular
• Molecularity: number of reactant molecules
involved in the elementary process
• Unimolecular: dissociation of a single molecule
• Bimolecular: collision of two molecules
• Termolecular: collision of three molecules at the
same time; very rare (why?)

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Characteristics of Elementary Characteristics of Elementary

Processes
2. In the rate law of an elementary process, the order
with respect to one reactant is equal to its
stoichiometric coefficient
• This does NOT apply for the overall reaction
Processes
3. They are reversible, and some may reach equilibrium
• Equilibrium means rate of forward process = rate
of reverse process
4. Certain species (called reaction intermediates) are
produced in one elementary process and consumed
in another

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Characteristics of Elementary
Reaction Intermediates
Processes
• ILLUSTRATION: Reaction mechanism for the 5. One elementary process may occur much more
conversion of ozone to dioxygen slowly than all the others
• Thus, it usually dictates the rate of the overall
reaction
Step 1: O3(g) ⟶ O2(g) + O(g)
• It is called the rate-determining step
Step 2: O3(g) + O(g) ⟶ O2(g) + O2(g)

OVERALL: 2 O3(g) ⟶ 3 O2(g)

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Deducing the Rate Law from

Profile for a Multistep Reaction
• Which is the rate-determining step?
the Mechanism
• For a multistep mechanism, the rate-determining step
gives the rate law of the overall reaction
• Two cases to consider:
1. Slow initial step followed by fast step/s
2. Fast initial step/s (that is/are in equilibrium)
followed by a slow step

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Case 1: Slow Initial Step Case 1: Slow Initial Step

• ILLUSTRATION: Consider the following overall • Reaction profile shows two peaks corresponding to the
reaction: elementary steps
H2(g) + 2 ICl(g) ⟶ I2(g) + 2 HCl(g) • Note that intermediate ≠ transition state
• The experimental rate law is
rate = k[H2][ICl]
• Proposed mechanism:
Step 1: H2 + ICl ⟶ HI + HCl (slow)
Step 2: HI + ICl ⟶ I2 + HCl (fast)
• Is this mechanism consistent with the rate law?

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Case 2: Fast Initial Step Case 2: Fast Initial Step

• ILLUSTRATION: Consider the overall reaction: • ILLUSTRATION: Consider the overall reaction:
2 NO(g) + Br2(g) ⟶ 2 NOBr(g) 2 NO(g) + Br2(g) ⟶ 2 NOBr(g)
• The experimental rate law is • The experimental rate law is
rate = k[NO]2[Br2] rate = k[NO]2[Br2]
• Proposed mechanism A: one step • Proposed mechanism B: two steps
Step 1: 2 NO(g) + Br2(g) ⟶ 2 NOBr(g) (slow) Step 1: NO(g) + Br2(g) ⇄ NOBr2(g) (fast, eqm)
• Is this mechanism consistent with the rate law? Step 2: NOBr2(g) + NO(g) ⟶ 2 NOBr(g) (slow)
• Is this mechanism plausible? • Is this mechanism consistent with the rate law?
• Is this mechanism plausible?

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Deducing the Rate Law from

Case 2: Fast Initial Step
the Mechanism
• ILLUSTRATION: Consider the overall reaction: • EXAMPLE 3.11: Consider the following overall reaction
2 NO(g) + Br2(g) ⟶ 2 NOBr(g) in the gas phase:
• The experimental rate law is 2 NO2 + F2 ⟶ 2 NO2F
rate = k[NO]2[Br2] Give the rate law that can be deduced from the
following proposed mechanism:
• Proposed mechanism C: two steps
Step 1: NO2 + F2 ⇄ NO2F2 (fast, eqm)
Step 1: NO(g) + NO(g) ⇄ N2O2(g) (fast, eqm)
Step 2: NO2F2 ⟶ NO2F + F (slow)
Step 2: N2O2(g) + Br2(g) ⟶ 2 NOBr(g) (slow)
Step 3: F + NO2 ⟶ NO2F (fast)
• Is this mechanism consistent with the rate law?
• Is this mechanism plausible?

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Steady-State Approximation Steady-State Approximation

• No assumptions on the relative rates of steps are necessary • ILLUSTRATION: Consider the overall reaction:
(e.g. “fast, equilibrium”, “slow”) 2 NO(g) + Br2(g) ⟶ 2 NOBr(g)
• To eliminate an intermediate from the rate law, a steady- • Proposed mechanism: two steps
state condition is applied to the intermediate
Step 1: NO(g) + Br2(g) ⇄ NOBr2(g) (fast)
• The intermediate (I) is produced and consumed at equal
rates; thus: Step 2: NOBr2(g) + NO(g) ⟶ 2 NOBr(g) (slow)
• We can derive a more accurate rate law using SSA
∆I • Is this mechanism consistent with the derived rate law
= rate of appearance of I − rate of disappearance of I = 0
∆𝑡 earlier (using the rate-determining step
approximation)?
• The rates of appearance and disappearance can be
obtained from the rate laws of elementary steps
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Catalysis Homogeneous Catalysis

• Catalyst: a substance that speeds up a reaction without • Consider the decomposition of hydrogen peroxide:
being consumed or produced in the reaction 2 H2O2(aq) ⟶ 2 H2O(l) + O2(g)
• It provides a pathway with lower activation energy • This is very slow, but can be catalyzed by many
• Two types of catalysis: substances such as iodide
• Homogeneous catalysis: the catalyst, reactants and • Proposed mechanism of iodide catalysis:
products are all in the same phase
Step 1: H2O2 + I– ⟶ OI– + H2O (slow)
• Heterogeneous catalysis: the catalyst, reactants
and products are present in different phases Step 2: H2O2 + OI– ⟶ H2O + I– + O2(g) (fast)
• Is this a plausible mechanism? What is the rate law?

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Homogeneous Catalysis Heterogeneous Catalysis

• The most common type is surface catalysis: gaseous
or aqueous reactants attach on a solid surface
• Steps involved in heterogeneous catalysis:
1. Adsorption (attachment) of reactants on sites
that are effective for catalysis (called active sites)
2. Diffusion of reactants along the surface
3. Reaction at an active site to form adsorbed
product
4. Desorption of the product

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Catalytic Hydrogenation of
Catalytic Converters
Ethylene

81 82

Reaction Profile for a Surface-

Catalyzed Reaction

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Enzymes as Biological Catalysts Enzymes as Biological Catalysts

• Enzymes: large proteins • Enzyme catalysis is described using “lock-and-key”
that catalyze specific model
biochemical reactions
• Example: The
decomposition of H2O2
can be catalyzed by the
enzyme called catalase
(shown at the right)
Protein Data Bank ID: 1DGB

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Enzymes as Biological Catalysts Enzymes as Biological Catalysts

• Michaelis–Menten mechanism:
Step 1: E + S ⇄ ES 𝑘 E S 𝑣 S
𝑣= =
Step 2: ES ⟶ E + P 𝐾 + S 𝐾 + S
• E = enzyme; S = substrate; ES = enzyme-substrate •𝐾 = = Michaelis
complex; P = product constant
• The result is the Michaelis–Menten equation: • Limiting cases:
• Low [S]: first-order wrt
𝑣=
𝑘 E S
=
𝑣 S substrate
𝐾 + S 𝐾 + S • High [S]: zero-order wrt
substrate

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