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SF Chem CHU22201.

Chemical Kinetics
2018/2019.
Prof. Mike Lyons
Room 3.2 Chemistry Building
School of Chemistry
Trinity College Dublin.
Email : melyons@tcd.ie
Course Summary.
•  Contact short but sweet. 5 Lectures in total (4 this week (wk3),
1 next week (wk4)), 3 tutorials next week (wk 4).
•  We revise quantitative aspects of JF kinetics and discuss some
new more advanced topics and introduce the mathematical
theory of chemical kinetics.
•  Topics include:
–  Lecture 1-3. Quantitative chemical kinetics, integration of rate
equations, zero, first, second order cases, rate constant . Graphical
analysis of rate data for rate constant and half life determination
for each case . Dependence of rate on temperature. Arrhenius
equation and activation energy. Kinetics of complex multistep
reactions. Parallel and consecutive reactions. Concept of rate
determining step and reaction intermediate.
–  Lecture 4-5. Enzyme kinetics (Michaelis-Menten case) and surface
reactions involving adsorbed reactants (Langmuir adsorption
isotherm).
•  If we have time we will cover the following topic:
–  Theory of chemical reaction rates : bimolecular reactions. Simple
Collision Theory & Activated Complex Theory.
Recommended reading.
•  Burrows et al Chemistry3, 1st edition, OUP (2009) Chapter 8. pp.339-403. 2nd edition,
OUP(2013) Chapter 9, pp.378-443, 3rd edition, Ch9, pp.382-443.
•  P.W. Atkins J. de Paula.The elements of physical chemistry. 5th Edition.
OUP (2009). Chapter 10, pp.219-243; Chapter 11, pp.244-269. 6th Edition OUP (2013),
Chapter 10, pp.235-260; Chapter 11, pp.261-286, 7th edition, Focus 6 pp.249-314.
•  P.W. Atkins and J. de Paula. Physical Chemistry for the Life Sciences. 2nd edition. OUP
(2011). Part II entitled The kinetics of life processes (Chapters 6,7,8, pp.217-310) is
especially good.
•  Both of these books by well established authors are clearly written with an excellent style and both
provide an excellent basic treatment of reaction kinetics with emphasis on biological examples. These
books are set at just the right level for the course and you should make every effort to read the
recommended chapters in detail. Also the problem sheets will be based on problems at the end of
these chapters!

•  P.W. Atkins, J. de Paula. Physical Chemistry. 9th Edition. OUP (2010).


Chapter 21, pp.782-830 ; Chapter 22, pp.831-875;
Chapter 23, pp.876-908.
P. Atkins, J de Paula, J Keeler, OUP 2018, Atkins’ Physical Chemistry 11th Edition, Focus 17
Chemical Kinetics pp.721-777. Focus 18 Reaction Dynamics, pp.779-821. especially Topic 18A
and 18B.
•  A more advanced and complete account of the course material. Much of chapter 22 is JS material.

•  M.J. Pilling and P/W. Seakins. Reaction Kinetics. OUP (1995).


•  Modern textbook providing a complete account of modern
chemical reaction kinetics. Good on experimental methods and theory.

•  M. Robson Wright An introduction to chemical kinetics. Wiley (2005)


•  Another modern kinetics textbook which does as it states in the title, i.e. provide a readable
introduction to the subject ! Well worth browsing through.
SF Chemical
Kinetics.
Lecture 1-3.
Quantitative Reaction
Kinetics.
Reaction Rate: The Central Focus of
Chemical Kinetics
The wide range of reaction rates.

Reaction rates vary from very fast to very slow : 1 femtosecond (fs)
from femtoseconds to centuries ! = 10-15 s = 1/1015 s !
Picosecond (10-12s)
techniques

Femtosecond
(10-15 s)techniques

Atkins de Paula, Elements Phys. Chem.


5th edition, Chapter 10, section 10.2, pp.221-222

Reactions studies under constant temperature conditions.


Mixing of reactants must occur more rapidly than reaction occurs.
Start of reaction pinpointed accurately.
Method of analysis must be much faster than reaction itself.
Chemical reaction kinetics.
reactants products
•  Chemical reactions involve the
forming and breaking of
chemical bonds.
H ( g)+ I2( g)→ 2HI( g)
2
•  Reactant molecules (H2, I2)
approach one another and
collide and interact with •  Thermodynamics tells us all
appropriate energy and about the energetic feasibility
orientation. Bonds are of a reaction : we measure the
stretched, broken and formed Gibbs energy ΔG for the chemical
and finally product molecules Reaction.
(HI) move away from one
another. •  Thermodynamics does not tell us
•  How can we describe the rate how quickly the reaction will
at which such a chemical proceed : it does not provide
transformation takes place? kinetic information.
Basic ideas in reaction kinetics.
•  Chemical reaction kinetics deals with the rate of velocity of chemical
reactions.

•  We wish to quantify
–  The velocity at which reactants are transformed to products
–  The detailed molecular pathway by which a reaction proceeds (the reaction
mechanism).

•  These objectives are accomplished using experimental measurements.

•  We are also interested in developing theoretical models by which the


underlying basis of chemical reactions can be understood at a
microscopic molecular level.

•  Chemical reactions are said to be activated processes : energy (usually


thermal (heat) energy) must be introduced into the system so that
chemical transformation can occur. Hence chemical reactions occur
more rapidly when the temperature of the system is increased.

•  In simple terms an activation energy barrier must be overcome before


reactants can be transformed into products.
Geometric definition of
reaction rate.
d[R]
R=−
Rate expressed as tangent line dt
To concentration/time curve at a
Particular time in the reaction.

d ⎡⎣ P ⎤⎦
R=
dt
2 H2O2 (aq) à 2 H2O (l) + O2 (g)
Reaction rate and reaction order.
•  The reaction rate (reaction velocity) R is quantified in terms
ofchanges in concentration [J] of reactant or product species J
with respect to changes in time.
•  The magnitude of the reaction rate changes (decreases) as the
reaction proceeds.
•  Rate of reaction is often found to be proportional to the molar
concentration of the reactants raised to a simple power (which
need not be integral). This relationship is called the rate
equation.
•  The manner in which the reaction rate changes in magnitude with
changes in the magnitude of the concentration of each
participating reactant species is called the reaction order.
•  Hence in other words:
–  the reaction order is a measure of the sensitivity of the reaction
rate to changes in the concentration of the reactants.
Working out a rate equation. k = 5.2 x 10-3 s-1

2N O ( g)→ 4NO2( g)+ O2( g)


2 5

T = 338 K

Initial rate is proportional to initial


concentration of reactant.
(rate)0 ∝ ⎡⎣ N2O5 ⎤⎦ k = rate constant
0
Initial rate determined by (rate)0 = k ⎡⎣ N2O5 ⎤⎦
evaluating tangent to 0

concentration versus time Rate d ⎡⎣ N2O5 ⎤⎦


curve at a given time t0. Equation. rate = − = k ⎡⎣ N2O5 ⎤⎦
dt
xA + yB k
⎯→
⎯ Products rate constant k

empirical rate
1 d ⎡⎣ A ⎤⎦ 1 d ⎡⎣ B ⎤⎦ α β
equation (obtained R = − =− = k ⎡⎣ A ⎤⎦ ⎡⎣ B ⎤⎦
from experiment) x dt y dt

α, β = reaction
stoichiometric orders for the
coefficients
reactants (got
Reaction order determination. experimentally)
Vary [A] , keeping [B] constant and Rate equation can not in
measure rate R. general be inferred from
Vary [B] , keeping [A] constant and the stoichiometric equation
for the reaction.
measure rate R.

Log R Log R

Slope = α Slope = β

Log [A] Log [B]


Integrated rate equation.
Burrows et al Chemistry3, Chapter 8, pp.349-356.
Atkins de Paula 5th ed. Section 10.7,10.8, pp.227-232

•  Many rate laws can be cast as differential equations which may then be
solved (integrated) using standard methods to finally yield an
expression for the reactant or product concentration as a function of
time.
•  We can write the general rate equation for the process A à Products
as
dc
− = kF(c)
dt
where F(c) represents some distinct function of the reactant
concentration c. One common situation is to set F(c) = cn where n =
0,1,2,… and the exponent n defines the reaction order wrt the reactant
concentration c.
•  The differential rate equation may be integrated once to yield the
solution c = c(t) provided that the initial condition at zero time which is
c = c0 is introduced.
Zero order kinetics. The reaction proceeds at the same rate R
regardless of concentration.

Rate equation : R R ∝ c0
units of rate constant k :
dc mol dm-3 s-1
R=− =k
dt
c
c = c0 when t = 0

integrate
using initial c0
condition half life t = τ 1/2 when c =
2

c(t) = −kt + c0 c τ 1/2 =


c0
τ 1/2 ∝ c0
slope = -k 2k
τ 1/ 2
c0 1
slope =
diagnostic 2k
plot c0
t
k
First order kinetics. A ⎯→
⎯ products First order differential
Initial rate equation.
concentration c0
dc
− = kc
rate = −
dc dt
dt
Initial condition

t = 0 c = c0
Solve differential
equation
via separation
of variables

First order reaction c(t) = c0 e− kt = c0 exp ⎡⎣ −kt ⎤⎦


(rate)t ∝ c
(rate)t = kc
k = first order Reactant concentration
rate constant, units: s-1 as function of time.
Half life τ½ c0
First order kinetics. t = τ 1/2 c=
2
θ = θ1/2 u = 1/ 2

ln2 0.693
τ 1/2 = =
k → s −1 k k

c(t) = c0 e− kt = c0 exp ⎡⎣ −kt ⎤⎦


Mean lifetime of reactant molecule
c(t)
u= = exp ⎡⎣ −θ ⎤⎦
1 1 1
c0 c ( t ) dt =
∞ ∞
τ=
c0 ∫
0 c0 ∫
0
c0 e− kt dt =
k
θ = kt
First order kinetics: half life.
u=
a u = 1
a0

t = τ 1/2 c = c0 / 2
In each successive period
of duration τ1/2 the concentration
of a reactant in a first order reaction
decays to half its value at the start
of that period. After n such periods, u = 0.5
the concentration is (1/2)n of its
initial value.

u = 0.25
τ 1/ 2 u = 0.125

ln2 0.693
τ 1/2 = =
k k

half life independent of


c0 initial reactant concentration
Second order kinetics: equal dm3mol-1s-1
k
reactant concentrations. 2A
⎯→
⎯ P
slope = k
1
separate variables
dc integrate
c
− = kc 2 1 1
dt = kt +
c c0
t = 0 c = c0 t
c0
half life t = τ 1/2 c= c0
2
c (t ) =
1+ kc0t
τ 1/2 =
1 τ 1/2
kc0
1
rate varies as
τ 1/2 ∝ square of reactant
c0
concentration
τ 1/2 ↓ as c0 ↑ c0
1st order kinetics 2nd order kinetics

u(θ ) − kt
u(θ ) c(t) =
c0
c(t) = c0 e 1+ kc0t
u(θ ) = e−θ 1
u(θ ) =
1+ θ

θ = kt θ = kc0t
1st and 2nd order kinetics : Summary .
Reaction Differential Concentration Diagnostic Half
rate equation variation with Equation Life
time

A ⎯⎯
1

k
dc c(t ) = ln c(t) = −k1t + ln c0 ln 2
Products
− = k1c c0 exp [ −k1t ]
τ 1/ 2 =
k1
dt

k2
2 A ⎯⎯→ dc c(t ) = 1 1 1
− = k2 c 2 = k2t + τ 1/ 2 =
Products c0 c(t ) c0 k2 c0
dt
1 + k2 c0t

ln c(t) Diagnostic
Slope = - k1 1/c(t)
τ½ 1st order Plots .
Slope = k2
2nd order

t t c0
n th order kinetics: equal reactant k
concentrations. nA ⎯→
⎯ P
1
separate variables
dc integrate c n−1
− = kc n
dt 1 1
= ( n − 1) kt +
t = 0 c = c0 c n−1 c0 n−1
n ≠1
n = 0, 2,3,….. rate constant k
(
slope = n −1 k )
obtained from slope
t
Half life
ln τ 1/2
2 −1 n−1
⎧⎪ 2 − 1 ⎫⎪
n−1
τ 1/2 = ⎬ − ( n − 1) ln c0
( ) 0
n − 1 kc n−1
ln τ 1/2 = ln ⎨
⎪⎩ ( n − 1) ⎪⎭
k

(
slope = − n −1 )
τ 1/2 ∝ c01−n reaction order n determined
from slope
n > 1 τ 1/2 ↓ as c0 ↑
n < 1 τ 1/2 ↑ as c0 ↑
ln c0
k
Second order kinetics: A + B ⎯→
⎯ P
Unequal reactant concentrations. Pseudo first
order kinetics
half life when b0 >>a0
rate equation
⎧ 1⎫
ln ⎨2− ⎬ 1
da db dp ⎩ ζ⎭ ζ >> 1 →0
R=− =− = = kab τ 1/2 =
dt dt dt ( )
ka0 ζ −1
ζ
ln2 ln2
b0 τ 1/2 ≅ =
initial conditions ζ= kb0 k ′
a0 k ′ = kb0

t = 0 a = a0 b = b0 a0 ≠ b0

dm3mol-1s-1 pseudo 1st order
integrate using rate constant
partial fractions

( )
F a,b slope = k

1 ⎧⎪ ⎛ b b0 ⎞ ⎫⎪
( )
F a,b = ⎨ln ⎜ ⎟ ⎬ = kt
b0 − a0 ⎩⎪ ⎝ a a0 ⎠ ⎭⎪
t
Temp Effects in Chemical
Kinetics.

Atkins de Paula
Elements P Chem 5th edition
Chapter 10, pp.232-234

Burrows et al Chemistry3,
Section 8.7,
pp.383-389.
Van’t Hoff expression:
TS

Energy
⎛ d ln K c ⎞ ΔU 0
⎜⎝ dT ⎟⎠ = RT 2
P
E
Standard change in internal
E’
energy:

ΔU 0 = E − E ′ R
ΔU0

k P
!!!
R↽!! ⇀
!P
k′
Reaction coordinate
k
Kc =
k′
d ln k E
= This leads to formal
⎛ d ⎛ k ⎞⎞ d ln k d ln k ′ ΔU 0
dT RT 2 definition of Activation
⎜⎝ dT ln ⎜⎝ k ′ ⎟⎠ ⎟⎠ = dT − dT = RT 2 d ln k ′ E′ Energy.
P =
dT RT 2
Temperature effects in chemical kinetics.
•  Chemical reactions are activated processes : they require an
energy input in order to occur.
•  Many chemical reactions are activated via thermal means.
•  The relationship between rate constant k and temperature T
is given by the empirical Arrhenius equation.
•  The activation energy EA is determined from experiment, by
measuring the rate constant k at a number of different
temperatures. The Arrhenius equation ⎡ EA ⎤
is used to construct an Arrhenius plot k = Aexp ⎢ − ⎥
⎢⎣ RT ⎥⎦

of ln k versus 1/T. The activation energy
Pre-exponential
is determined from the slope of this plot. factor
ln k EA
Slope = −
⎛ d lnk ⎞ ⎛ ⎞ R
2 d lnk
E A = −R ⎜ ⎟ = RT ⎜

(
⎜⎝ d 1/T ) ⎟⎠ ⎝ dT ⎟⎠ 1
T
In some circumstances the Arrhenius Plot is curved which implies that
the Activation energy is a function of temperature.
Hence the rate constant may be expected to vary with temperature
according to the following expression.

⎡ E ⎤
k = aT exp ⎢ −
m

⎣ RT ⎦
We can relate the latter expression to the Arrhenius parameters A and EA
as follows.
E
ln k = ln a + mlnT −
RT
⎛ d ln k ⎞ ⎧m E ⎫
E A = RT 2 ⎜ ⎟ = RT 2 ⎨ + 2⎬
= E + mRT
⎝ dT ⎠ ⎩ T RT ⎭
E = E A − mRT

Hence ⎡ E ⎤ ⎡ E ⎤
k = aT mem exp ⎢ − A ⎥ = Aexp ⎢ − A ⎥
⎣ RT ⎦ ⎣ RT ⎦ Svante August
A = aT mem Arrhenius
Consecutive reaction : Case I.
Intermediate formation fast, intermediate decomposition slow.

k2
Case I . κ= << 1
k1 TS II
k << k1
2
TS I
k k
A ⎯⎯
1
→ B ⎯⎯
2
→C ΔGI‡ ΔGII‡

energy
I : fast II : slow
rds
A
‡ ‡
ΔGI << ΔGII B
C

Step II is rate determining reaction co-ordinate


since it has the highest
activation energy barrier. The reactant species A will be
more reactive than the intermediate B.
Consecutive reactions Case II: k2
Intermediate formation slow, intermediate decomposition fast. κ=
k1
k k

A ⎯⎯
1
→ B ⎯⎯
2
→C
k2
κ= >> 1 key parameter
Case II . k1
k >> k1
Intermediate B fairly reactive.
2 [B] will be small at all times.
k k
A ⎯⎯
1
→ B ⎯⎯
2
→C TS I

I : slow rds II : fast TS II


energy ΔGI‡
ΔGI‡ >> ΔGII‡
ΔGII‡
Step I rate determining A
since it has the highest B
activation energy barrier. C

reaction co-ordinate
k >> k2 Rate Determining Step
1
k1 k2
A ⎯⎯
→ B ⎯⎯
→C
Fast Slow

•  Reactant A decays rapidly, concentration of intermediate species B


is high for much of the reaction and product C concentration rises
gradually since B--> C transformation is slow .

k2 >> k1 Rate Determining


Step
k1 k2
A ⎯⎯
→ B ⎯⎯
→C
Slow Fast
•  Reactant A decays slowly, concentration of intermediate species B
will be low for the duration of the reaction and to a good approximation
the net rate of change of intermediate concentration with time is zero.
Hence the intermediate will be formed as quickly as it is removed.
This is the quasi steady state approximation (QSSA).
Parallel reaction mechanism. A ⎯⎯
1
→X
k

•  We consider the kinetic analysis of a concurrent A ⎯


k2

→Y
or parallel reaction scheme which is often met in

real situations. k1, k2 = 1st order rate constants
•  A single reactant species can form two We can also obtain expressions
distinct products. for the product concentrations
We assume that each reaction exhibits 1 order x(t) and y(t).
st

kinetics.
•  Initial condition : t= 0, a = a0 ; x = 0, y = 0 .
dx
dt
(
= k1a = k1a0 exp ⎡⎣ − k1 + k2 t ⎤⎦ )
( )
t
•  Rate equation: x(t ) = k1a0 ∫ exp ⎡⎣ − k1 + k2 t ⎤⎦ dt
0

da
( )
R = − = k1a + k2a = k1 + k2 a = kΣ a
ka
{ (
x(t ) = 1 0 1− exp ⎡⎣ − k1 + k2 t ⎤⎦
k1 + k2
) }
dt
dy
(
= k2a = k2a0 exp ⎡⎣ − k1 + k2 t ⎤⎦ )

( )
a(t ) = a0 exp ⎡⎣ −kΣt ⎤⎦ = a0 exp ⎡⎣ − k1 + k2 t ⎤⎦
dt
t
( )
y(t ) = k2a0 ∫ exp ⎡⎣ − k1 + k2 t ⎤⎦ dt
0

•  Half life: τ = ln2 = ln2


1/2
kΣ k1 + k2
ka
{ (
y(t ) = 2 0 1− exp ⎡⎣ − k1 + k2 t ⎤⎦
k1 + k2
) }

•  All of this is just an extension of simple Final product analysis x(t ) k1
yields rate constant ratio. Lim =
1st order kinetics. t→∞ y(t ) k2

Parallel Mechanism: k1 >> k2 Parallel Mechanism: k2 >> k1

1.0

κ = 0.1
normalised concentration

0.8
x(t)
u(τ)
0.6 v(τ)
w(τ)

0.4
a(t) κ = k2 /k1
/

0.2
y(t)
0.0
0 1 2 3 4 5 6

τ = k1t

k2
κ= = 0.1
k1
k1
= 10 =
( )
v ∞
k w(∞)
2
Reaching Equilibrium on the
Macroscopic and Molecular Level

N2O4
NO2
N2O4 (g) 2 NO2 (g)
colourless brown
Chemical Equilibrium :
a kinetic definition.
Concentrations time
•  Countless experiments with chemical Concentrations vary invariant
systems have shown that in a state of with time
equilibrium, the concentrations of
reactants and products no longer change ⎡⎣ NO2 ⎤⎦ t ↑ ⎡⎣ NO2 ⎤⎦
eq
with time.
⎡N O ⎤ ↓
•  This apparent cessation of activity occurs ⎣ 2 4 ⎦ t ⎡⎣ N2O4 ⎤⎦
because under such conditions, all eq
reactions are microscopically reversible.
•  We look at the dinitrogen tetraoxide/ Kinetic Equilibrium
nitrogen oxide equilibrium which regime state

concentration
occurs in the gas phase. NO2

N2O4 (g) 2 NO2 (g) t → ∞


N2O4
colourless brown
Equilibrium:
Kinetic analysis. t →∞ ! "
R=R
! time
R = k ⎡⎣ N2O4 ⎤⎦
2
k ⎡⎣ N2O4 ⎤⎦ = k ′ ⎡⎣ NO2 ⎤⎦
eq eq
" 2 2
R = k ′ ⎡⎣ NO2 ⎤⎦ ⎡⎣ NO2 ⎤⎦ k Equilibrium
eq
= =K constant
Valid for any time t ⎡⎣ N2O4 ⎤⎦ k ′

k
First order reversible reactions : A B
understanding the approach to chemical equilibrium. k'

Rate equation
u+ v =1
da
= −ka + k ′b τ = 0 u = 1 v = 0
dt
Rate equation in normalised form
Initial condition

t = 0 a = a0 b = 0 du 1
+u =
dτ 1+ θ
Mass balance condition
Solution produces the concentration expressions


∀t a + b = a0
()
uτ =
1
1+ θ
{
1+ θ exp ⎡⎣ −τ ⎤⎦ }
Introduce normalised variables.

()
v τ =
θ
1+ θ
{
1− exp ⎡⎣ −τ ⎤⎦ }
u=
a
a0
v=
b
a0
( )
τ = k + k′ t θ =
k
k′ (
v τ ) ⎧⎪ 1− exp ⎡ −τ ⎤ ⎫⎪
Q (τ ) = =θ ⎨ ⎣ ⎦

u(τ ) ⎩⎪ 1+ θ exp ⎡ −τ ⎤
⎣ ⎦ ⎭⎪
Reaction quotient Q
First order reversible reactions: approach to equilibrium.

Kinetic
regime
1.0

0.8
Product B Equilibrium
concentration

0.6
u (τ) (
K =Q τ →∞ )
v (∞)
v (τ)
0.4
Reactant A
=
0.2 u( ∞ )

0.0
0 2 4 6 8

= (k+k')t
ττ=(k+k’)t
Understanding the difference between reaction quotient Q and
Equilibrium constant K.
12
Approach to
Equilibrium
10
Q<θ
8
θ = 10 Equilibrium
Q=K=θ
Q(τ)
Q(τ)

0
0 2 4 6 8

ττ =
=(k+k’)t
(k+k')t

Q (τ ) =
(
v τ ) ⎧⎪ 1− exp ⎡ −τ ⎤ ⎫⎪
=θ ⎨ ⎣ ⎦
⎬ t → ∞ Q→ K =θ =
k
K=
( )
v ∞


u(τ ) ⎪⎩ 1+ θ exp ⎡ −τ ⎤
⎣ ⎦ ⎪⎭ k′
( )
u ∞
QSSA: a fluid flow analogy.
•  QSSA illustrated via analogy
with fluid flow.
•  If fluid level in tank is to
remain constant then rate of
inflow of fluid from pipe 1 P1
must balance rate of outflow Fluid level
from pipe 2.
•  Reaction intermediate
concentration equivalent to
fluid level. Inflow rate
equivalent to rate of
formation of intermediate P2
and outflow rate analogous to
rate of removal of
intermediate.
•  Detailed mathematical analysis of complex
Quasi-Steady State Approximation.
reaction mechanisms is difficult. QSSA
Some useful methods for solving sets of
coupled linear differential rate equations k k
include matrix methods and Laplace Transforms. A ⎯⎯
1
→ X ⎯⎯
→P
2

•  In many cases utilisation of the quasi steady


state approximation induction
leads to a considerable simplification in the period Consecutive reactions k1 = 0.1 k2 .
kinetic analysis.
1.0

The QSSA assumes that after an initial

Normalised concentration
u(τ)
induction period (during which the
A P
concentration x of intermediates X rise
from zero), and during the major part 0.5

of the reaction, the rate of change of w(τ)


concentrations of all reaction
intermediates are negligibly small.
v(τ)

0.0
Mathematically , QSSA implies 0.0 0.5 1.0

τ = k1t
τ = k1t

dx intermediate X
= RX formation − RX removal ≅ 0
dt concentration
approx. constant
RX formation = RX removal

Atkins de Paula P Chem, 9th Edition,
Chapter 23,Catalysis, pp.876-908.

SF Chemical Kinetics.

Lecture 3-4
Catalysis:
Heterogeneous Catalysis &
Biocatalysis.
Lecture preview.
•  In this lecture we focus attention on the
catalysis of chemical reactions.
•  We consider:
–  Heterogeneous catalysis on solid surfaces
–  Enzymatic bio-catalysis . Michaelis-Menten single
enzyme/substrate kinetics.
•  Common concept: Adduct formation / Binding
Interaction between catalyst and reactant.
Catalysis.
•  Catalysis involves the enhancement of the
rate of a reaction by a substance, which is
not consumed in the reaction. It turns out
that the vast majority of all industrial
chemical reactions involve surfaces as the
catalysts. The kind of processes involved
range from hydrogenation of
hydrocarbons to detoxification of
exhaust gases. The catalytic converter in
an automobile is a classic example.
•  The image presented across illustrates
the general principles: a particular metal
surface (in this case, a Pt-Rh alloy) is
known to catalyze the desired reaction. In
order to maximize the surface area of
the metal per weight,
small particles are used. You can almost
count the atoms in the particle shown,
which was from a real catalyst and was
studied by Scanning Electron Microscopy.
The particle shown has 500-600 atoms,
based on a rough estimate from the
number of atoms at its circumference.
Oxide substrates are also a general
characteristic of such catalysts.
http://www.pt.hut.fi/teke/opetus/uusitutkinto/ymparistokatalyysi/luentokalvot/hUT2006%20Introduction.pdf
http://www.pt.hut.fi/teke/opetus/uusitutkinto/ymparistokatalyysi/luentokalvot/hUT2006%20Introduction.pdf
http://www.pt.hut.fi/teke/opetus/uusitutkinto/ymparistokatalyysi/luentokalvot/hUT2006%20Introduction.pdf
Catalysis: general comments.
•  The overall change in free energy
•  Catalysts come in a variety of forms ΔG0 for the catalytic reaction equals
varying from atoms and molecules to that of the uncatalyzed reaction.
large structures such as enzymes Hence the catalyst does not effect
and zeolites. the equilibrium constant (recall that
•  The catalyst offers an alternative ΔG0 = -RT ln K) for the reaction A +B
low energy pathway for the reaction, à P. Thus if a reaction is
which is perhaps more complex, but thermodynamically unfavourable, a
energetically more favourable. catalyst cannot change the situation.
A catalyst changes the kinetics but
•  The activation energy for the not the thermodynamics of a
catalytic reaction is significantly reaction.
smaller than that of the uncatalyzed
reaction. Hence the rate of the •  The catalyst accelerates both the
catalyzed reaction is much larger. forward and the reverse reaction to
the same extent. If a catalyst
•  Sabatier Principle: accelerates formation of product P
–  The successful combination of from reactants A and B, it will do
catalyst and reaction is that in which the same for the decomposition of P
the interaction between catalyst and
reacting species is not too weak but into A and B.
also not too strong.
Catalysis.
•  A catalyst accelerates the rate of a
reaction without itself being
consumed in the process.
separation
•  The catalyst achieves its function by
forming bonds with the reacting A B P
molecules and allowing these to
react to form a product, which
detaches from the catalyst, and
leaves it unaltered such that it is P
available for the next reaction. catalyst
•  Hence the elementary steps involved catalyst
in a catalytic process involve:
–  Chemical bonding bonding
–  Chemical reaction
–  Separation
•  Catalysis is subdivided into 3 sub- A B
areas:
–  Homogeneous catalysis catalyst reaction
–  Biocatalysis
–  Heterogeneous catalysis.
Potential energy
A + B P Diagram for
Heterogeneously
Catalyzed reaction.
Non-catalytic
pathway
Activation
barrier
energy

ΔG † NC

ΔG †C Catalytic
pathway

A B
AB P
catalyst catalyst P
catalyst catalyst
bonding reaction separation

Reaction co-ordinate
Surface reactions.
•  Diffusion of reactants to the active surface.
•  Adsorption of one or more reactants onto
the surface.
•  Surface reaction .
•  Desorption of products from the surface.
•  Diffusion of products away from the
surface.
Catalysis at solid surfaces

gas phase
pathway

energy
EG

EA

gas phase ED
reactants
ES
adsorbed
gas phase Ej = activation G : gas phase reaction
reactants adsorbed products energy for step j. A : adsorption
surface products S : surface reaction
catalysed D : desorption
pathway Reaction intermediates stabilized via bonding
to catalytic surface sites.
The Metal-Catalyzed Hydrogenation
of Ethylene H C CH (g) + H (g) H3C CH3 (g)
2 2 2
reaction between surface migration
C2 H 4 ads H •
ads adsorbed species

H ads

dissociative
adsorption

H 2C • − CH 3 ads

H ads

How do molecules bond to
surfaces?
•  Two principal modes of adsorption of
molecules to surfaces.
–  Physical Adsorption : the only bonding is by weak
Van der Waals - type forces. There is no
significant redistribution of electron density in
either the molecule or at the substrate surface.
–  Chemisorption : a chemical bond, involving
substantial rearrangement of electron density, is
formed between the adsorbate and substrate. The
nature of this bond may lie anywhere between the
extremes of virtually complete ionic or complete
covalent character.
Potential energy versus distance curves for physisorption
and chemisorption.

The weak physical adsorption forces and associated


long-range attraction will be present to varying
degrees in all adsorbate / substrate systems.
However, in cases where chemical bond formation
between the adsorbate and substrate can also
occur, the PE curve is dominated by a much deeper
chemisorption minimum at shorter values of d .

Combine physisorption and


chemisorption curves.

The depth of the chemisorption well is a measure of the


strength of binding to the surface - in fact it is a direct
representation of the energy of adsorption, whilst the
location of the global minimum on the horizontal axis
corresponds to the equilibrium bond distance (re ) for the
adsorbed molecule on this surface.
The energy of adsorption is negative, and since it
corresponds to the energy change upon adsorption it is
better represented as ΔE(ads). However, you will also often
find the depth of this well associated with the enthalpy of
adsorption, ΔH(ads).
Terminology.
•  Substrate - frequently used to describe the solid surface onto
which adsorption can occur; the substrate is also occasionally
(although not here) referred to as the adsorbent.
•  Adsorbate - the general term for the atomic or molecular
species which are adsorbed (or are capable of being adsorbed)
onto the substrate.
•  Adsorption - the process in which a molecule becomes adsorbed
onto a surface of another phase (note - to be distinguished from
absorption which is used when describing uptake into the bulk of
a solid or liquid phase)
•  Coverage - a measure of the extent of adsorption of a species
onto a surface (unfortunately this is defined in more than one
way ! ). Usually denoted by the lower case Greek "theta", θ
•  Exposure - a measure of the amount of gas which as surface has
seen; more specifically, it is the product of the pressure and
time of exposure (normal unit is the Langmuir, where 1 L = 10-6
Torr s ).
Typical Characteristics of Adsorption Processes

Physisorption
Chemisorption

Virtually unlimited
Temperature Range Near or below the condensation
(but a given molecule may
(over which adsorption point of the gas
effectively adsorb only over a
occurs) (e.g. Xe < 100 K, CO2 < 200 K)
small range)
Related to factors like molecular
Wide range (related to the
mass and polarity but typically
Adsorption Enthalpy chemical bond strength) -
5-40 kJ mol-1 (i.e. ~ heat of
typically 40 - 800 kJ mol-1
liquefaction)
Crystallographic Specificity
(variation between different Marked variation between Virtually independent of surface
surface planes of the same crystal planes atomic geometry
crystal)
Often dissociative Non-dissociative
Nature of Adsorption
May be irreversible Reversible
Saturation Uptake Limited to one monolayer Multilayer uptake possible
Very variable - often an Fast - since it is a non-activated
Kinetics of Adsorption
activated process process
Irving Langmuir Employed at General Electric (industrial
(1881 - 1957) research).
Examined oxygen adsorption on tungsten
filaments of light bulbs.
1932: Nobel Prize in Chemistry.

Ag

dynamic
surface equilibrium
Aads

1915. Langmuir adsorption


Isotherm.
Kp
θ=
1+ Kp
Adsorption at gas/solid interface.
Adsorption. Term used to describe the process whereby a molecule (the
adsorbate) forms a bond to a solid surface (an adsorbent).

Fractional surface coverage


N number of sites occupied by adsorbate
θ θ= S
When θ = 1, NS = NΣ and an NΣ total number of adsorption sites

adsorbed monolayer is formed.
The fractional coverage θ depends A (g)
on pressure of adsorbing gas phase species.
This θ = θ (p) relationship is called an adsorption dynamic
isotherm. equilibrium
surface Aads
Langmuir Adsorption Isotherm.
Simple approach to quantitatively describe an adsorption
process at the gas/solid interface. Number of
N Σ = N S + NV Vacant sites
Assumptions :
•  solid surface is homogeneous and contains a number of equivalent sites, each
of which is occupied by a single adsorbate molecule
•  a dynamic equilibrium exists between gas phase reactant and adsorbed species
•  no interactions between adsorbed species
•  adsorbed species localised, ΔHads is independent of coverage θ
associative adsorption
kA adsorption rate constant
A (g) + S Aads
kD desorption rate constant
K measures affinity
kA of a particular
A2 (g) + S 2 Aads kA molecule for an
kD K=
kD adsorption site.
surface adsorption site
dissociative adsorption
At equilibrium : RA = RD

(
k A p 1− θ = kDθ )
Rate of adsorption :


(
RA = k A pNV = k A p 1− θ N Σ ) Kp
Langmuir adsorption
isotherm :
θ= associative adsorption.
pressure
fractional coverage 1+ Kp
slope = 1/K
of vacant sites 1
Rate of desorption : 1 1 θ
= 1+ 1 1
R = k N = kDθ N Σ
D D S θ Kp p
fractional surface coverage
A similar analysis can be done for dissociative adsorption.

Adsorption
( )
2
rate RA = k A pN 1− θ 2
Σ 1
Desorption RD = kD N Σ2θ 2 θ
rate

1
At equilibrium : RA = RD S=
K 1
( )
2
k A p 1− θ = kDθ 2 p

θ2 kA
Adsorption isotherm = p = Kp
(1− θ ) kD
2
for dissociative 1 1
adsorption. = 1+
Kp θ Kp
θ=
1+ Kp

high p Kp >> 1
Langmuir Adsorption Isotherm.
limit : 1+ Kp ≅ Kp
monolayer
formed θ → 1
1.0

0.8
Surface coverage θ K large
0.6

K = 10
0.4 K=1
K = 0.1

0.2 K small
Low p limit :
Henry Law 0.0
0.0 0.5 1.0 1.5 2.0
Kp << 1 P/atm
1+ Kp ≅ 1
θ ≅ Kp
Kp
θ=
1+ Kp
Adsorption Energetics

Adsorption of a gas on a solid is EA


an exothermic process : Δ Hads is ED
negative.
A(g)
Both adsorption and desorption
processes follow the Arrhenius
equation. ΔHads
adsorption pre-exponential factor

⎡ EA ⎤ Aads
k A = AA exp ⎢ − activation energy for
⎥ adsorption
⎢⎣ RT ⎥⎦
⎡ ED ⎤ activation energy for
kD = AD exp ⎢ − ⎥ desorption
⎢⎣ RT ⎥⎦ kA AA ⎡ ΔHads ⎤
K = = exp ⎢ −
temperature (K) ⎥
kD AD ⎢⎣ RT ⎥⎦
desorption pre-exponential factor
ΔH = E A − E D
R = gas constant = 8.314 J mol-1 K-1 ads
How is ΔHads measured ? entropy of adsorption ΔHads ΔSads
0 0

lnK = − +
RT R
ΔGads
0
= −RT lnK = ΔHads
0
−TΔSads
0
⎛ ∂lnK ⎞ ΔHads
0

⎜⎝ ∂T ⎟⎠ = RT 2
entalphy of adsorption θ
Gibbs energy of adsorption
Langmuir adsorption assumed constant surface coverage
⎛ ∂ln p ⎞ ΔHads
0

θ constant surface ⎜⎝ ∂T ⎟⎠ = − RT 2
Kp = coverage θ
1− θ
⎡ ⎛ p ⎞ ⎤ ΔH 0 ⎧⎪ 1 1 ⎫⎪
⎧ θ ⎫ ⎢ln ⎜ 1 ⎟ ⎥ = ads
⎨ − ⎬
lnK + ln p = ln ⎨ ⎬ p
⎢ ⎝ 2 ⎠ ⎥⎦θ R ⎪⎩ T1 T2 ⎪⎭
⎩ 1− θ ⎭ ⎣
1.0
⎛ ∂lnK ⎞ ⎛ ∂ln p ⎞
⎜⎝ ∂T ⎟⎠ + ⎜⎝ ∂T ⎟⎠ = 0 T2 Determine adsorption
θ θ
Isotherm curves at
⎛ ∂ln p ⎞ ⎛ ∂lnK ⎞ T1 various temperatures.
= − θ 0.5
θ

⎜⎝ ∂T ⎟⎠ ⎜⎝ ∂T ⎟⎠
θ θ Measure values of p and T
at a constant surface
0.0
coverage.
0 1 2 Using this idea, p1, p2, T1
p and T2 can be measured so
p2 p1
ΔHads can be determined.
Constant θ Ln p
⎛ ∂ln p ⎞ ΔHads
⎜ ⎟ = −

(
⎜⎝ ∂ 1/T ) ⎟⎠
θ
R

Read off p,T data at constant


coverage. 1/T
High T
Plot of ln p versus 1/T at
constant surface coverage
is linear.
Slope of plot enables one
Low T to evaluate ΔHads.
This can be repeated for
various set values of the surface
coverage, to enable ΔHads to be
Determine adsorption isotherm determined over the entire
at various temperatures. range of surface coverage θ .
Kinetics of surface reactions
•  We probe the reaction kinetics
of surface processes assuming
Langmuir adsorption isotherm.
•  Two principal types of reaction pA
mechanism are usually B
considered: A
–  Langmuir- Hinshelwood fast RDS
fast
–  Eley- Rideal. khet
ΘΑ
•  In the Langmuir-Hinshelwood
mechanism the reactants are all
adsorbed on the surface and
react at the surface.
•  In the Eley-Rideal mechanism
one has reaction between a pA
reactant in the gas phase and a A
reactant adsorbed on the pB AB
surface. B
RDS
khet
fast
ΘΑ
Langmuir - Hinshelwood Kinetics
1915
Langmuir
Isotherm

1927
Kinetics of
Catalytic
Reactions

Cyril Norman Irving Langmuir


Hinshelwood 1881 - 1957
1897 - 1967 Nobel Prize 1932
Nobel Prize 1956
Langmuir-Hinshelwood

A P B

Eley-Rideal

A B

P
Kinetics of surface reactions. Langmuir-Hinshelwood Mechanism

Unimolecular: single molecular species A adsorbs on surface,


reacts and the product P does not adsorb.
A(g) → Aads → P(g)
Reaction Surface coverage of adsorbed gas
rate R = kθ A Surface coverage
related to gas
K A pA
θA = pressure p via
Langmuir adsorption
1+ K A p A isotherm
kK A p A
R= Example: decomposition of NH3 on W
1+ K A p A surfaces. Rate 1st order at low p, while
as pressure increases it changes to zero order
Limiting situations. corresponding to saturation kinetics.

High pressures. Low pressures.


Rate depends

Kp >> 1
Rate independent of
Gas pressure p Kp << 1 linearly on gas
Pressure p
Zero order kinetics. First order kinetics.
Adsorption process
R ≅ kKp
Adsorption rate very
R ≅ k large when p is high.
is rate determining
when p is low.
Decomposition step rds. Decomposition is fast.
kKp
R=
1+ Kp
Competitive adsorption and bimolecular surface kinetics.

A B 2 different gas phase reactants compete


for adsorption sites S.
k1
A(g) + S Aads k
Aads + Bads ⎯→
⎯ C ads
k-1
k2

Catalyst surface B(g) + S Bads
k-2 Bimolecular surface
Assuming an adsorption/desorption
reaction
equilibrium for each gas we get:

θA
K A pA
= K A pA θA =
1− θ A − θ B 1+ K A pA + K B pB

θB K B pB
= K B pB θB =
1− θ A − θ B 1+ K A pA + K B pB

k1
KA = kK AK B pA pB
k−1 dc
RΣ = = kθ Aθ B =
dt
( )
2
k2
KB = 1+ K A pA + K B pB

k−2
LH model bimolecular reaction
dc kK AK B pA pB
RΣ = = kθ Aθ B =
Maximum rate occurs where dt
( )
2
θA = θB = 0.5 1+ K A pA + K B pB

For constant PB
rate

Rate limited by
surface concentration of A
Rate limited by
surface concentration of B

pA
θΒ << θΑ
θΒ >> θΑ
Eley-Rideal Mechanism.
Mechanism describes a surface reaction in pA
which one reactant is adsorbed while A
the other is in the gas phase. pB AB
B
A(g) → Aads RDS
khet
Aads + B(g) → P(g) fast
ΘΑ
An adsorbed molecule may react
directly with an impinging gas
molecule by a collisional mechanism

Reaction rate R is dependent on the Rate always 1st order wrt pB.
pressure of B pB, and the surface 2 limiting cases for reaction order
coverage of A θA. wrt pA.
When KA (ΔHads) is small or pA is small
We assume that B and product P do then KApA <<1 and R = kKApApB.
not competitively bind for surface sites Rate is 1st order wrt pA.
with A. When KA (ΔHads) is large or pA is large
then KApA >>1 and R = kpB.
kK A p A pB Rate is zero order wrt pA.
R = kθ A pB = Competitive adsorption of products
1+ K A p A can complicate the kinetics.
Diagnosis of mechanism
If we measure the reaction rate as a function of the coverage by A, the
rate will initially increase for both mechanisms.
Eley-Rideal: rate increases until surface is covered by A.
Langmuir-Hinshelwood: rate passes a maximum and ends up at zero,
when surface covered by A.
The reaction B + S ó B-S
cannot proceed when A blocks all sites.
Catalyst Preparation
For a catalyst the desired properties are
•  high and stable activity
•  high and stable selectivity
•  controlled surface area and porosity
•  good resistance to poisons
•  good resistance to high temperatures and temperature fluctuations.
•  high mechanical strength
•  no uncontrollable hazards

Once a catalyst system has been identified, the parameters in the


manufacture of the catalyst are
•  If the catalyst should be supported or unsupported.
•  The shape of the catalyst pellets. The shape (cylinders, rings, spheres,
monoliths) influence the void fraction, the flow and diffusion
phenomena and the mechanical strength.
•  The size of the catalyst pellets. For a given shape the size influences
only the flow and diffusion phenomena, but small pellets are often much
easier to prepare.
•  Catalyst based on oxides are usually activated by reduction in H2 in the
reactor.
Ammonia synthesis

A: Steam reforming
B: High temperature water-gas shift
C: Low temperature water-gas shift
D: CO2 absorption
E: Methanation
F: Ammonia synthesis
G: NH3 separation.
Ammonia Synthesis

Fe/K catalyst

exothermic
Mechanism

1 N2(g) + * N 2*
2 N 2* + * 2N*
3 N* + H* NH* + *
4 NH* + H* NH2* + *
5 NH2* + H* NH3* + *
6 NH3* NH3(g) + *
7 H2(g) + 2* 2H*

Step 2 is generally rate-limiting. Volcano curve is


therefore apparent with d-block metals as catalysts.
Ru and Os are more active catalysts, but iron is
used.
Biocatalysis: Kinetics of enzyme reactions.

Enzymes are very specific biological catalysts. This material is


A catalyst is a substance that increases the rate of a described in most
Biochemistry texts.
reaction without itself being consumed by the process.
•  A catalyst lowers the Gibbs energy of activation ΔG ‡ by providing a different
mechanistic pathway by which the reaction may proceed. This alternative mechanistic
path enhances the rate of both the forward and reverse directions of the reaction.
•  The catalyst forms an intermediate with the reactants in the initial step of the reaction
( a binding reaction), and is released during the product forming step.
•  Regardless of the mechanism and reaction energetics a catalyst does not effect ΔH or
ΔG of the reactants and products. Hence catalysts increase the rate of approach to
equilibrium, but cannot alter the value of the thermodynamic equilibrium constant.

EA lowered
A reactant molecule acted upon
catalyst absent by an enzyme is termed a substrate.
energy

The region of the enzyme where the


ΔEA substrate reacts is called the active
reactants catalyst present site. Enzyme specificity depends on
the geometry of the active site and the
products spatial constraints imposed on this region
ΔH by the overall structure of the enzyme
thermodynamics molecule.
unchanged
reaction coordinate
Space filling models of
Enzyme lock/key mechanism : the two conformations of
the enzyme hexokinase.
natural molecular recognition. (a) the active site is not
occupied. There is a cleft in
the protein structure that allows
the substrate molecule glucose
to access the active site.
(b) the active site is occupied.
The protein has closed around
the substrate.

hexokinase
glucose
Classification of enzymes.
Amperometric Glucose Sensors
•  Enzymes are very specific biological
catalysts.
•  They interact with substrates via the
Michaelis/Menten mechanism.
•  If enzymes can be incorporated and
immobilized within a matrix located next
to an electrode surface, then it is
possible to combine the specificity of
enzyme catalysis with the many
advantages of amperometric detection.
•  We focus attention of glucose oxidase
and the amperometric detection of blood
glucose, since the glucose sensor is well
developed commercially.

•  A. Heller, B. Feldman, Electrochemical glucose


sensors and their applications in diabetes
management. Chem. Rev. 2008, in press.
•  J. Wang, Electrochemical glucose biosensors.
Chem. Rev., 108 (2008) 814-825.
•  J. Wang, Glucose biosensors: 40 years of
advances and challenges. Electroanalysis, 13
(2001) 983-988.
•  J. Wang, In vivo glucose monitoring: towards
‘sense and act’ feedback loop individualized
medical systems. Talanta, 75 (2008) 636-641.
Redox enzymes.
•  Redox enzyme contains •  Flavoproteins are most often
tightly bound redox active studied.
prosthetic group (e.g. flavin, •  They consist of ca. 80
haem, quinone) that remains different enzymes containing
bound to the protein either
throughout redox cycle. –  Flavin adenine dinucleotide
–  Prosthetic group = non amino (FAD)
acid component of –  Flavin mononucleotide (FMN)
conjugated protein.
at the active site.
•  Redox enzymes exist in both
oxidised and reduced forms. •  The flavin unit is strongly
associated with the protein
•  Redox enzymes can be structure and is sometimes
subclassified in terms of the covalently bound to the amino
redox centres present in the acid residues in enzyme.
enzyme.
Dimeric structure of glucose oxidase
Glucose oxidase GOx.
b-D-glucose: oxygen
1-oxidoreductase
EC1.1.3.4) : GOx .

GOx is a dimeric protein


with MW = 160 kDa.
Contains one tightly bound
flavin adenine dinucleotide
FAD unit per monomer as
cofactor. FAD is not
covalently bound and can be
released from the holo
protein following
denaturation.
FAD exhibits redox activity.
Gox exhibits a very high
degree of specificity for monomeric unit
β-D-glucose.
redox active
region

protein sheath

FAD active site

Structure of FAD redox site in GOx.


Enzyme catalysed reaction:
Variation of reaction rate with substrate (reactant)
concentration.
Rate variation adopts shape of rectangular hyperbola.
1.2
Ψ = RΣ Rmax = RΣ kc [E]Σ

1.0

Saturated enzyme
Ψ=RΣ/k erate

0.8
c Σ

kinetics
Normalized

0.6

Unsaturated enzyme
0.4 kinetics

0.2
Normalized substrate concentration
0.0
0 10 20 30 40 50

u=c/KM This is an example of a


complex rate equation, where
the reaction rate varies with
In electrochemical biosensor output have current (rate) reactant concentration
vs substrate concentration. in a non linear way.
Time course of enzyme catalyzed reaction.

Assume that [S] >> [E]

Note logarithmic timescale.

Note linear timescale.


Single substrate Michaelis-Menten Kinetics.
Enzyme-substrate complex
Rate

Also termed kc or turnover


number = max number of
enzymatic reactions catalyzed kc/KM measures catalytic efficiency of enzyme.
per second. Maximum value corresponds to
Diffusion control reaction between
S and E in solution (1010 M-1s-1).
Note: Biochemistry texts use υ
as symbol for reaction rate (velocity).
SF Chemical Kinetics.

Lecture 5.
Microscopic theory of chemical
reaction kinetics.
Microscopic theories of
chemical reaction kinetics.
•  A basic aim is to calculate the rate constant for a chemical reaction
from first principles using fundamental physics.
•  Any microscopic level theory of chemical reaction kinetics must
result in the derivation of an expression for the rate constant that
is consistent with the empirical Arrhenius equation.
•  A microscopic model should furthermore provide a reasonable
interpretation of the pre-exponential factor A and the activation
energy EA in the Arrhenius equation.
•  We will examine two microscopic models for chemical reactions :
–  The collision theory.
–  The activated complex theory.
•  The main emphasis will be on gas phase bimolecular reactions since
reactions in the gas phase are the most simple reaction types.
References for Microscopic Theory
of Reaction Rates.
•  Effect of temperature on reaction rate.
–  Burrows et al Chemistry3, Section 8.7, pp.383-389.
•  Collision Theory/ Activated Complex Theory.
–  Burrows et al Chemistry3, Section 8.8, pp.390-395.
–  Atkins, de Paula, Physical Chemistry 9th edition,
Chapter 22, Reaction Dynamics. Section. 22.1, pp.
832-838.
–  Atkins, de Paula, Physical Chemistry 9th edition,
Chapter 22, Section.22.4-22.5, pp. 843-850.
SCT : a summary.
•  The major problem with SCT is that the threshold energy E* is very
difficult to evaluate from first principles.
•  The predictions of the collision theory can be critically evaluated by
comparing the experimental pre-exponential factor with that computed
using SCT.
•  We define the steric factor P as the ratio between
the experimental and calculated A factors.
P=A A
•  We can incorporate P into the SCT
exp calc

expression for the rate constant. ⎡ E*⎤


•  For many gas phase reactions k = Pz AB
exp ⎢− ⎥
⎣ RT ⎦
P is considerably less than unity.
•  Typically SCT will predict that Acalc will be in ⎡ E*⎤
k = Pz AA exp ⎢ − ⎥
the region 1010-1011 Lmol-1s-1 regardless of ⎣ RT ⎦

the chemical nature of the reactants and products.
•  What has gone wrong? The SCT assumption of hard sphere collision
neglects the important fact that molecules possess an internal structure.
It also neglects the fact that the relative orientation of the colliding
molecules will be important in determining whether a collision will lead to
reaction.
•  We need a better theory that takes molecular structure into account. The
activated complex theory does just that .
Transport
Summary of SCT. property
Energy criterion

A,B encounters ⎡ E*⎤


k = Pz AB exp ⎢ − ⎥
1/2 ⎣ RT ⎦
⎧⎪ 8kBT ⎫⎪ ⎡ E*⎤
k = N Aσ ⎨ ⎬ exp ⎢−
⎪⎩ π µ ⎪⎭

⎣ RT ⎦ ⎡ E*⎤
k = Pz AA exp ⎢ − ⎥
⎡ E*⎤
= z AB exp ⎢ − ⎥ ⎣ RT ⎦
⎣ RT ⎦
Steric factor
(Orientation requirement)
A,A encounters Weaknesses:
•  No way to compute P from molecular
parameters
1/2
⎧⎪ kBT ⎫⎪ •  No way to compute E* from first principles.
⎡ E*⎤
k = 2N Aσ ⎨ ⎬ exp ⎢− ⎥ Theory not quantitative or predictive.
⎪⎩ π m ⎪⎭ ⎣ RT ⎦ Strengths:
• Qualitatively consistent with observation
⎡ E*⎤ (Arrhenius equation).
= z AA exp ⎢ − ⎥
⎣ RT ⎦ •  Provides plausible connection between
microscopic molecular properties and
macroscopic reaction rates.
•  Provides useful guide to upper limits for rate
constant k.
Course Summary
•  Basic terms in reaction kinetics: reaction order, reaction rate.
•  Simple rate equations: zero, first, second order kinetics
•  Rate equations for more complex reactions
–  Consecutive reactions
–  Parallel Reactions
–  Third order reactions
–  Equilibrium
–  Steady State Analysis of complex reactions
•  Catalytic reactions
–  Surface reactions & Heterogeneous catalysis
–  Bio-catalysis & Enzyme kinetics
•  Temperature Dependence of Reaction Rate
•  The theory of reaction kinetics
–  Simple Collision Theory (SCT)