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Chemical Kinetics
2011/2012.
Dr Mike Lyons
Course Summary.
Contact short but sweet. 5 Lectures in total (4 this week, 1 next
week, 3 tutorials next week).
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 1-2. 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 3,4. Enzyme kinetics (Michaelis-Menten case) and surface
reactions involving adsorbed reactants (Langmuir adsorption
isotherm).
Lecture 5. Theory of chemical reaction rates : bimolecular
reactions. Simple Collision Theory & Activated Complex Theory.
Recommended reading.
P.W. Atkins and J. de Paula. Physical Chemistry for the Life Sciences. 1st
edition. OUP (2005). Part II entitled The kinetics of life processes (Chapters
6,7,8) is especially good.
A more advanced and complete account of the course material. Much of chapter 24 is
JS material.
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!
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 1-2.
Quantitative Reaction
Kinetics.
1 femtosecond (fs)
= 10-15 s = 1/1015 s !
Picosecond (10-12s)
techniques
Femtosecond
(10-15 s)techniques
reactants
products
H 2 ( g ) I 2 ( g ) 2HI ( g )
Thermodynamics tells us all
about the energetic feasibility
of a reaction : we measure the
Gibbs energy DG for the chemical
Reaction.
Thermodynamics does not tell us
how quickly the reaction will
proceed : it does not provide
kinetic information.
We wish to quantify
Reaction Rate.
Reactant
concentration
Product
concentration
d R d P
dt
dt
[R]t
time
Geometric definition of
reaction rate.
Rate expressed as tangent line
To concentration/time curve at a
Particular time in the reaction.
d [ R]
dt
d P
dt
rate = -
dO3
d[NO]
d[ NO2]
d[O2]
==+
=+
dt
dt
dt
dt
aA bB pP qQ
Rate
1 d A
1 d B
a dt
b dt
1 d Q
1 d P
q dt
p dt
RJ
DJ 1 d J
D
t
0
J
Dt
J dt
1
lim
2 H 2 ( g ) O2 ( g ) 2 H 2O( g )
R
1 d H 2
d O2 1 d H 2O
2 dt
dt
2 dt
2 N 2O5 ( g ) 4 NO2 ( g ) O2 ( g )
T = 338 K
(rate) 0 N 2O5 0
(rate) 0 k N 2O5 0
Rate
Equation.
rate
k
xA yB
Products
empirical rate
equation (obtained
from experiment)
stoichiometric
coefficients
k = rate constant
d N 2O5
k N 2O5
dt
rate constant k
1 d A
1 d B
k A B
x dt
y dt
, = reaction
orders for the
reactants (got
experimentally)
Rate equation can not in
general be inferred from
the stoichiometric equation
for the reaction.
Log R
Log R
Slope =
Slope =
Log [A]
Log [B]
H 2 X 2 2 HX
X I , Br , Cl
H 2 I 2 2 HI
d HI
k H 2 I 2
dt
H 2 Br2 2 HBr
R
d HBr k H 2 Br2
k HBr
dt
1
Br2
1/ 2
H 2 Cl2 2 HCl
R
d HCl
1/ 2
k H 2 Cl2
dt
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 Products
as
dc
dt
kF (c )
10
R c0
Rate equation :
dc
R k
dt
c c0 when t 0
integrate
using initial
half life
condition
c(t ) kt c0
t 1/ 2 when c
1/ 2
slope = -k
c0
1/ 2 c0
2k
1/ 2
c0
slope
diagnostic
plot
k
A
products
dc
dt
1
2k
c0
rate
c0
2
dc
kc
dt
Initial condition
t 0 c c0
Solve differential
equation
Via separation
of variables
(rate)t c
(rate)t kc
k = first order
rate constant, units: s-1
11
t 1/ 2
c0
2
u 1/ 2
1/ 2
k s
1/ 2
ln 2 0.693
k
k
kt
1
c0
a
a0
1
c t dt c
0
c0e kt dt
u 1
t 1/ 2
In each successive period
of duration t1/2 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,
the concentration is (1/2)n of its
initial value.
1
k
c c0 / 2
u 0.5
u 0.25
u 0.125
1/ 2
1/ 2
c0
ln 2 0.693
k
k
half life independent of
initial reactant concentration
12
dm3mol-1s-1
2A
P
k
slope = k
dc
kc 2
dt
t 0 c c0
half life
separate variables
integrate
1
1
kt
c
c0
t 1/ 2
1/ 2
1
kc0
1/ 2
1
c0
c0
2
t
c t
1/ 2
1/ 2 as c0
1
c
c(t ) c0e kt
u ( ) e
kt
c0
1 kc0t
c0
rate varies as
square of reactant
concentration
c(t )
c0
1 kc0t
u ( )
1
1
kc0t
13
k1
A
Products
k2
2 A
Products
ln c(t)
Differential
rate equation
dc
k1c
dt
dc
k2 c 2
dt
Concentration
variation with
time
c(t )
c0 exp k1t
c(t )
c0
1 k2 c0t
Slope = - k1 1/c(t)
ln c(t ) k1t ln c0
1
1
k2t
c(t )
c0
1/2
Slope = k2
1/ 2
1/ 2 c01 n
n 1 1/ 2 as c0
n 1 1/ 2 as c0
ln 1/ 2
1/ 2
1
k2 c0
Diagnostic
Plots .
k
nA
1
c n 1
n 1
n 1 kt
1
c0 n1
rate constant k
obtained from slope
Half life
2n 1 1
n 1 kc0n1
ln 2
k1
c0
n = 0, 2,3,..
1/ 2
2nd order
separate variables
integrate
n 1
Half
Life
1st order
dc
kc n
dt
t 0 c c0
Diagnostic
Equation
2n 1 1
ln
n 1 ln c0
n
1
k
slope n 1k
t
ln 1/ 2
slope n 1
ln c0
14
t 0 c c0
k
nA
t 1/ 2
Rate equation
Reaction
Order
dc
dt
kc
ln 0 kt
c t
s-1
ln 2
k
kc 2
1
1
kt
c t
c0
dm3mol-1s-1
1
kc0
kc3
1
1
2kt 2
c2 t
c0
dm6mol-2s-1
3
2kc0 2
kc n
1
1
n 1 kt n1
c n1
c0
1 2n 1 1
n 1 kc0 n 1
k
A B
Pseudo first
order kinetics
when b0 >>a0
half life
rate equation
1
ln 2
ka0 1
da
db dp
R
kab
dt
dt dt
1/ 2
initial conditions
b
0
a0
t 0 a a0
b b0
1
1/ 2
dm3mol-1s-1
F a, b
1
b0 a0
b b0
kt
ln
a
a
0
F a, b
ln 2 ln 2
kb0
k
k kb0
a0 b0
integrate using
partial fractions
c0
2
slope = k
15
16
TS
DU
d ln K c
2
dT P RT
DU 0 E E
k
k
DU0
P
P
Reaction coordinate
k
Kc
k
d k
d ln k d ln k DU
dT ln k dT dT RT 2
P
d ln k
E
dT
RT 2
d ln k
E
dT
RT 2
d ln k
d ln k
RT 2
E A R
d
1
/
T
dT
ln k
Slope
EA
R
1
T
17
18
E
k aT m exp
RT
We can relate the latter expression to the Arrhenius parameters A and EA
as follows.
ln k ln a m ln T
E
RT
E
d ln k
2 m
E A RT 2
E mRT
RT
2
dT
T RT
E E A mRT
Hence
E
E
k aT m em exp A A exp A
RT
RT
m m
A aT e
Consecutive Reactions .
Mother / daughter radioactive
decay.
Po Pb Bi
218
214
Svante August
Arrhenius
k1
k2
A
X
P
Mass balance requirement:
214
k1 5 103 s 1
k2 6 104 s 1
p a0 a x
The solutions to the coupled
equations are :
da
k1a
dt
dx
k1a k 2 x
dt
dp
k2 x
dt
x(t )
k1a0
exp k1t exp k2t
k 2 k1
k1a0
exp k1t exp k2t
k 2 k1
19
Case I .
k2
1
k1
TS II
k 2 k1
TS I
I : fast
DGI <<
energy
k1
k2
A
X
P
II : slow
rds
DGI
DGII
DGII
X
P
reaction co-ordinate
Step II is rate determining
since it has the highest
activation energy barrier. The reactant species A will be
more reactive than the intermediate X.
Case I .
k2
1
k1
k 2 k1
k1
k2
A
X
P
a
u
a0
x
v
a0
p
w
a0
Normalised concentration
1.2
k2/ k1 = 0.1
1.0
u = a/a0
v = x/a0
Intermediate X
0.8
w = p/a0
0.6
Reactant A
0.4
Product P
0.2
0.0
0
10
k1t
Concentration of intermediate
significant over time course of
reaction.
20
k2
k1
k1
k2
A
X
P
Case II .
k
2 1
k1
key parameter
Intermediate X fairly reactive.
[X] will be small at all times.
k 2 k1
k1
k2
A
X
P
DGI >>
II : fast
DGII
TS II
DGI
energy
I : slow rds
TS I
DGII
A
k1
k2
A
X
P
reaction co-ordinate
1.2
normalised concentration
Case II .
k
2 1
k1
k 2 k1
Intermediate X
is fairly reactive.
Concentration of
intermediate X
will be small at
all times.
1.0
Product P
0.8
u=a/a0
v=x/a0
0.6
w=p/a0
Reactant A
0.4
0.2
= k 2/k1 = 10
Intermediate X
0.0
0
10
= k1t
normalised concentration
1.2
u=a/a0
1.0
v =x/a0
Intermediate concentration
is approximately constant
after initial induction period.
w=p/a0
0.8
0.6
0.4
0.2
0.0
0.0
0.2
0.4
0.6
0.8
1.0
= k1t
21
k1 k2
k1
k2
A
X
P
Fast
Slow
k2 k1
Rate Determining
Step
k1
k2
A
X
P
Slow
Fast
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).
k1
A
X
k2
We consider the kinetic analysis of a concurrent
A
Y
or parallel reaction scheme which is often met in
st
k1, k2 = 1 order rate constants
real situations.
A single reactant species can form two
We can also obtain expressions
distinct products.
for the product concentrations
We assume that each reaction exhibits 1st order x(t) and y(t).
kinetics.
Initial condition : t= 0, a = a0 ; x = 0, y = 0
. Rate equation:
da
k1a k2 a k1 k2 a k a
dt
dx
k1a k1a0 exp k1 k 2 t
dt
x(t ) k1a0
x(t )
exp k
t
k 2 t dt
k1a0
1 exp k1 k2 t
k1 k 2
dy
k 2 a k 2 a0 exp k1 k 2 t
dt
y (t ) k 2 a0
y (t )
exp k
t
k 2 t dt
k 2 a0
1 exp k1 k2 t
k1 k 2
x(t ) k1
All of this is just an extension of simple Final product analysis
Lim
22
normalised concentration
1.0
Theory
0.1
v 0.9079
a(t)
0.8
x(t)
u()
v()
w()
0.6
0.4
= k2 /k1
/
0.2
w 0.0908
y(t)
0.0
0
= k1t
k2
0.1
k1
k1
v
10
k2
w()
normalised concentration
1.0
Theory
u()
v()
w()
0.6
0.4
a(t)
0.2
k2
10
k1
v() 0.0909
x(t)
0.0
0
w() 0.9091
y(t)
10
0.8
= k1t
k1
v
0.1
k2
w()
23
N2O4
NO2
N2O4 (g)
2 NO2 (g)
colourless
brown
Chemical Equilibrium :
a kinetic definition.
N2O4 (g)
2 NO2 (g)
colourless
Kinetic analysis.
R k N 2O4
2
R k NO2
Valid for any time t
brown
Equilibrium:
t
Concentrations vary
with time
NO2 t
N 2O4 t
concentration
RR
k N 2O4 eq k NO2 eq
NO2 eq2 k
K
N 2O4 k
Kinetic
regime
Concentrations time
invariant
NO2 eq
N 2O4 eq
Equilibrium
state
NO2
t
N2O4
time
Equilibrium
constant
24
k
A
B
k'
u v 1
0 u 1 v 0
da
ka k b
dt
Initial condition
t 0 a a0
b0
du
1
u
d
1
t a b a0
u
v
a
a0
b
a0
k k t
k
k
1
1 exp
1
1 exp
Reaction quotient Q
1 exp
1 exp
concentration
0.8
Equilibrium
Product B
K Q
v
0.6
u ()
v ()
0.4
Reactant A
0.2
0.0
0
(k+k')t
25
Approach to
Equilibrium
Q<
10
10
Q()
Equilibrium
Q=K=
6
4
2
0
0
= (k+k')t
1 exp
1 exp
t Q K
k
k
v
u
Operating at low
temperature is generally
associated with the idea of
high selectivity (this is
termed kinetic control).
Conversely, operating at high
temperature is associated
with low selectivity and
corresponds to
Thermodynamic control.
Time is also an important
parameter. At a given
temperature, although the
kinetically controlled product
predominates at short times,
the thermodynamically
Refer to JCE papers dealing with this
controlled product will
topic given as extra handout.
predominate if the reaction
time is long enough.
26
Short reaction
times
Temperature effect.
Kinetic control.
DG*j
k j A exp
RT
Thermodynamic control.
27
d R
dt
d P1
dt
d P2
dt
k1 k2 R k1 P1 k2 P2
k1 R k1 P1
k2 R k2 P2
Short time
Approximation.
Neglect k-1, k-2
terms.
P1
R R 0 exp k1 k2 t
k R
P1 1 0 1 exp k1 k2 t
k2 R 0
k1 k2
1 exp k k t
1
P1
P2
P1
P2
k1 R 0
k1 k2
k2 R 0
k1 k2
P1 k1
P2 k2
t
1
k1 k2
K1 R 0
1 K1 K 2
P2
k1 k2
P2
d R d P1 d P2
0
dt
dt
dt
R 0
R
1 K1 K 2
Kinetic control
Limit.
K 2 R 0
1 K1 K 2
K1
K2
Thermodynamic
control limit.
1 k2 1 k1 exp t 2 k1 2 k2 exp t
1
2
1 1 2
2 2 1
12
k k
k k
k k
P1 R 0 1 2 1 1 2 exp 1t 1 2 2 exp 2t
2 2 1
12 1 1 2
k k k k
k k
P2 R 0 1 2 2 1 1 exp 1t 2 2 1 exp 2t
2 2 1
12 1 1 2
k1k2
R R 0
1,2
2 4
2
k1 k2 k1 k2
k1k2 k1k 2 k1k2
4
1 1 2
2
28
k1
k2
A
X
P
dx
RX formation RX removal 0
dt
RX formation RX removal
Normalised concentration
1.0
u()
0.5
w()
v()
0.0
0.0
0.5
1.0
= k1t
intermediate X
concentration
approx. constant
P1
Fluid level
P2
29
k2
k-1
Rate
equations
du
u v
d
dv
u v
d
dw
v
d
a
u
a0
x
v
a0
p
w
a0
u v w 1
0 u 1 v w 0
k 1
k1
k2
k1
k1 t
w 1
exp exp
exp exp
1
dv
0
d
u ss vss 0
exp exp
u ss
du ss
u ss
d
vss
u ss exp
exp
vss
dwss
vss
exp
d
wss
d
exp
0
1 exp
30
normalised concentration
1.2
1.0
0.4
0.0
0.01
0.1
10
k2
u()
v()
w()
0.2
X
k-1
0.8
0.6
k1
100
log
Concentration versus log time curves
for reactant A, intermediate X, and
product P when the rate equations
are solved using the QSSA.
Values used for the rate constants
are the same as those used above.
QSSA reproduces the concentration
profiles well and is valid.
normalised concentration
1.2
0.8
uss ()
0.6
v ss ()
wss ()
0.4
0.2
X
0.0
0.01
normalised concentration
u()
v()
w()
0.2
0.0
10
k2
0.4
0.1
100
k-1
0.6
10
k1
1.0
0.01
0.1
log
1.2
0.8
1.0
100
log
1.2
normalised concentration
1.0
0.8
uss ()
0.6
v ss ()
wss ()
0.4
0.2
0.0
0.01
0.1
10
100
log
31