Lecture 26

Kinetics
Elementary Reactions
Reaction Order
Multi-step
Multi step processes
processes, Intermediates
Steady State Approximation
 Reaction Order
• The power to which a the concentration of a
species is raised in the rate law is the reaction
order.
d The
h overallll order
d is the
h sum off allll off the
h
powers of all reactants.
Examples:
1. v = k[NO]2[O2] First order in O2,
Second order in NO, Third order overall.
2. v = k[A]1/2[B]2 Half order in A, Second order
in B, 2 1/2 order overall.
• The order does not need to be an integer.
R ti order
Reaction d and
d molecularity
l l it
Reaction order is an empirical quantity.
Molecularity refers to an elementary reaction
as a step in a reaction mechanism.
The rate law of an elementary step
can be deduced directly from the reaction.
Unimolecular reactions are first order.
A → Products d[A]/dt = -k[A]
Bimolecular reactions are second order.
A + B → Products d[A]/dt = -k[A][B]
 A example:
An l 2NO + O2 2NO2
The formation of nitric oxide is a termolecular
reaction, i.e. three molecules must collide in
order for the products to be formed. In this
example the reaction is also the elementary
step and so the rate law is v = k[NO]2[O2] as
stated earlier. In this case the reaction is
third order because off the ffact that three
molecules must combine simultaneously.
However, theh reaction stoichiometry
h may not
always indicate the molecularity of the reaction.
 Q
Question:
ti Reaction
R ti Order
Od
What is the order of the reaction:
2 H2 + O2 2 H2O
A. First order
B. Second order
C. Third order
D. Unknown
 Q
Question:
ti Reaction
R ti Order
Od
What is the order of the reaction:
2 H2 + O2 2 H2O
A. First order
B. Second order
C. Third order
D. Unknown
 Q
Question2:
ti 2 Reaction
R ti Order
Od
The detailed mechanism of many enzymes has
been shown to include a rate determining
step:
E+S ES
What is the order of the overall reaction?
A. First order
B. Second order
C. Third order
D. Unknown
k
 Q
Question2:
ti 2 Reaction
R ti Order
Od
The detailed mechanism of many enzymes has
been shown to include a rate determining
step:
E+S ES
What is the order of the overall reaction?
A. First order
B. Second order
C. Third order
D. Unknown
k
 P ll l First
Parallel Fi Order
O d Reactions
R i
• A → B and d A → C so that:
h
A • d[A]/dt = -(k1+k2)[A]
k1 • d[B]/dt = k1[A]
B
• d[C]/dt = k2[A]
k2 • Solve for [A] first:
[A] = [A] 0exp{ – (k 1 + k 2)t }
then
C
d[B]
= k 1[A] 0exp{ – (k 1 + k 2)t }
dt
d[C]
= k 2[A] 0exp{ – (k 1 + k 2)t }
dt
 P ll l First
Parallel Fi Order
O d Reactions
R i
• The
h solutions
l are:
A k 1[[A]] 0
k1 [B] = 1 – exp{ – (k 1 + k 2)t }
k1 + k2
B k 2[A] 0
[[C]] = 1 – exp{
p{ – ((k 1 + k 2))t }
k2 k1 + k2

• The production of B and C

occurs with a constant
C
proportion:
[ ] k1
[B]
=
[C] k 2
 Sequential first-order reactions
C
Consecutive
i elementary
l reactions
i

A • A → B → C rate equations
k1 are:
B • d[A]/dt = -k1[A]
• d[B]/dt = k1[A] - k2[B]
k2 • d[C]/dt = k2[B]
• Either k1 or k2 can be the rate
C limiting step.
 Sequential first-order reactions
C
Consecutive
i elementary
l reactions
i

A • First solve eqn. for A

k1 [[A]] = [[A]] oe – k 1t
B • Substitute into eqn. for B
d[B]
[ ]
= k 1[A] – k 2[B] = k 1[A] oe – k 1t – k 2[B]
k2 dt
k 1[A] o – k 1t
[B] = e – e – k 2t
k2 – k1
C • Similarly for C

[C] = [A] o 1 – 1 (k e – k 1t – k e – k 2t)

2 1
k2 – k1
Populations
l as a function
f off time
• The population as a function
of time is given by the
solutions
l ti to
t the
th sequential
ti l
first order reactions.
A - -Green
[A](t) Initial • The case shown is
[B](t)
B - Intermediate
IYellow
Yt ll di t
intermediate with k1 = 1.5k2.
C - -Red
[C](t) Final • The population of B grows
and reaches a maximum and
then decays.

Time
 Rate determining step
• If k2 >> k1 then the first (A → B) step
becomes the rate-limiting g step.
p
• If the A → B step is rate limiting then little or
no B will be observed even though g it is
formed on the reaction path.
• If k1 >> k2 then the second ((B → C)) step p
becomes the rate limiting step.
• If the B → C step is rate limiting then there
will be a significant build-up of the
intermediate state B.
St d t t approximation
Steady-state i ti
• Equations representing kinetic networks of more than
three states are not soluble analytically.
• One means of pushing the techniques as far as
possible using analytical solutions is to set the
derivatives of intemediates equal to zero:
d[Intermediate]/dt = 0
• The build
build-up
up of intermediate B shown in the figure
(two slides back) implies that the steady state
pp
approximation does not work for the system
y shown
there.
 Application of the
steady-state
t d t t approximation
i ti
• The steady state approximation can be applied to the
consecutive reaction scheme
k1 k2
A → B → C.
if the
th concentration
t ti off B iis ffairly
i l constant.
t t

• The result of setting d[B]/dt = 0 is:

k1[A] - k2[B] = 0 and
d[C]/dt = k1[A]. Since d[A]/dt = - k1[A] we see that
d[C]/dt = - d[A]/dt andd [C]=(1
[C] (1 - exp{-k
{ k1t})
 Question: Rate schemes
h
Which rate equation describes the rate of
disappearance of A?
k1 k2
B A C
k-1 k
D
3

A. d[A]/dt = -(k1+ k2 + k3)[A] + k-1[B]

B d[A]/dt = (k1+ k2 + k3)[A] - k-11[B]
B.
C. d[A]/dt = - k1[B] - k2[C] - k3[D] + k-1[A]
D. d[A]/dt
[ ]/ = k1[[B]] + k2[[C]] + k3[[D]] - k-11[[A]]
 Question: Rate schemes
h
Which rate equation describes the rate of
disappearance of A?
k1 k2
B A C
k-1 k
D
3

A. d[A]/dt = -(k1+ k2 + k3)[A] + k-1[B]

B d[A]/dt = (k1+ k2 + k3)[A] - k-11[B]
B.
C. d[A]/dt = - k1[B] - k2[C] - k3[D] + k-1[A]
D. d[A]/dt
[ ]/ = k1[[B]] + k2[[C]] + k3[[D]] - k-11[[A]]
Example using the steady state
approximation
i ti
For the following folding scheme involving a
single intermediate determine the rate of
appearance of the folded form F.
k1 k2
U↔I→F
k-1
d[F]/dt = k2[I]
d[I]/dt = k1[U] - (k2 + k-1)[I]
d[U]/dt = -k1[U] + k-1[I]
Example using the steady state
approximation
i ti
Assuming that you have information that allows
you to use the steady state approximation
determine the form of d[F]/dt in terms of [U].
k1k2
U↔I→F
k-1
A d[F]/dt = [U] k1 k2 /(k2 + k-1)
A.
B. d[F]/dt = [U] k1 k2
C d[F]/dt = [U] (k2 + k-1)/k1 k2
C.
D. d[F]/dt = [U] (k2 + k-1)
Example using the steady state
approximation
i ti
Assuming that you have information that allows
you to use the steady state approximation
determine the form of d[F]/dt in terms of [U].
k1 k2
U↔I→F
k-1
A d[F]/dt = [U] k1 k2 /(k2 + k-1)
A.
B. d[F]/dt = [U] k1 k2
C d[F]/dt = [U] (k2 + k-1)/k1 k2
C.
D. d[F]/dt = [U] (k2 + k-1)
Example using the steady state
approximation
The equations below show the reasoning
behind the solution:
k1 k2
U↔I→F
k-1
d[I]/dt = k1[U] - (k2 + k-1)[I] = 0
k1[U] = (k2 + k-1)[I]
[I] = [U] k1/(k2 + k-1)
d[F]/dt = k2[I] = [U] k1 k2 /(k2 + k-1)
Biexponential kinetics result when the
steady-state approximation fails

• We cannot apply the steady state

approximation
pp if the concentration of B
changes significantly during the process
k1 k2
A → B → C.
• In this case we must solve the rate equations
q
• In general, for N processes the result will be
kinetics with N exponential time constants.
Here: [B](t) = Φ1e-k1t + Φ2e-k2t
 Photochemistry

• The intensity, I is measured in power per

unit area of photons per second per unit
area. The intensity is given in photons/s/m2
or einsteins/s/m
i t i / / 2.
• 1 einstein = 1 mole of photons.
• To
T convertt th
the iintensity
t it iin W/ m2 to
t tto
intensity in number of photon we use the
relation: h
hc
Ephoton = hν =
λ
 Photochemistry

• Beer-Lambert law is:

I = Io10 –A
, A = ε lc , c = [E]
• The concentration is c or [E]
• The intensity of absorbed light is Io – I.
I
• The extinction coefficient ε has units of
M-11cm-11. The exctinction coefficient
depends on the frequency ε(ω). Often ε is
abu a d at
tabulated a the peak
p a ofo absorption
abso p o
spectrum.
 Photochemistry

• Therefore, the rate of excitation of the

excited state of molecule E is:
d[E] 1000 – A 1000
– = φ(Io – I) = φIo(1 – 10 )
dt l l
• The quantum yield is φ.
• 1000 converts from cm3 to L
 Photochemistry

• We use the approximation:

≈ 1 – 2.303A
–A
10
• Thus,
d[E] 2303φIoε[E]
– =
dt NA
• Photoexcitation is a pseudo-first order
process where the excitation rate constant
is:
s 2303φIoε
k=
NA
 Competing or parallel
ll l processes

S1 • Decay of the singlet S1 state

can occur either radiatively by
fluorescence (kf ) or by internal
hν kf kIC conversion (kIC).
• d[S1]/dt = -(k
(kf + kIC)[S1]
• The overall decay rate constant
S0 is the sum of the rate constants.
Photoexcitation The fluorescence quantum yield
followed by return is
to the S0 ground state.
kf
Φ=
k f + k IC
 Question: Quantum yield
ld

The observed fluorescence quantum yield of

Rhodamine is Φf = 0.7. The observed lifetime is
13.0 ns. What is the intrinsic fluorescence lifetime?
A. 18.6 ns
B 13
B. 13.0
0 ns
C. 9.1 ns
D 0
D. 0.7
7 ns
 Question: Quantum yield
ld

The observed fluorescence quantum yield of

Rhodamine is Φf = 0.7. The observed lifetime is
13.0 ns. What is the intrinsic fluorescence lifetime?
A. 18.6 ns
B 13
B. 13.0
0 ns
C. 9.1 ns
D 0
D. 0.7
7 ns