11/13/2008
Lecture 25
Kinetics
Experimental techniques
Definition of Rate
First Order Processes
Exponential Decay
Time scales for experimental
measurement of reaction kinetics
• Spectroscopy is a key tool for monitoring
reaction progress on rapid time scales.
• Flash p photolysis
y is a convenient method for
initiating a time-dependent process with real-
time acquisition as rapid as ten femtoseconds.
• Rapid mixing flowed reactions can be
monitored at fixed distances with 100 μs time
resolution.
• Stopped-flow has a 1 ms mixing time.
• Quenching method suitable for slow reactions.
Rates of appearance
• For a chemical reaction d[J]/dt = njvj where nj
is the stoichiometric coefficient.
• Example: A + 2B + 3C → D + 2E
• If - d[A]/dt = v, then the rate of disappearance
is - d[B]/dt = 2v, - d[C]/dt = 3v and the rate
of appearance is d[D]/dt = v and d[E]/dt = 2v.
Experimental Techniques
• Monitor reaction progress using
pressure, conductivity,
spectrophotometry etc
spectrophotometry, etc. in real time
time.
• Quench reaction after a given time by
rapid cooling or solvent trapping.
• Initiate process by flow, stopped-flow,
rapid mixing or flash photolysis.
Definition of rate
• For any given reaction, e. g. A + B → C
• Rate of consumption of A is vA =- d[A]/dt
• Rate of formation of C is vC = d[C]/dt.
d[C]/dt
• Sign convention, reactants are consumed
and therefore d[Reactant]/dt < 0.
• In general for any species vj=1/njd[J]/dt
where nj is the stoichiometric coefficient.
Rates of appearance
• For a chemical reaction d[J]/dt = njνj where nj
is the stoichiometric coefficient.
• Example: A + 2B + 3C → D + 2E
• If v = - d[A]/dt, 2v = - d[B]/dt, 3v = - d[C]/dt
then v = d[D]/dt and 2v = d[E]/dt using the
correct sign convention.
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Rate Law Units of the rate constant

The rate is proportional to concentrations. The units of rate constant are always such
Example: The rate law is v = k[A][B] where that they convert into a rate expressed as
each reactant is raised to the first power
power. concentration divided by time.
time
The coefficient k is called the rate constant. Rate = k [A] [B]
(mol L-1 s-1) = (L mol-1 s-1)(mol L-1)(mol L-1)
The rate law can be determined by the
isolation method. The reaction is run in an Rate = k [A]2 [B]
excess of all but one reactant to determine (mol L-1 s-1) = (L2 mol-2 s-1)(mol2 L-2)(mol L-1)
the dependence on concentration.

Question Question
What are the units of k in vA = k[A]? What are the units of k in vA = k[A]?
A. mol L-1 s-1 A. mol L-1 s-1

B. L mol-1 s-1 B. L mol-1 s-1

C. mol L-1 C. mol L-1

D. s-1 D. s-1

First-order Kinetics First-order Kinetics

• A first order rate process: d[A]/dt = -k[A]. • A first order rate process: d[A]/dt = -k[A].

d [A]
= – k dt ′ [A](t )
[A] ln = – kt
[A] 0
[A](t )
d [A] t

=–k dt ′
[ A] 0 [A] 0 [A](t ) = [A] 0e – kt
ln ([A](t )) – ln ([A] 0) = – kt

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First-order Kinetics Half-life and rate constant

• The first order rate constant is given by The half-life for 238U is 4.5 x 109 years.
d[A]/dt = -k[A]. What is the rate constant for radioactive
• The solution is [A]=[A]0e-ktkt. d
decay off 238U.
U
• Known as single exponential kinetics. A. 1.5 x 10 year-1
-10

Half-life B. 7.5 x 10-9 year-1

• kτ1/2 = -ln([A]0/2[A] 0) = -ln(1/2) is the C. 2.25 x 109 year-1
definition of a half-life. τ1/2 = ln(2)/k D. 1.5 x 10-9 year-1

Half-life and rate constant Exponential kinetics

The half-life for 238U is 4.5 x 109 years.
What is the rate constant for radioactive exp{-t/2}
d
decay off 238U.
U exp{ t}
exp{-t}
exp{-2t}
A. 1.5 x 10 year-1
-10

B. 7.5 x 10-9 year-1

C. 2.25 x 109 year-1
D. 1.5 x 10-9 year-1 An exponential process is typical of first order kinetics.
Decay of radioactive nuclei is the textbook example.

Exponential kinetics Exponential kinetics

on [A](t)

on [A](t)

exp{-t/2} exp{-t/2} k = 1/2

exp{ t}
exp{-t} exp{ t}
exp{-t} k=1
Concentratio

Concentratio

exp{-2t} exp{-2t} k = 2

On the y-axis we can plot population or concentration. An exponential process has a 1/e time that corresponds
These are two ways of saying the same thing. to τ = 1/k, where k is the rate constant.

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Exponential kinetics Exponential kinetics

on [A](t)

on [A](t)
slope = d e – kt = – ke – kt
dt
Concentratio

Concentratio
(Seconds)

We focus on the exponential process with a rate constant The initial rate is the slope at time zero. This is given by
of k = 1 s-1. the blue line in the figure. It is obtained from the derivative.

Exponential kinetics Exponential kinetics

on [A](t)
on [A](t)

slope = d e – kt = – ke 0 = – k slope = d e – kt = – ke – k = – 1e
dt dt
HERE: slope = – 1 HERE: slope = – 1/e , e = 2.7182
Concentratio
Concentratio

rate = 1 mol/L/s rate = 0.367 mol/L/s

The initial rate is the slope at time zero. This is given by At t = 1 second the slope is again given by the derivative
the blue line in the figure. It is obtained from the derivative. at 1 second. Now the rate is smaller.

k = 1 per second
t = 1 second
on [A](t)

on [A](t)

slope = d e – kt = – ke – k = – 1e slope = d e – kt = – ke – k = – 1e
dt dt
HERE: slope = – 1/e , e = 2.7182 HERE: slope = – 1/e , e = 2.7182
Concentratio

Concentratio

rate = 0.367 mol/L/s rate = 0.367 mol/L/s

At t = 1 second the slope is again given by the derivative At t = 1 second the slope is again given by the derivative
at 1 second. Now the rate is smaller. at 1 second. Now the rate is smaller.

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Exponential kinetics Exponential kinetics

on [A](t)

on [A](t)
slope = d e – kt = – ke – 2k = – 12 slope = d e – kt = – ke – 2k = – 12
dt e dt e
HERE: slope = – 1/e 2 , e = 2.7182 HERE: slope = – 1/e 2 , e = 2.7182
Concentratio

Concentratio
rate = 0.135 mol/L/s rate = 0.135 mol/L/s
RATE CONSTANT = 1 s-1

At t = 2 seconds the slope is again given by the derivative At t = 2 seconds the slope is again given by the derivative
at 2 seconds. The continues to decrease as A is used up. at 2 seconds. The continues to decrease as A is used up.

Question Question
A first order process occurs with a rate constant A first order process occurs with a rate constant
of 0.1 s-1. If the initial concentration [A]0 = 1 M of 0.1 s-1. If the initial concentration [A]0 = 1 M
what is the concentration after 30 seconds? what is the concentration after 30 seconds?
A. 0.5 M A. 0.5 M
B. 0.05 M B. 0.05 M
C. 0.005 M C. 0.005 M
D. 0.0005 M D. 0.0005 M

Approach to equilibrium Approach to equilibrium

• A → B and B → A
A • Rate equations are:
• d[A]/dt = -k1[A] + k-1[B]
• d[B]/dt = k1[A] - k-11[B]
• Simultaneous solutions of
k-1 k1 these equations leads to a
rate constant of
k1 + k-1.
• Equilibrium is approached
as the sum of the forward
B and reverse rate constants.
Let x be the deviation from equilibrium
x = [A] – [A]eq = [B]eq – [B]
then [A] = [A]eq+ x and [B] = [B]eq – x
Rate equations are:
-d[A]/dt = k1[A] - k-1[B] = k1([A]eq+ x) - k-1([B]eq – x)
and
-d[A]eq/dt = k1[A]eq - k-1[B]eq = 0
Therefore,
-dx/dt = (k1+ k-1)x
x’/x = exp{ - (k1+ k-1)t }

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Principle of microscopic reversibility Question

• A → B and B → A
A • The equilibrium constant for A protein folds with a rate constant of 100 s-1. At the
such a process can be “melt temperature” the free energy of the folding
related for the forward and transition is, ΔGo = 0. What is the observed rate
reverse rate constants. constant for folding at this temperature?
k-1 A. 100 s-1
k1 k1 B. 200 s-1
K= C. 50 s-1
k –1
D. 0 s-1
• From before:
B k obs = k 1 + k –1

Question Summary of first-order processes

A protein folds with a rate constant of 100 s-1. At the

1. First-order processes have an exponential time course.
“melt temperature” the free energy of the folding
2. The rate constant k can be related to a 1/e time τ
transition is, ΔGo = 0. What is the observed rate
or a half time τ1/2. k = 1/
half-time 1/τ, k = ln(2)/ τ1/2.
constant for folding at this temperature?
3. The units of the rate constant are s-1.
A. 100 s-1
4. The approach to equilibrium is the sum of forward
B. 200 s-1
and reverse rate constants.
C. 50 s-1
5. The rate v is the instantaneous change (slope).
D. 0 s-1
6. The units for the rate are moles/liter/sec (Ms-1).