5.

60 Spring 2005 Lecture Summary #27 page1

Complex Reactions and Mechanisms (continued)

II) Consecutive or Series Reactions (1st order)

k1 k2
A B C

d[A] d[C]
 = k1[A] = k2 [B]
dt dt

d[B]
= k1[A]  k 2 [B]
dt
Assume initial concentration [A]0 and [B]0 = [C]0 = 0

Step 1: we already know the solution for [A]

[A] = [A]o e k1t

Step 2: substitute [A]t in expression for d[B]/dt, solve for [B]:

k1[A]o  k t  k t
[B] =
k2  k1
( e  e ) with k1  k2
1 2

Step 3: we could substitute [B]t in the expression for d[C]/dt and

integrate, but we're smarter than that. Just use conservation of
mass, [A] + [B] + [C] = constant at all times:
� 1 
[C] = [A]o 1

(2
k e k t
1
k e k t
)
2

 
1
k 2
k1

Conc. [C]

[A]

[B]max

[B]

tmax Time
5.60 Spring 2005 Lecture Summary #27 page2

ln(k1 /k 2 ) k1
= with k1  k 2 [B]max =
B
B
tmax [A]o e k t
1 max

k1  k 2 k2

Limiting cases:

i) k1 = k 2 (homework)

ii) k1 >> k2 (B formed much faster than it decays or

reacts)

[A] = [A]o e k1t [B] � [A]o e k2t

[C] � [A]o (1  e k2t )

Conc. [A] [C]

[B]

Time

k2
B C is the rate determining step
5.60 Spring 2005 Lecture Summary #27 page3

iii) k1 << k2 (B reacts much more rapidly than it is

formed)

k1
[A] = [A]o e k1t [B] � [A]
k2

[C] � [A]o  [A]

Conc. [A] [C]

[B]

Time

k
A ��1 � B is the rate limiting step
5.60 Spring 2005 Lecture Summary #27 page4

III) Reversible Reactions are reactions in which the

product of one reaction can proceed to re-form the
original substance.

k1
A B
k-1

Examples are cis �• trans isomerization, and

disproportionation of H2 + I2 �• 2 HI.
In such cases an equilibrium can be established,

[B]
K eq = eq

[ A] eq

If 1st order, Rforward = Rf = k1[A]

Rbackward = Rb = k-1[B]

At Equilibrium, R f = Rb � k1[A]eq = k-1[B]eq

k1
Keq =
k 1

This is an important connection between kinetics and

equilibrium thermodynamics known as detailed balancing. This
tells us that it is not the case that nothing is reacting at
equilibrium, but that forward and reverse reactions are
proceeding at the same overall rates, thus keeping the
concentrations of A and B constant.
 5.60 Spring 2005 Lecture Summary #27 page5

a) 1st order reversible reactions

��
A���
k d[A]
�B  = k1[A]  k1[B]
1
k -1
dt
[B] = [B]o + ([A]o – [A])
So
d[A]
 = k1[A]  k1 ( [B] o + [ A] o  [ A] )
dt
d[A]
At Equilibrium, =0
dt

k1
[ A] eq
=
k1 + k1
( [ B ] o+ [ A ] o )

d ( [ A]  [ A] eq ) d ( [ A] )

dt
=
dt
(
= ( k1 + k1 ) [ A]  [ A] eq )
[ A]  [ A] eq
= ( [ A] o )
 [ A] eq e( k +k
1 1 )t

Conc ln (|[A] - [A]eq|)

[A]0 > [A]eq

[A]eq Slope = -(k1+k-1)

[A]0 < [A]eq

time time
5.60 Spring 2005 Lecture Summary #27 page6

k1
We can measure: Keq = and k1 + k 1 � kobs
k 1

And extract k1 and k-1

b) Higher order reactions

k2
e.g. A+B C 2nd order forward reaction,
k-1
1st order reverse reaction

d[A] [C ]eq k2
 = k2 [A][B]  k 1 [C] , K= , K=
dt [A]eq [B]eq k 1

This should be another simple closed form result, right?

After a bit of calculation, we get…

a closed form expression involving the integral of a
quadratic equation !

So we need to find a different approach.