Chemistry 0330

Problem Set 6 Solutions

1. The rate law will have the form

[ 2]
dO " #
-
dt
= k obs [NO] [O 2 ]
for some constants kobs, , and . Going from the first set of initial concentrations to the
second multiplies the initial [NO] by 3.00 and leaves the initial [O2] alone. Since this
17 16 2
change multiplies the initial rate by (1.80 x10 / 2.00 x10 ) = 9.00 = (3.00) ,

= 2

Similarly, going from the first set of initial concentrations to the third multiplies the
initial [NO] by 2.50 and the initial [O2] by 2.50. Since this change multiplies the initial
rate by
17 16
(3.13 x10 / 2.00 x10 ) = 15.6

2 3
(2.50) (2.50) = (2.50) (2.50) = 15.6 = (2.50) , thus

= 1

We can now read off the rate constant from any one of the three sets of initial
concentrations. From the first set

16 -3 -1
initial rate = 2.00 x10 molecules cm s

18 -3 2 18 -3
= kobs (1.00 x10 molecules cm ) (1.00 x10 molecules cm ) ,

-38 -2 6 -1
kobs = 2.00 x10 molecules cm s

So, the initial rate we want to find has the value

 -38 -2 6 -1
k obs [NO]2 O2 [ ] = (2.00 x10 molecules cm s )

18 -3 2 18 -3
(6.21 x10 molecules cm ) (7.36 x10 molecules cm )

18 -3 -1
= 5.68 x10 molecules cm s

14
2. Radioactive decay exhibits first order kinetics, so the concentration of C decays
exponentially

14 14 -kt
[ C](t) = [ C]0 e ,

with the value of the rate constant k determined by the half-life t1/2 = 5730 years

-4 -1
k = ln 2 / t1/2 = 1.210 x 10 years .

14
For the C to be invisible to this technique, it must have decayed to less than 1% of its
starting (natural-abundance) level. Thus the elapsed time must be at least as long as the
time t

14 14 -kt
[ C](t) / [ C]0 = 0.01 = e ,

ln (0.01)
t = - = 38, 000 years
1.210 x 10-4 years-1

3. (a) If the first (forward) step is rate-determining, then the rate of the overall reaction is

[ ]
d Br
2
-
dt
= k1 Br2[ ] , the desired rate law with k " = k1

(b) The fractional order suggests a fast equilibrium. Suppose the second (forward) step is
rate-determining. Then the rate of production of HBr can be written

d[HBr]
dt
= k 2 [Br] H2 [ ]
but if the first step is a fast equilibrium
 1
" k %2 1
[Br]2 k
= 1 , so [Br] = $$ 1 '' Br2 2
[ ]
[Br2 ] k
-1 # k-1 &

Thus

1
" k %2 1
d[HBr]
= k 2$$ 1 '' H2 [ ][ ]
Br2 2 , which is the desired rate law with
dt # k -1 &

1
# k &2
k " = k 2 %% 1 ((
$ k-1 '

4. The third step is rate-determining, so

[
d COCl
2 ]
dt
[ ]
= k 3 [COCl] Cl2 ,

but we need to write the intermediate [COCl] in terms of reactants. Since the first two
steps are fast equilibria

[Cl]2 k1 [COCl] k
= , = 2
[Cl2 ] k-1 [Cl] [CO] k-2

Combining these two tells us that

1
" k % " k %2 1
[COCl] = $$ 2 '' $$ 1 '' [CO] Cl2 2 [ ]
# k-2 & # k -1&

and hence the rate law is

1
[
d COCl
2 ] " k % " k %2
$ 2 ' $ 1 '
3
[ ]
2
3
2 [ ]
dt
= k3 $
k ' $ k ' [CO] Cl2 = kobs [CO] Cl2
# -2 & # -1 &

The two intermediates involved in the mechanism are COCl and Cl.
5. The mechanism proposed by your friend (!) is

k
"" 1#
A + B M
$"
k" "
-1
k
A + M "" 2 # Products

which makes the overall rate the rate of the last step (regardless of whether the last step is
slow or not)

d[Products]
= k 2 [A] [M] .
dt

The only problem thats left is finding [M], the concentration of the intermediate.

(a) If the first step is a fast equilibrium

k1 [M ] k
= [M] = 1 [A] [B]
k
-1
[ A] [B] k -1

making the rate

d[Products] k k 2
= 1 2 [A] [B]
dt k -1

(b) On the other hand, at steady state the net rate of change of [M] is 0

d[M]
= k1 [A] [B] - k -1 [M] - k 2 [ A] [M] = 0
dt

k1 [A] [B]
[M] =
k -1 + k 2 [A]

Plugging this, more complicated, expression into our basic equation for the overall rate
gives us an equation that looks quite different

2
d[Products] k1 k2 [A] [B]
=
dt k + k [A ]
-1 2
(c) However, as you can see by staring at the two formulas, both of these expressions lead
to the precisely the same results in the limit that the denominator is dominated by its first
term (k-1). That is, the two expressions are exactly the same if

k2 [A] << k-1 .

To put it another way, you get the same answers if the concentration of A is small.