FOCUS 7

KINETICS

7A.2 (a) 1/2; (b) 1/3; (c) 1/6

7A.4 (a) Rate of iodide consumption = 4.5 × 3 = 13.5

= 1.4 × 10 μmol. L . s
(b) Rate of sulfate formation = 4.5 × 2 = 9.0 = 0.9 × 10 μmol. L . s

7A.6 (b) The rates are calculated from the slopes of the lines drawn tangent to
the curve at each point. Doing this by hand on the graph leads to a fair
amount of error in determination of the slopes. One can also determine the
values by taking the derivative of the curve fitted to the data points
followed by insertion of the specific time values into the derivative
equation. Fitting the data to [N2O5] = A(e−B.t) shows the constants A and B
to be 2.1514 and 0.1224, respectively.
d eu du
From calculus,  eu .
dx dx
Therefore the derivative of A(e−B.t) with respect to t gives −AB(e−B.t).
The instantaneous rates are, therefore:

Time Rate, mmolL−1s−1

0.00 −0.2633
1.11 −0.2299
2.22 −0.2007
3.33 −0.1752
4.44 −0.1529
420 Focus 7 Kinetics

(a) and (c)

Concentration vs. Time

2.5
concentration, mmol/L 2

1.5
N 2O 5
N2O5

NO
NO22
1
O
O22
0.5

0
0 2 4 6

time, h

7A.8 (a) rate (Torrs−1) = koPo = ko

ko = Torrs−1
(b) rate (Torrs−1) = k1P
k1 = (Torrs−1)/Torr = s−1
(c) rate (Torrs−1) = k2P2
k2 = (Torrs−1)/(Torr2) = Torr-1 s−1

.
7A.10 Rate = k C H = 5.55 × 10 s
. .

Rate = 7.6 × 10 mol C H L s

7A.12 (a) The units of the rate constant indicate that the reaction is second-order:
2
 0.54 L   0.51 g  1 mol NO 2 
rate  k [NO 2 ]   2
    
 mol s   0.18 L  46.01 g NO 2 
= 2.0 × 10−3 mol·L−1·s−1
820 2
(b) The rate increases by a factor of    2.59
510 

The new rate is (2.0  10 3 mol L1  s 1 )(2.59)  5.2  10 3 mol L1  s 1
The rate changes by (5.2 - 2.0)  10 -3 mol L1  s 1  3.2  10 3 mol L1  s 1
 Focus 7 Kinetics 421

7A.14 Rate = k[Fe2+]a[O2]b[H3O+]c where the orders a, b, and c are to be

determined. When the concentration of Fe2+ was doubled, the rate
increased by a factor of 8; that is, 2a = 8, so a = 3.
When the concentration of both Fe2+ and O2 doubled, the rate increased by
a factor of 16; that is, 23  2b = 16, so b = 1.
When the concentration of all three reactants doubled, the rate increased
by a factor of 32; that is, 23  21  2c = 32, so c = 1.
Therefore, the rate law is rate = k[Fe2+]3[O2][H3O+].

7A.16 (a)
a
rate 1 12.6  0.6 
  
rate 2 1.4  0.2 
9   3
a

a2
b
rate 1 12.6  0.3 
  
rate 3 4.2  0.1
3   3
b

b 1
Therefore, the reaction is second-order with respect to A and first-order
with respect to B.
The overall order of the reaction is 3.

(b) Rate = k[A]2[B]1

(c) Using data from experiment 2:

1.4 mol L−1 s−1 = k (0.20 mol L−1)2 (0.30 mol L−1)
k = 116.7 L2 mol−2 s−1 = 120 L2 mol−2 s−1

(d) Rate 4 = (116.7 L2 mol−2 s−1) (0.17 mol L−1)2 (0.25 mol L−1)
Rate 4 = 0.84 mol L−1 s−1
422 Focus 7 Kinetics

7A.18 (a)
a
rate 2 5.44  3.44 
  
rate 1 0.68  1.72 
8   2
a

a3
b
rate 1 0.68  2.44 
 
rate 3 2.8  10 2
 0.10 
24.3   24.4
b

b 1
Therefore, the reaction is third-order with respect to A and first-order with
respect to C.
The overall order of the reaction is 4.

(b) Rate = k[A]3[C]

(c) Using data from experiment 1:

0.68 mol L−1 s−1 = k (1.72 mol·L−1)3 (2.44 mol·L−1)
k = 5.48 × 10−2 L3·mol−3·s−1 = 5.5 × 10−2 L3·mol−3·s−1

(d) Rate 4 = (5.5 ×10−2 L3·mol−3·s−1)(2.91 mol·L−1)3(1.33 mol·L−1)

Rate 4 = 1.79 mol·L−1·s−1 = 1.8 mol·L−1·s−1

7B.2 ln kt

[A]t = [A]0 −kt = (0.100 mol∙L−1)∙ .

= 2.7 × 10−3 mol∙L−1

 
 [A] 
 [A]0  ln 0 

ln  1
 [A] 
 [A]t  
 4
0 
  ln 4  0.0111 min 1
7B.4 (a) k 
t t 125 min
 Focus 7 Kinetics 423

(b)
 0.00132 mol D  2 mol A 
[ A]t  0.0421(mol A)  L-1    
 1L  1 mol D 
 0.03946 mol  L-1  0.0395 mol  L-1

 0.0421 mol  L-1 

ln 
-1 
0.03946 mol  L   1.028  10  3 s -1  1.0  10  3 s -1
k 
63 s
(c)
 0.015 mol F  3 mol A 
[A]t  0.080(mol A)  L-1    
 1L  1 mol F 
 0.035 mol  L-1

 0.080 mol  L-1 

ln 
-1 
0.035 mol  L 
k 
11.4 min
 7.25  10  2 min 1
 7.2  10  2 min 1 or  7.3  10  2 min 1

0.693 0.693
7B.6 (a) t1/ 2    4.6 s
k 0.15 s1

(b) [N 2 O5 ]t  [N 2 O5 ]0 e kt  0.0567 mol  L1  e


 0.15s-1  2.0 s 

 [A]   [N O ] 
ln  0  ln  2 5 0  ln  0.0567 
(c) t   [A]t    [N 2 O5 ]t    0.0135   9.6 s
k k 0.15 s 1
 1 min 
 (9.6 s)    0.16 min
 60 s 
424 Focus 7 Kinetics

. .
7B.8 t1/2 = = = 559 min
.

(a) ; therefore, 2 half-lives elapse.

t = 2 × 559 min = 1120 min

(b) t = − = 1400 min
.

7B.10 (pyruvate decarboxylase)

pyruvate(aq) CO2(g)

First-order reaction, ln . We can calculate the moles of CO2(g)

produced using the ideal gas equation and subtract this from the initial
pyruvate ion concentration to obtain the remaining pyruvate ion
concentration. The pressure of the gas goes from zero to 100 Pa. The
volume available to the gas in the 500. mL flask is 500. mL – 200. mL =
300. mL. We ignore any CO2(g) dissolved in the solution.
pV (100 Pa) /(101.325  103 Pa atm 1 )  (0.300 L)
 nCO2 
RT (0.082 L atm K 1 mol 1 )  (293 K)
nCO2  1.232  105 mol
Initial moles pyruvate  3.23  103 mol.L-1 (0.200 L)  6.46  104 mol
Remaining moles pyruvate  6.46  104 mol - 1.232  105  6.337  104 mol
[pyruvate]0 = 3.23  103 mol.L-1
6.337  104 mol
[pyruvate]t =  3.168  103 mol.L-1
0.200 L
 [pyruvate]0   3.23  103 mol.L-1 
ln    ln  3 -1 
 kt
 [pyruvate]t   3.168  10 mol.L 
3.23
ln  k  522 s
3.168
k  3.71  105 s1
 Focus 7 Kinetics 425

7B.12 (a) time, s [I2](molL−1) 1/[I2](molL−1)

0 0.00100 1000
1 0.00043 2300
2 0.00027 3700
3 0.00020 5000
4 0.00016 6300

7000

6000

5000
1/[I2],Lmol-1

4000

3000

2000

1000

0
0 1 2 3 4

time, s

(b) It can be seen that a plot of 1/[I2] versus time is a straight line with an
intercept of 1000 Lmol−1 and a slope of 1300 Lmol−1s−1. Therefore, the
reaction is second-order, with a rate constant k = 1.3 × 103 Lmol−1s−1.

7B.14 Start by finding an expression for the half-life of a second-order reaction:

[A]0
[A]t 
1  [A]0 kt
[A]t1 / 2 1 1
 
[A]0 1  [A]0 kt1/ 2 2
Therefore, 1  [A]0 kt1/ 2  2, [A]
kt1/ o2 kt 1, =
1/2 and
1

Also, for a second-order reaction, .

426 Focus 7 Kinetics

1 1
(a) k    4.0 L  mol1  s 1
t1/ 2 [A]0 100 s   2.5  10 mol  L 
3 1

(b) [A]t = 0.300 mol·L−1 – 0.010 mol·L−1 = 0.29 mol·L−1

1 1
-1

k  0.290 mol.L 0.300 mol.L-1  5.75  10 4 L  mol 1  s 1
200 s

7B.16 (a)
C2H6 (g)  2CH3 (g)
0.693 0.693
t1/2    0.350 h
k 1.98
(b)

 [N O ]   2.26  10 3 mol/0.5 L 
ln 2 5 0  ln 
 [ N 2O5 ]   1.45  10  4 mol/0.5 L 
t   1.39 h
k 1.98 h -1

(c)
Because the volume is fixed :
 mass 0   1.98  1 h 
ln   kt    (42 min) = 1.39
 mass left   h  60 min 
mass 5.44 mg
mass left = 1.39 0   1.36 mg
e 4.01

7B.18 Using equations introduced in the previous problem:

1 1
(a) t1/ 2    9.3 s
k[A]0  0.54 L  mol  s1  0.20 mol  L1 
1

(b) 1
16 [A]0   0.0625  0.20 mol  L1   0.0125 mol  L1  [A]

1 1 1 1L
 
[A]t [A]0  1
0.200 mol  L1  1.4  102 s
t  0.0125 mol  L
k 0.54 L  mol 1  s 1

(c) 19 [A]0  0.111...  0.20 mol  L1  0.022 mol  L1 = [A]
 Focus 7 Kinetics 427

1 1 1 1L
 
[A]t [A]0 0.022 mol  L1 0.200 mol  L1
t   74.9 s
k 0.54 L  mol1  s 1

1 d[A]
7B.20 rate    k[A]2
a dt
d[A]
  ak dt
[A]2
integrate from [A]0 at t = 0 to [A]t at t :
[A]t d[A] t
 [A]0 [A]2
 ak  dt
0

[A]0 1  [A]t 1  akt , and [A]t 1  akt  [A]0 1

7B.22 Given: , we can derive an expression for the amount of time

needed for the initial concentration of A, [A]0 to decrease by half. Begin

by obtaining the integrated rate law for an nth-order reaction by separation
of variables.

To obtain an expression for the half-life, let [A]t = [A]0 and t = t1/2:

Solving for the half-life:

7C.2 (a) Rate = k[OH][NO2][N2] termolecular

(b) Rate = [ClO–][H2O] bimolecular

7C.4 The overall reaction is C4H9Br + 2 H2O → C4H9OH + H3O+ + Br -

Intermediates: C4H9+ and C4H9OH2+
428 Focus 7 Kinetics

7C.6 (a) Overall reaction: B + C → BC

(b) Rate law Molecularity
Step 1 rate k1[A2]
= unimolecular
2
Step 2 rate k2[A] [B]
= termolecular
Step 3 rate k3[A2B][C]
= bimolecular
(c) Intermediates are produced and consumed within reaction mechanism:
A and A2B
(d) A2

7C.8 The second step is rate-determining; therefore:

Rate k[I−][HClO], but HClO is an intermediate and must be eliminated.
=
k1[ClO−][H2O] = k1[HClO][OH−]

Because H2O is the solvent, [H2O] is constant; therefore:

=
Rate

7C.10 The rate increases in proportion to the first power of [O2] and to the
second power of [NO]. Therefore, for 2 NO(g) + O2(g) → 2 NO2(g), we
can write this: rate = k[NO]2[O2]
First, consider mechanism (a):
Step 1
kkf kf [NO3 ]

NO + O2 ⇌

f

 NO3 ; Keq   ; [NO3 ]  Keq [NO][O2 ]
krr
k
kr [NO][O2 ]
Step 2
NO + NO3 → 2 NO2 (slow and therefore rate-controlling)
Rate = k2[NO][NO3] = k2Keq [NO]2[O2], or
 Focus 7 Kinetics 429

Rate = k[NO]2[O2], with k = k2Keq, which agrees with the experimental

results.
In mechanism (b), step 1 is rate-controlling and is second-order with
respect to [NO] but does not involve [O2]. Because the other reactions are
fast, the expected rate equation is rate = k[NO]2, but this does not agree
with the observed rate law.

7C.12 (a) True; (b) True; (c) True

7C.14 The overall rate of formation of A is rate =  k[A]2  k [B]2 because the
first reaction reduces [A], while the second increases [A]. Given the 1:1
stoichiometry of the reaction, if no B was present at the beginning of the
reaction, [A] and [B] at any time are related by the equation
[A]  [B]  [A]o , where [A]o is the initial concentration of A.

At equilibrium, the equilibrium concentration of A will be [A]eq, the

equilibrium concentration of B will be [A]0 − [A]eq and the rate of the
forward reaction will equal the rate of the reverse reaction:

or (Eq. A)

Immediately prior to reaching equilibrium, the concentration of A will be

 Aeq    . At that point, the rate of formation of A will be:

Rate = (Use Eq. A to cancel terms.)

The limit as  approaches 0 is a function of k and k  .
430 Focus 7 Kinetics

7D.2 k = rate constant at T  = 630 K

 k   6.0  105 
R ln    0.08314 kJ  K  mol  ln 
1 1

 k  2.4  106 
Ea  
1 1   1 1 
     
T T   575 K 630 K 
Ea  1.8  102 kJ  mol1

7D.4 (a) Prepare the following table and graph.

T, K 1/T, K1 k, s1 ln k
660 1.52  103 7.2  104 7.2
680 1.47  103 2.2  103 6.1
720 1.39  103 1.7  102 4.1
760 1.32  103 0.11 2.2
Ea 1
ln k = ln A  
R T
The slope of the plot can be determined from a graphing program using a
least-squares fitting routine or from two points on the graph.

-1

-2

-3
ln k

-4

-5

-6

-7

-8
0.0013 0.00135 0.0014 0.00145 0.0015 0.00155

1/T, K-1

The slope from the graphing program held here gave a value for the slope
of 2.52  104. From two points:
 Focus 7 Kinetics 431

Ea [2.2  (7.2)]K
Slope of plot =   = 2.5  104 K
R (1.32  1.52)  10 3

Ea = slope  R = 2.5  104 K  8.314  103 kJK1mol1 = 2.1  102

kJmol1
1
(b) By inspecting the graph (T = 400C = 673 K; = 1.49  103), we
T
can adequately estimate:
ln k = 6.5, k = 2  103 s1
The value of k can also be calculated as follows:
 k  E  1 1   1 1 
ln    a     2.5  104 K    4.3
 k  R T T    673 K 760 K 
k 0.11
= 70 (one significant figure), k = = 2  103
k 70

7D.6
 k   E  1 1  E  T 'T 
ln    a     a  
 k  R  T T   R  TT  
 k   384 kJ  mol1  1143.15 K  973.15 K 
ln     3 1

1  
 k   8.314  10 kJ  K  mol  973.15 K  1143.15 K 
 k 
ln    1.2  103
k
k   1.2  103  5.5  10  4 s-1  6.4  10 1 s 1

7D.8 (a) The equilibrium constant will be given by the ratio of the rate constant
of the forward reaction to the rate constant of the reverse reaction:
k 52.4 L  mol 1  h 1
K   1.63
k  32.1 L  mol 1  h 1
(b) The reaction is exothermic—the forward reaction has a lower
activation barrier than the reverse reaction.
(c) Raising the temperature will increase the rate constant of the reaction
with the higher activation barrier more so than the reaction with the
432 Focus 7 Kinetics

lower energy barrier. We expect the rate of the reverse reaction to go up

substantially more than the forward reaction in this case.
k will increase less than k, and consequently the equilibrium constant K
will decrease. This is consistent with Le Chatelier’s principle.

7E.2 (a) A catalyst will provide a different rate law because an alternative
reaction pathway will be introduced.
(b) The equilibrium constant will not be affected. A catalyst will affect the
forward and backward rate constants in the same magnitude, so the
equilibrium constant will not change.

7E.4 (a) cat, catalyzed; uncat, uncatalyzed

Ea,cat = 52 Ea = 0.69 Ea
75
/ .
. /
/ = =

∙
. ∙ / ∙ /
=
3
kJK 1 mol 1
e .

= 1 × 106
(b) The last step of the calculation is repeated with T = 300 K:
/ .
. /
/ = =

∙
. ∙ / ∙ /
=
3
kJK 1 mol 1
e .

= 1 × 104
The rate enhancement is lower at higher temperatures.

7E.6 Overall reaction:

CH3COOCH2CH3(aq)  H2O(aq)  CH3COOH(aq)  CH3CH2OH(aq)
The intermediate is ethoxide ion, CH3CH2O. The catalyst is OH.

7E.8 (a) True

(b) True
 Focus 7 Kinetics 433

(c) False. The equilibrium constant for a reaction is unaffected by the

presence of a catalyst.
(d) False. The pathway of a reaction is altered by a catalyst, but the
beginning and ending points are the same, so the amount of energy
released (or gained) is not affected by the presence of a catalyst.

7E.10 The Michaelis−Menten mechanism of enzyme reaction:

k1
E + S ⇌ ES
k’1

k2
ES   E + product
Where E, S, and ES represent the enzyme, substrate, and
enzyme−substrate complex, respectively. The Michaelis constant:
k1  k2
KM 
k1
If this constant increases, the rates of the two reactions that lead to
decomposition of the enzyme−substrate complex increase compared to the
rate of the enzyme−substrate formation reaction. Therefore, a high
Michaelis constant indicates an unstable enzyme−substrate complex.

7.2 The ratio of [B]/[C] will increase as the temperature increases because the
formation of B has a larger activation energy which is more easily
overcome at higher temperatures.

5 s 1 )(18000 s )
7.4 (a) [A]t = [A]0kt = (0.120 mol·L1) e(3.6 10
= 6.28 × 102 mol·L1
(b) [A]t = 3[B]t
[B]t = 1/3 [A]t = 2.09 × 102 mol·L1
[B]t
ln  kt
[B]0
434 Focus 7 Kinetics

0.0209 mol.L1
ln  k (18000 s)
0.240 mol·L1
=k 1.36 × 104 s1 = 1.4 × 104 s1

7.6 (a) Bimolecular

(b) Unimolecular
(c) Trimolecular

7.8 Step 2 is the slow step. We can show this by the following analysis.
Step 1 N2 + H2 → N2H2 (fast)
Step 2 H2 + N2H2 → N2H4 (slow)
Reaction rate is determined by slowest step; therefore, the
rate = k2 [H 2 ][N 2 H 2 ] .
Assuming step 1 is fast enough to reach equilibrium:
[N H ]
K1 = 2 2 and [N2H2] = K1[N2][H2].
[N 2 ][H 2 ]
Substituting for [N2H2] in the above rate equation gives:
k1k2
Rate = k 2 [H 2 ]K1[N 2 ][H 2 ] = k [N 2 ][H 2 ]2 where k =
k1/

7.10 The overall reaction is 2 CH3C(O)CH3CH3C(O)CH2C(OH)(CH3)2.

The intermediates:
+ +
O H O H O H OH

H3C C CH3 H3C C CH2 H3C C CH2 C CH3

CH3
The hydrogen ion serves as a catalyst for the reaction.

7.12 (a)
T, K 1/T, K1 k, 103 Lmol1s1 ln(k  103) ln k
297 0.003 37 4.8 1.57 5.34
301 0.003 32 7.8 2.05 4.85
 Focus 7 Kinetics 435

305 0.003 28 13.0 2.56 4.34

309 0.003 24 20.0 3.00 3.91
313 0.003 19 32.0 3.47 3.44

3.5

3
ln(kx103)

2.5

1.5

0.5

0
0.00315 0.0032 0.00325 0.0033 0.00335 0.0034

1/T, K-1´10-3

Ea
ln k = ln A 
RT
Slope of straight line above (the ordinates are given as ln k)
(3.47  1.57) K E
slope of line = = 1.1  105 K =  a
0.003 19  0.003 37 R
Ea = (1.1  105 K)(8.314 51  103 kJK1mol1) = 91 kJmol1

(b) T = 310 K; 1/T = 3.23  103 K1

From the plot, ln (k  103)  3.10; k  103  22; k  2.2  102 Lmol1s1

(c) The balanced equation is sucrose(aq)  glucose(aq)  fructose(aq).

We will use the enthalpies of formation for the solid, based upon the
assumption that the solvation of the sugars is negligible. In fact, this is not
unreasonable, because the solvation energy of the sucrose should largely
436 Focus 7 Kinetics

compensate for the solvation of the glucose and fructose in the Hess’ law
calculation.
Hrxn = 1268 kJmol1  1266 kJmol1  (2222 kJmol1)
= 312 kJmol1
The overall reaction profile will be:

sucrose Ea  91 kJ  mol1

o
H rxn  312 kJ  mol1

glucose + fructose

7.14 (a) The mechanism assumed is:

k1
E + S ⇌ ES
k’1

k2
ES   E+P
Where E is the free enzyme, S is the substrate, ES is the enzyme−substrate
complex, and P is the product.
The rate-determining step is the formation of products from the activated
complex ES, so we can write:
rate k2 [ES]
=
But because ES is an intermediate, we cannot leave it in the final rate
expression. We will make a steady-state approximation to determine the
concentration of ES in solution. We also realize that [E]0 is the starting
concentration of enzyme. Because a significant portion of the enzyme
will be bound to the substrate, the actual concentration of E at any given
time will be equal to [E]0  [ES].
In the steady-state approach, the rate of formation of the activated
complex ES added to its rate of disappearance will be set equal to 0.
Rate of formation of ES is k1[E][S] = k1([E]0  [ES])[S].
 Focus 7 Kinetics 437

Rate of disappearance of ES is k2 [ES]  k1[ES]:

k1([E]0  [ES])[S]  (k2 [ES]  k1[ES]) = 0
k1([E]0  [ES])[S]  (k2  k1)[ES] = 0
k1([E]0  [ES])[S] = (k2  k1)[ES]
k1[E]0[S]  k1[ES][S] = (k2  k1)[ES]
(k2  k1)[ES]  k1[ES][S] = k1[E]0[S]
[ES](k2  k1  k1[S]) = k1[E]0[S]
k1 [E]0 [S]
=
[ES]
k2  k1  k1 [S]
The rate expression:
k2 k1 [E]0 [S]
Rate k2[ES] =
=
k  k   k [S]
2 1 1

Dividing both numerator and denominator by k1, we obtain:

k2 [E]0 [S]
=
Rate
k2  k1
+[S]
k1

k2 [E]0 [S]

KM  [S]

(b) It is easy to confirm that the rate is independent at high concentrations

of substrate by noting that under these conditions [S] >> KM, so that KM +
[S]  [S]. The [S] in numerator and denominator will cancel, leaving the
rate equal to k2[E]0.

7.16 According to collision theory, the rate of a reaction is dictated by the

frequency of collisions and the fraction of collisions that supply
sufficient energy to initiate the reaction.
Rate of reaction = (collision frequency) (fraction with sufficient energy)
The collision frequency is calculated thus:
Collision frequency =
438 Focus 7 Kinetics

where the relative velocity, vrel, is:

1/ 2
 8RT 
vrel  
 πμ 
and the fraction of collisions providing at least enough energy to
overcome the activation energy for the reaction is given by:

Fraction with sufficient energy =

If we take the reactants to be A and B, the ratio of reaction rates is:

rate (320 K)   vrel , 320 K  N A [A][B] e  Ea

2 R 320 K
= 
rate (300 K)   vrel , 300 K  N A2 [A][B] e  Ea R 300 K

  8 R  320 K 1 / 2  2
    N A [A][B]  E
 πμ   e a R 320 K
=   R 300 K
  8 R  300 K 1 / 2  2 e  Ea
    N A [A][B]
 πμ  

Canceling terms that are not dependent on the temperature, this
expression simplifies to:

rate (320 K)  320 K 

1/ 2 R320 K
e  Ea
= 
rate (300 K)  300 K 1/ 2 e Ea R300 K

 1.033  e
 Ea R320 K    Ea R300 K 

 1 1 
 25 kJmol -1

0.0083145 kJ K -1 mol-1   
 1.033  e  300 K 320 K 

 1.9

7.18 The reaction profile as given:

Potential Energy

A B
C

Reaction Coordinate
 Focus 7 Kinetics 439

(a) Overall, the reaction is exothermic. The product possesses less

potential energy than the reactant.
(b) There are two intermediates, B and C.
(c) There are three activated complexes: one lies at the maximum in the
curve between the reactant A and the intermediate B; one, between the
intermediates B and C; and a third, between the intermediate C and the
final product D.
(d) The reaction to form C from B would be rate-limiting, as this step has
the largest activation barrier.
(e) The reaction to form D from C would be the fastest, as the energy
released on going from the activated complex between the intermediates B
and C to the intermediate C is sufficient to send C over the final reaction
barrier to D.

7.20 Let P = pollutant

(a) Rate = R  k[P]eq = 0 at equilibrium
R
[P]eq =   
k
(b) Because [P]eq is constant, there is no overall half-life, but on average,
for an individual molecule, there is a 50% probability that it will have
decayed after t1/2 where:
0.693
t1/2 =
k

k1
7.22 CH3OH  H+ ⇌ CH3OH2+
k’1
+ k1

CH3OH2  Br   CH3Br  H2O
(a) The rate law will be based upon the second step, which is the slow step
of the reaction.
Rate k2[CH3OH2+][Br]
=
The rate law cannot be left in this form because CH3OH2+ is a reactive
intermediate. We can express the concentration of CH3OH2+ in terms of
440 Focus 7 Kinetics

the reactants and products, using the fast equilibrium established in the
first step.
k1 [CH3 OH 2  ]
K= 
k1 [CH3 OH][H ]
+

k1
[CH3OH2+] = [CH3OH][H+]
k 
1

Then:
k2 k1
=
Rate [CH3OH][H+][Br]
k 
1

(b) The steady-state approximation is similar to the fast equilibrium

approach, except that k2 may not be very much smaller than k1. This
means that the rate of the reaction to final products is fast enough to
disturb the equilibrium established in the pre-equilibrium step. To use this
approximation, we set the rate of formation of the intermediate equal to its
rate of disappearance:
rate of formation of CH3OH2+ = k1[CH3OH][H+]
rate of disappearance of CH3OH2+ = k1[CH3OH2+] + k2[CH3OH2+][Br]
k1[CH3OH2+]  k2[CH3OH2+][Br] = k1[CH3OH][H+]
[CH3OH2+](k1  k2[Br]) = k1[CH3OH][H+]
k1[CH3 OH][H + ]
+
[CH3OH2 ] =
k   k [Br - ]
1 2

We place this expression in the same rate law as in part (a).

k2 k1 [CH3 OH][H + ][Br  ]
=
rate
k   k [Br  ]
1 2

(c) When k2 is very much less than k1, the expressions will be the same.
They will also be the same at low concentrations of Br.
(d) At high concentrations of Br, the steady-state approximation rate will
have k2[Br] >> k1. Under those conditions, the rate law becomes
 Focus 7 Kinetics 441

rate k1[CH3OH][H+]. The fast equilibrium rate law would not change at
=
high concentrations of Br.

7.24 From the second-order reactions and their activation energies,

H—H < N≡N. A H—H bond is expected to be weaker than a N≡N. There
is no activation energy for the recombination of two methyl radicals, since
no bond is being broken. From the gas phase energies of activation we
find that, N—O < C—N < N=O < C—H < C—C for relative bond
enthalpies. Generally, single bonds are weaker than double bonds,
heteroatom−heteroatom bonds are weaker than heteroatom−carbon bonds
which are weaker than carbon−carbon bonds. These general rules explain
the relative bond enthalpies elucidated from the gas phase activation
energies. From the second order, aqueous energetics, C—Br < C—O.
Since bromine is a larger atom, the orbital overlap between carbon and
bromine will be nonideal and this bond will be weaker than the bond
between carbon and oxygen. The reaction of CO2 with OH- does not
involve any breaking of bonds; rather, the cylindrical CO2 must become
more trigonal planar as the OH- approaches and the C=O becomes a C—O
but is not broken entirely.

rate at 28C k  t 48 h
7.26   
rate at 5C k t 4 h

 k  E  1 1 
We use ln    a    and solve for Ea .
 k  R T T
 k   48 
R ln   (8.314  10 3 kJ  K 1  mol 1 ) ln  
Ea  k  4   75 kJ  mol 1
1 1  1 1 
     
 T T   278 K 301 K 
442 Focus 7 Kinetics

7.28
dN
 bN  dN
dt
dN
 dt
bN  dN
N t
dN
 bN  dN 0 dt
N0


N t
dN

N0
N (b  d ) 0
 dt

N t
dN
N N  (b  d )0 dt
0

N N
ln  ( b  d )t OR  e ( b d ) t
N0 N0
Since linear plots are easier to analyze than nonlinear plots, we plot ln N
N
versus time. In other words, we use ln  (b  d )t , where :
N0
ln N  (b  d )t  ln N 0
y  mx  c
The slope, m = b – d, and the y-intercept, c = ln N0.

22.5

22.0

21.5
lnN

21.0

lnN=3.293+0.00953t
20.5

20.0

1750 1800 1850 1900 1950 2000

Time, t

This model as a whole fits the data quite well.

 Focus 7 Kinetics 443

7.30 (a) Overall reaction: O3 + O → 2O2

(b) Rate law Molecularity
Step 1 rate = k[O3][NO] bimolecular
Step 2 rate = k[NO2][O] bimolecular
(c) Reaction intermediate: NO2
(d) Catalyst: NO

7.32
sp
sp3 H

H C N C

polar
(a) H methyl isonitrile

sp
sp3 H

H C C N

polar
H cyanomethane
(b) To convert from one isomer to the other, a single C—N bond is
broken and a single C—C bond is formed, giving an approximate
enthalpy of reaction of:
305 kJ  mol1  348 kJ  mol1  43 kJ  mol1 .
Cyanomethane is the more stable isomer.

(c) The rate constant at 300 K is found using:

Substituting into this equation, we find:

Solving for k':

444 Focus 7 Kinetics

k' = 4.04 × 10−15 s−1

At this rate, the time required to reduce the initial concentration of the
isomer by 75% is found by:
[CH3 NC]t
ln  ln(0.75)  k  t  4.04  1015 s 1  t
[CH3 NC]0
t  7.12  1013 s
(d) Since ΔHo for this isomerization reaction is exothermic (−43 kJ·mol−1),
the reaction profile has the product lower than the reactant.
(e) We begin by finding the rate constant at which the concentration of the
isomer will reduce by 75% in one hour:
[CH 3 NC]t  60 min  60 s 
ln  ln(0.75)  k  t  k  1 h   
[CH3 NC]0  h  min 
Solving for k :
k  7.99  105 s 1
We can now determine at what temperature this rate constant is reached
using the equation from part (c) above:

Solving for T:
T = 474 K
(f) Argon serves as a collision partner. Collisions between the CH3NC(g)
and argon atoms provide the energy needed to overcome the activation
energy and allow the isomerization reaction to proceed toward products.
The argon atoms also serve as an energy sink, accepting the energy
released during the isomerization reaction.
(g) At high argon concentrations, collisions resulting in reaction are
between the CH3NC(g) and argon atoms:
 Focus 7 Kinetics 445

CH3NC(g) + Ar(g) → CH3CN(g) + Ar(g)

Given this elementary reaction, one would predict that the reaction was
first-order with respect to CH3NC(g) concentration and would appear first-
order overall if the concentration of Ar(g) was large and unchanging. If,
however, the concentration of Ar(g) was greatly reduced, the
isomerization reaction would also proceed through collisions between
CH3NC(g) molecules, making the reaction second-order with respect to
CH3NC(g).