Chemical Kinetics: Questions

CHAPTER 12
CHEMICAL KINETICS
Questions
10. The average rate decreases with time because the reverse reaction occurs more frequently as
the concentration of products increase. Initially, with no products present, the rate of the
forward reaction is at its fastest, but as time goes on, the rate gets slower and slower since
products are converting back into reactants. The instantaneous rate will also decrease with time.
The only rate that is constant is the initial rate. This is the instantaneous rate taken at t ≈ 0. At
this time, the amount of products is insignificant, and the rate of the reaction only depends on
the rate of the forward reaction.
11. One experimental method to determine rate laws is the method of initial rates. Several
experiments are carried out using different initial concentrations of reactants, and the initial
rate is determined for each experiment. The results are then compared to see how the initial
rate depends on the initial concentrations. This allows the orders in the rate law to be
determined. The value of the rate constant is determined from the experiments once the orders
are known.
The second experimental method utilizes the fact that the integrated rate laws can be put in the
form of a straight-line equation. Concentration versus time data are collected for a reactant as
a reaction is run. These data are then manipulated and plotted to see which manipulation gives
a straight line. From the straight-line plot we get the order of the reactant, and the slope of the
line is mathematically related to k, the rate constant.
12. a. T2 > T1; as temperature increases, the distribution of collision energies shifts to the right.
That is, as temperature increases, there are fewer collision energies with small energies and
more collisions with large energies.
b. As temperature increases, more of the collisions have the required activation energy
necessary to convert reactants into products. Hence, the rate of the reaction increases with
increasing temperature.
13. All of these choices would affect the rate of the reaction, but only b and c affect the rate by
effecting the value of the rate constant k. The value of the rate constant depends on temperature.
The value of the rate constant also depends on the activation energy. A catalyst will change the
value of k because the activation energy changes. Increasing the concentration (partial
pressure) of either O2 or NO does not affect the value of k, but it does increase the rate of the
reaction because both concentrations appear in the rate law.
447
448 CHAPTER 12 CHEMICAL KINETICS
14. a. Activation energy and ΔE are independent of each other. Activation energy depends on
the path reactants to take to convert to products. The overall energy change ΔE only
depends on the initial and final energy states of the reactants and products. ΔE is path-
independent.
b. The rate law can only be determined from experiment, not from the overall balanced
reaction.
c. Most reactions occur by a series of steps. The rate of the reaction is determined by the
rate of the slowest step in the mechanism.
15. In a unimolecular reaction, a single reactant molecule decomposes to products. In a bimolecular

reaction, two molecules collide to give products. The probability of the simultaneous collision
of three molecules with enough energy and the proper orientation is very small, making
termolecular steps very unlikely.
16. The most common method to experimentally determine the differential rate law is the method
of initial rates. Once the differential rate law is determined experimentally, the integrated rate
law can be derived. However, sometimes it is more convenient and more accurate to collect
concentration versus time data for a reactant. When this is the case, then we do “proof” plots
to determine the integrated rate law. Once the integrated rate law is determined, the differential
rate law can be determined. Either experimental procedure allows determination of both the
integrated and the differential rate law; and which rate law is determined by experiment and
which is derived is usually decided by which data are easiest and most accurately collected.
x
Rate 2 k[A]2x  [A] 
17. = x
=  2 
Rate1 k[A]1  [A]1 
The rate doubles as the concentration quadruples:
2 = (4)x, x = 1/2
The order is 1/2 (the square root of the concentration of reactant).
For a reactant that has an order of −1 and the reactant concentration is doubled:
Rate 2 1
= (2) −1 =
Rate1 2
The rate will decrease by a factor of 1/2 when the reactant concentration is doubled for a −1
order reaction. Negative orders are seen for substances that hinder or slow down a reaction.
18. Some energy must be added to get the reaction started, that is, to overcome the activation
energy barrier. Chemically what happens is:
Energy + H2 → 2 H
The hydrogen atoms initiate a chain reaction that proceeds very rapidly. Collisions of H2 and
O2 molecules at room temperature do not have sufficient kinetic energy to form hydrogen atoms
and initiate the reaction.
CHAPTER 12 CHEMICAL KINETICS 449
19. Two reasons are:

(1) The collision must involve enough energy to produce the reaction; that is, the collision
energy must be equal to or exceed the activation energy.
(2) The relative orientation of the reactants when they collide must allow formation of any
new bonds necessary to produce products.
20. a. The blue plot is the catalyzed pathway. The catalyzed pathway has the lower activation.
This is why the catalyzed pathway is faster.
b. ∆E1 represents the activation energy for the uncatalyzed pathway.
c. ∆E2 represents the energy difference between the reactants and products. Note that ∆E2 is
the same for both the catalyzed and the uncatalyzed pathways. It is the activation energy
that is different for a catalyzed pathway versus an uncatalyzed pathway.
d. Because the products have a higher total energy as compared to reactants, this is an
endothermic reaction.
21. Enzymes are very efficient catalysts. As is true for all catalysts, enzymes speed up a reaction
by providing an alternative pathway for reactants to convert to products. This alternative
pathway has a smaller activation energy and hence, a faster rate. Also true is that catalysts are
not used up in the overall chemical reaction. Once an enzyme comes in contact with the correct
reagent, the chemical reaction quickly occurs, and the enzyme is then free to catalyze another
reaction. Because of the efficiency of the reaction step, only a relatively small amount of
enzyme is needed to catalyze a specific reaction, no matter how complex the reaction.
22. The enzyme lactase catalyzes the breakdown of the sugar lactose found in dairy products.
Without sufficient lactase, individuals with lactose intolerance are unable to fully digest the
lactose sugar in milk. This can result in diarrhea, gas, and bloating after eating or drinking dairy
products.
23. The speed (kinetics) of a reaction is independent of the enthalpy change for the reaction. The
combustion of carbohydrates has a lower activation energy, which is why it is the faster process.
24. The slope of the ln k versus 1/T plot (with temperature in Kelvin) is equal to −Ea/R. Because
Ea for the catalyzed reaction will be smaller than Ea for the uncatalyzed reaction, the slope of
the catalyzed plot should be less negative.
Exercises
Reaction Rates
25. The coefficients in the balanced reaction relate the rate of disappearance of reactants to the rate
of production of products. From the balanced reaction, the rate of production of P4 will be 1/4
the rate of disappearance of PH3, and the rate of production of H2 will be 6/4 the rate of
disappearance of PH3. By convention, all rates are given as positive values.
− ∆[PH 3 ] − (−0.048 mol/2.0 L)

Rate = = = 2.4 × 10 −3 mol/L•s
∆t s
Δ[P4 ] 1 Δ[PH 3 ]
=− = 2.4 × 10 −3 /4 = 6.0 × 10 −4 mol/L•s
Δt 4 Δt
Δ[H 2 ] 6 Δ[PH 3 ]
=− = 6(2.4 × 10 −3 )/4 = 3.6 × 10 −3 mol/L•s
Δt 4 Δt
26. Using the coefficients in the balanced equation to relate the rates:
∆[H 2 ] ∆[ N 2 ] ∆[ NH 3 ] ∆[ N 2 ]
=3 and = −2
∆t ∆t ∆t ∆t
1 ∆[H 2 ] 1 ∆[ NH 3 ] ∆[ NH 3 ] 2 ∆[H 2 ]
So : − = or =−
3 ∆t 2 ∆t ∆t 3 ∆t
Ammonia is produced at a rate equal to 2/3 of the rate of consumption of hydrogen.
− ∆[H 2 O 2 ] − (0.500 M − 1.000 M)

27. a. Average rate = = = 2.31 × 10 −5 mol/L•s
∆t (2.16 × 10 s − 0)
4
From the coefficients in the balanced equation:

Δ[O 2 ] 1 Δ[H 2 O 2 ]
=− = 1.16 × 10 −5 mol/L•s
Δt 2 Δt
− ∆[H 2 O 2 ] − (0.250 − 0.500) M
b. = = 1.16 × 10 −5 mol/L•s
∆t (4.32 × 10 4 − 2.16 × 10 4 ) s
Δ[O 2 ]
= 1/2 (1.16 × 10 −5 ) = 5.80 × 10 −6 mol/L•s
Δt
Notice that as time goes on in a reaction, the average rate decreases.
28. 0.0120/0.0080 = 1.5; reactant B is used up 1.5 times faster than reactant A. This corres-ponds
to a 3 to 2 mole ratio between B and A in the balanced equation. 0.0160/0.0080 = 2; product
C is produced twice as fast as reactant A is used up, so the coefficient for C is twice the
coefficient for A. A possible balanced equation is 2A + 3B → 4C.
29. a. The units for rate are always mol/L•s. b. Rate = k; k must have units of mol/L•s.
2
mol  mol  mol  mol 
c. Rate = k[A], = k  d. Rate = k[A]2, = k 
Ls  L  Ls  L 
k must have units of s −1 . k must have units of L/mol•s.
e. L2/mol2•s
1/ 2
mol  mol   mol 
30. Rate = k[Cl]1/2[CHCl3], = k    ; k must have units of L1/2/mol1/2•s.
Ls  L   L 
Rate Laws from Experimental Data: Initial Rates Method

31. a. In the first two experiments, [NO] is held constant and [Cl2] is doubled. The rate also
doubled. Thus the reaction is first order with respect to Cl2. Or mathematically, Rate =
k[NO]x[Cl2]y.
0.36 k (0.10) x (0.20) y (0.20) y
= = , 2.0 = 2.0y, y = 1
0.18 k (0.10) x (0.10) y (0.10) y
We can get the dependence on NO from the second and third experiments. Here, as the
NO concentration doubles (Cl2 concentration is constant), the rate increases by a factor of
four. Thus the reaction is second order with respect to NO. Or mathematically:
1.45 k (0.20) x (0.20) (0.20) x
= = , 4.0 = 2.0x, x = 2; so Rate = k[NO]2[Cl2].
0.36 k (0.10) x (0.20) (0.10) x
Try to examine experiments where only one concentration changes at a time. The more
variables that change, the harder it is to determine the orders. Also, these types of problems
can usually be solved by inspection. In general, we will solve using a mathematical
approach, but keep in mind that you probably can solve for the orders by simple inspection
of the data.
b. The rate constant k can be determined from the experiments. From experiment 1:
2
0.18 mol  0.10 mol   0.10 mol 
= k    , k = 180 L2/mol2•min
L min  L   L 
From the other experiments:
k = 180 L2/mol2•min (second exp.); k = 180 L2/mol2•min (third exp.)
The average rate constant is kmean = 1.8 × 102 L2/mol2•min.
12.5 × 10 −6 k (0.080) x (0.040) y

32. a. Rate = k[I−]x[S2O82−]y; = , 2.00 = 2.0x, x = 1
6.25 × 10 −6 k (0.040) x (0.040) y
12.5 × 10 −6 k (0.080)(0.040) y
= , 2.00 = 2.0y, y = 1; Rate = k[I−][S2O82−]
6.25 × 10 −6 k (0.080)(0.020) y
b. For the first experiment:
12.5 × 10 −6 mol  0.080 mol  0.040 mol 

= k   , k = 3.9 × 10−3 L/mol•s
Ls  L  L 
Each of the other experiments also gives k = 3.9 × 10−3 L/mol•s, so kmean
= 3.9 × 10−3 L/mol•s.
33. a. Rate = k[NOCl]n; using experiments two and three:

2.66 × 10 4 k (2.0 × 1016 ) n
= , 4.01 = 2.0n, n = 2; Rate = k[NOCl]2
6.64 × 103 k (1.0 × 1016 ) n
2
5.98 × 10 4 molecules  3.0 × 1016 molecules 
b. = k   , k = 6.6 × 10−29 cm3/molecules•s
cm 3 s  3 
 cm 
The other three experiments give (6.7, 6.6, and 6.6) × 10−29 cm3/molecules•s,
respectively. The mean value for k is 6.6 × 10−29 cm3/molecules•s.
6.6 × 10 −29 cm 3 1L 6.022 × 10 23 molecules 4.0 × 10 −8 L
c. × × =
molecules s 1000 cm 3 mol mol s
34. Rate = k[N2O5]x; the rate laws for the first two experiments are:
2.26 × 10−3 = k(0.190)x and 8.90 × 10−4 = k(0.0750)x
(0.190) x
Dividing the two rate laws: 2.54 = = (2.53)x, x = 1; Rate = k[N2O5]
(0.0750) x
Rate 8.90 × 10 −4 mol/L • s
k = = = 1.19 × 10−2 s−1
[N 2 O 5 ] 0.0750 mol/L
The other experiments give similar values for k. kmean = 1.19 × 10−2 s−1
7.91 × 10 −2 k (0.12) x (0.18) y

35. a. Rate = k[I−]x[OCl−]y; = = 2.0x, 2.00 = 2.0x, x = 1
3.95 × 10 − 2 k (0.060) x (0.18) y
3.95 × 10 −2 k (0.060)(0.18) y
= , 4.00 = 2.0 × 2.0y, 2.0 = 2.0y, y = 1
9.88 × 10 −3 k (0.030)(0.090) y
Rate = k[I−][OCl−]
7.91 × 10 −2 mol  0.12 mol  0.18 mol 

b. From the first experiment: = k  , k = 3.7 L/mol•s
Ls  L  L 
All four experiments give the same value of k to two significant figures.
3.7 L 0.15 mol 0.15 mol
c. Rate = × × = 0.083 mol/L • s
mol s L L
36. Rate = k[NO]x[O2]y; comparing the first two experiments, [O2] is unchanged, [NO] is tripled,
and the rate increases by a factor of nine. Therefore, the reaction is second order in NO (32 =
9). The order of O2 is more difficult to determine. Comparing the second and third
experiments:
3.13 × 1017 k (2.50 × 1018 ) 2 (2.50 × 1018 ) y
=
1.80 × 1017 k (3.00 × 1018 ) 2 (1.00 × 1018 ) y
1.74 = 0.694(2.50)y, 2.51 = 2.50y, y = 1
Rate = k[NO]2[O2]; from experiment 1:
2.00 × 1016 molecules/cm3•s = k(1.00 × 1018 molecules/cm3)2

× (1.00 × 1018 molecules/cm3)
k = 2.00 × 10−38 cm6/molecules2•s = kmean

2
2.00 × 10 −38 cm 6  6.21 × 1018 molecules  7.36 × 1018 molecules
Rate = 
×   ×
molecules2 s cm 3  cm 3
 
Rate = 5.68 × 1018 molecules/cm3•s
37. a. Rate = k[Hb]x[CO]y
Comparing the first two experiments, [CO] is unchanged, [Hb] doubles, and the rate
doubles. Therefore, x = 1, and the reaction is first order in Hb. Comparing the second and
third experiments, [Hb] is unchanged, [CO] triples, and the rate triples. Therefore, y = 1,
and the reaction is first order in CO.
b. Rate = k[Hb][CO]
c. From the first experiment:
0.619 µmol/L•s = k(2.21 µmol/L)(1.00 µmol/L), k = 0.280 L/µmol•s
The second and third experiments give similar k values, so kmean = 0.280 L/µmol•s
0.280 L 3.36 μmol 2.40 μmol
d. Rate = k[Hb][CO] = × × = 2.26 µmol/L•s
μmol s L L
38. a. Rate = k[ClO2]x[OH−]y; from the first two experiments:
2.30 × 10−1 = k(0.100)x(0.100)y and 5.75 × 10−2 = k(0.0500)x(0.100)y
(0.100) x
Dividing the two rate laws: 4.00 = = 2.00x, x = 2
(0.0500) x
Comparing the second and third experiments:
2.30 × 10−1 = k(0.100)(0.100)y and 1.15 × 10−1 = k(0.100)(0.0500)y
(0.100) y
Dividing: 2.00 = = 2.0y, y = 1
(0.050) y
The rate law is Rate = k[ClO2]2[OH−].
2.30 × 10−1 mol/L•s = k(0.100 mol/L)2(0.100 mol/L), k = 2.30 × 102 L2/mol2•s = kmean
2
2.30 × 10 2 L2  0.175 mol  0.0844 mol
b. Rate = ×  × = 0.594 mol/L•s
mol 2 s  L  L
Integrated Rate Laws

39. The first assumption to make is that the reaction is first order. For a first order reaction, a
graph of ln[H2O2] versus time will yield a straight line. If this plot is not linear, then the
reaction is not first order, and we make another assumption.
Time [H2O2] ln[H2O2]

(s) (mol/L)
0 1.00 0.000
120. 0.91 −0.094
300. 0.78 −0.25
600. 0.59 −0.53
1200. 0.37 −0.99
1800. 0.22 −1.51
2400. 0.13 −2.04
3000. 0.082 −2.50
3600. 0.050 −3.00
Note: We carried extra significant figures in some of the natural log values in order to reduce
round-off error. For the plots, we will do this most of the time when the natural log function
is involved.
The plot of ln[H2O2] versus time is linear. Thus the reaction is first order. The rate law and
integrated rate law are Rate = k[H2O2] and ln[H2O2] = −kt + ln[H2O2]0.
We determine the rate constant k by determining the slope of the ln[H2O2] versus time plot
(slope = −k). Using two points on the curve gives:
Δy 0 − (3.00)
slope = −k = = = −8.3 × 10−4 s−1, k = 8.3 × 10−4 s−1
Δx 0 − 3600.
To determine [H2O2] at 4000. s, use the integrated rate law, where [H2O2]0 = 1.00 M.
 [H 2 O 2 ] 
ln[H2O2] = −kt + ln[H2O2]0 or ln   = −kt
 [H 2 O 2 ]0 
 [H O ] 
ln  2 2  = −8.3 × 10−4 s−1 × 4000. s, ln[H2O2] = −3.3, [H2O2] = e−3.3 = 0.037 M
 1.00 
40. a. Because the ln[A] versus time plot was linear, the reaction is first order in A. The slope of
the ln[A] versus time plot equals −k. Therefore, the rate law, the integrated rate law, and
the rate constant value are:
Rate = k[A]; ln[A] = −kt + ln[A]0; k = 2.97 × 10−2 min−1

b. The half-life expression for a first order rate law is:

ln 2 0.6931 0.6931
t1/2 = = , t1/2 = = 23.3 min
k k 2.97 × 10 − 2 min −1
c. 2.50 × 10−3 M is 1/8 of the original amount of A present initially, so the reaction is 87.5%
complete. When a first-order reaction is 87.5% complete (or 12.5% remains), then the
reaction has gone through 3 half-lives:
100% → 50.0% → 25.0% → 12.5%; t = 3 × t1/2 = 3 × 23.3 min = 69.9 min

t1/2 t1/2 t1/2
Or we can use the integrated rate law:
 [A]   2.50 × 10 −3 M 
ln  = − kt , ln 
 2.00 × 10 − 2 M  = −(2.97 × 10 min )t
−2 −1
 [ A ]0   
ln(0.125)
t= = 70.0 min
− 2.97 × 10 − 2 min −1
41. Assume the reaction is first order and see if the plot of ln[NO2] versus time is linear. If this
isn’t linear, try the second-order plot of 1/[NO2] versus time because second-order reactions
are the next most common after first-order reactions. The data and plots follow.
Time (s) [NO2] (M) ln[NO2] 1/[NO2] ( M −1 )

0 0.500 −0.693 2.00
1.20 × 103 0.444 −0.812 2.25
3.00 × 103 0.381 −0.965 2.62
4.50 × 103 0.340 −1.079 2.94
9.00 × 103 0.250 −1.386 4.00
1.80 × 104 0.174 −1.749 5.75
The plot of 1/[NO2] versus time is linear. The reaction is second order in NO2.
1 1
The rate law and integrated rate law are: Rate = k[NO2]2 and = kt +
[ NO 2 ] [ NO 2 ]0
The slope of the plot 1/[NO2] vs. t gives the value of k. Using a couple of points on the plot:
∆y (5.75 − 2.00) M −1
slope = k = = = 2.08 × 10 −4 L/mol•s
∆x (1.80 × 10 4 − 0) s
To determine [NO2] at 2.70 × 104 s, use the integrated rate law, where 1/[NO2]o = 1/0.500 M
= 2.00 M −1 .
1 1 1 2.08 × 10 −4 L
= kt + , = × 2.70 × 104 s + 2.00 M −1
[ NO 2 ] [ NO 2 ]0 [ NO 2 ] mol s
1
= 7.62, [NO2] = 0.131 M
[ NO 2 ]
42. a. Because the 1/[A] versus time plot was linear, the reaction is second order in A. The slope
of the 1/[A] versus time plot equals the rate constant k. Therefore, the rate law, the
integrated rate law, and the rate constant value are:
1 1
Rate = k[A]2; = kt + ; k = 3.60 × 10−2 L/mol • s
[A] [A]0
1
b. The half-life expression for a second-order reaction is: t1/2 =
k[A]0
1
For this reaction: t1/2 = −2 −3
= 9.92 × 103 s
3.60 × 10 L/mol • s × 2.80 × 10 mol/L
Note: We could have used the integrated rate law to solve for t1/2, where
[A] = (2.80 × 10−3/2) mol/L.
c. Because the half-life for a second-order reaction depends on concentration, we must use
the integrated rate law to solve.
1 1 1 3.60 × 10 −2 L 1
= kt + , −
= ×t +
[A] [A]0 7.00 × 10 M4 mol s 2.80 × 10 −3 M
1.43 × 103 − 357 = (3.60 × 10−2)t, t = 2.98 × 104 s
43. a. Because the [C2H5OH] versus time plot was linear, the reaction is zero order in C2H5OH.
The slope of the [C2H5OH] versus time plot equals −k. Therefore, the rate law, the
integrated rate law, and the rate constant value are: Rate = k[C2H5OH]0 = k; [C2H5OH]
= −kt + [C2H5OH]0; k = 4.00 × 10−5 mol/L•s
b. The half-life expression for a zero-order reaction is t1/2 = [A]0/2k.

[C 2 H 5 OH]0 1.25 × 10 −2 mol/L
t1/2 = = = 156 s
2k 2 × 4.00 × 10 −5 mol/L • s
Note: We could have used the integrated rate law to solve for t1/2, where
[C2H5OH] = (1.25 × 10−2/2) mol/L.
c. [C2H5OH] = −kt + [C2H5OH]0 , 0 mol/L = −(4.00 × 10−5 mol/L•s)t +

1.25 × 10−2 mol/L
1.25 × 10 −2 mol/L
t= = 313 s
4.00 × 10 −5 mol/L • s
44. From the data, the pressure of C2H5OH decreases at a constant rate of 13 torr for every 100. s.
Because the rate of disappearance of C2H5OH is not dependent on concentration, the reaction
is zero order in C2H5OH.
13 torr 1 atm
k= × = 1.7 × 10 −4 atm/s
100. s 760 torr
The rate law and integrated rate law are:
 1 atm 
Rate = k = 1.7 × 10 −4 atm/s; PC 2 H 5OH = −kt + 250. torr   = −kt + 0.329 atm
 760 torr 
At 900. s: PC 2 H 5OH = −1.7 × 10 −4 atm/s × 900. s + 0.329 atm = 0.176 atm = 0.18 atm = 130 torr
45. The first assumption to make is that the reaction is first order. For a first-order reaction, a graph
of ln[C4H6] versus t should yield a straight line. If this isn't linear, then try the second- order
plot of 1/[C4H6] versus t. The data and the plots follow:
Time 195 604 1246 2180 6210 s

[C4H6] 1.6 × 10−2 1.5 × 10−2 1.3 × 10−2 1.1 × 10−2 0.68 × 10−2 M
ln[C4H6] −4.14 −4.20 −4.34 −4.51 −4.99
1/[C4H6] 62.5 66.7 76.9 90.9 147 M −1
Note: To reduce round-off error, we carried extra significant figures in the data points.
The natural log plot is not linear, so the reaction is not first order. Because the second-order
plot of 1/[C4H6] versus t is linear, we can conclude that the reaction is second order in
butadiene. The rate law is:
Rate = k[C4H6]2
1 1
For a second-order reaction, the integrated rate law is = kt + .
[C 4 H 6 ] [C 4 H 6 ]0
The slope of the straight line equals the value of the rate constant. Using the points on the
line at 1000. and 6000. s:
144 L/mol − 73 L/mol
k = slope = = 1.4 × 10−2 L/mol•s
6000. s − 1000. s
46. a. First, assume the reaction to be first order with respect to O. Hence a graph of ln[O]
versus t would be linear if the reaction is first order.
t (s) [O] (atoms/cm3) ln[O]

0 5.0 × 109 22.33
10. × 10−3 1.9 × 109 21.37
20. × 10−3 6.8 × 108 20.34
30. × 10−3 2.5 × 108 19.34
Because the graph is linear, we can conclude the reaction is first order with respect to O.
b. The overall rate law is Rate = k[NO2][O].
Because NO2 was in excess, its concentration is constant. Thus, for this experiment, the
rate law is Rate = k′[O], where k′ = k[NO2]. In a typical first-order plot, the slope
equals −k. For this experiment, the slope equals −k′ = −k[NO2]. From the graph:
19.34 − 22.23
slope = = −1.0 × 102 s−1, k′ = −slope = 1.0 × 102 s−1
(30. × 10 −3 − 0) s
To determine k, the actual rate constant:
k′ = k[NO2], 1.0 × 102 s−1 = k(1.0 × 1013 molecules/cm3)
k = 1.0 × 10−11 cm3/molecules•s

47. Because the 1/[A] versus time plot is linear with a positive slope, the reaction is second order
with respect to A. The y intercept in the plot will equal 1/[A]0. Extending the plot, the y
intercept will be about 10, so 1/10 = 0.1 M = [A]0.
48. a. The slope of the 1/[A] versus time plot in Exercise 45 will equal k.
(60 − 20) L/mol
Slope = k = = 10 L/mol•s
(5 − 1) s
1 1 10 L 1
= kt + = × 9s + = 100, [A] = 0.01 M
[A] [A]o mol s 0.1 M
1
b. For a second-order reaction, the half-life does depend on concentration: t1/2 =
k [A]0
1
First half-life: t1/2 = =1s
10 L 0.1 mol
×
mol s L
Second half-life ([A]0 is now 0.05 M): t1/2 = 1/(10 × 0.05) = 2 s
Third half-life ([A]0 is now 0.025 M): t1/2 = 1/(10 × 0.025) = 4 s
49. a. [A] = −kt + [A]0; if k = 5.0 × 10−2 mol/L•s and [A]0 = 1.00 × 10−3 M, then:
[A] = −(5.0 × 10−2 mol/L•s)t + 1.00 × 10−3 mol/L

[A]0
b. = −(5.0 × 10−2)t1/2 + [A]0 because at t = t1/2, [A] = [A]o/2.
2
0.50(1.00 × 10 −3 )
−0.50[A]0 = −(5.0 × 10−2)t1/2, t1/2 = = 1.0 × 10−2 s
5.0 × 10 − 2
[A]0
Note: We could have used the t1/2 expression to solve (t1/2 = ).
2k
c. [A] = −kt + [A]0 = −(5.0 × 10−2 mol/L•s)(5.0 × 10−3 s) + 1.00 × 10−3 mol/L
[A] = 7.5 × 10−4 mol/L
[A]reacted = 1.00 × 10−3 mol/L − 7.5 × 10−4 mol/L = 2.5 × 10−4 mol/L
[B]produced = [A]reacted = 2.5 × 10−4 M
50. a. The integrated rate law for this zero-order reaction is [HI] = −kt + [HI]0.
 1.20 × 10 −4 mol  
[HI] = −kt + [HI]0, [HI] = −   ×  25 min × 60 s  + 0.250 mol
 Ls   min  L
 
[HI] = −0.18 mol/L + 0.250 mol/L = 0.07 M
[HI]0
b. [HI] = 0 = −kt + [HI]0, kt = [HI]0, t =
k
0.250 mol/L
t= = 2080 s = 34.7 min
1.20 × 10 − 4 mol/L • s
51. If [A]0 = 100.0, then after 65 s, 45.0% of A has reacted, or [A] = 55.0. For first order
reactions:
 [A] 
 = − kt , ln
55.0 
ln  = −k(65 s), k = 9.2 × 10−3 s−1
 [ A ]0  100 . 0 
ln 2 0.693
t1/2 = = = 75 s
k 9.2 × 10 −3 s −1
52. a. When a reaction is 75.0% complete (25.0% of reactant remains), this represents two half-
lives (100% → 50% → 25%). The first-order half-life expression is t1/2 = (ln 2)/k. Because
there is no concentration dependence for a first-order half-life, 320. s = two half-lives, t1/2
= 320./2 = 160. s. This is both the first half-life, the second half-life, etc.
ln 2 ln 2 ln 2
b. t1/2 = , k = = = 4.33 × 10 −3 s −1
k t1/ 2 160. s
At 90.0% complete, 10.0% of the original amount of the reactant remains, so [A] =
0.100[A]0.
 [A]  0.100[A]0 ln(0.100)
ln  = − kt, ln = −(4.33 × 10 −3 s −1 )t, t = = 532 s
 [A]0  [A] 0 − 4.33 × 10 −3 s −1
53. For a first-order reaction, the integrated rate law is ln([A]/[A]0) = −kt. Solving for k:
 0.250 mol/L 
ln  = −k × 120. s, k = 0.0116 s −1
 1.00 mol/L 
 0.350 mol/L 
ln  = −0.0116 s −1 × t, t = 150. s
 2.00 mol/L 
 [A]  ln 2 0.693
54. ln  = − kt; k = = = 0.0124 d −1
 [ A ]0 t 1/ 2 56. 0 days
 1.41 × 10 −7 mol/L 
ln  = −(0.0124 d−1)t, t = 519 days
 8.75 × 10 −5 mol/L 
 
55. The integrated rate law for a second order reaction is 1/[A] = kt + 1/[A]0. Using the integrated
rate law:
_
1 1 (50. 10.) L/mol
= 0.40 L/mol•min × t + , t = = 1.0 × 102 min
0.020 mol/L 0.10 mol/L 0.40 L/mol • min
56. a. The integrated rate law for a second order reaction is 1/[A] = kt + 1/[A]0, and the half-
life expression is t1/2 = 1/k[A]0. We could use either to solve for t1/2. Using the
integrated rate law:
1 1 1.11 L/mol
= k × 2.00 s + , k = = 0.555 L/mol•s
(0.900/2) mol/L 0.900 mol/L 2.00 s
1 1 8.9 L/mol
b. = 0.555 L/mol•s × t + , t = = 16 s
0.100 mol/L 0.900 mol/L 0.555 L/mol • s
57. Successive half-lives double as concentration is decreased by one-half. This is consistent

with second-order reactions, so assume the reaction is second order in A.
1 1 1
t1/2 = , k= = = 1.0 L/mol•min
k[A]0 t1 / 2 [A]0 10.0 min(0.10 M )
1 1 1.0 L 1
a. = kt + = × 80.0 min + = 90. M −1 , [A] = 1.1 × 10 −2 M
[A] [A]0 mol min 0.10 M
b. 30.0 min = 2 half-lives, so 25% of original A is remaining.
[A] = 0.25(0.10 M) = 0.025 M
58. The consecutive half-life values of 24 hours, then 12 hours, show a direct relationship with
concentration; as the concentration decreases, the half-life decreases. Assuming the drug
reaction is either zero, first, or second order, only a zero order reaction shows this direct
relationship between half-life and concentration. Therefore, assume the reaction is zero order
in the drug.
[A]0 [A]0 2.0 × 10 −3 mol/L
t1/2 = , k = = = 4.2 × 10 −5 mol/L•h
2k 2t1/2 2(24 h)
59. Because [V]0 >> [AV]0, the concentration of V is essentially constant in this experiment. We
have a pseudo-first-order reaction in AV:
Rate = k[AV][V] = k′[AV], where k′ = k[V]0
The slope of the ln[AV] versus time plot is equal to −k′.

k′ 0.32 s −1
k′ = −slope = 0.32 s−1; k = = = 1.6 L/mol•s
[V]0 0.20 mol/L
60. Because [B]0 >> [A]0, the B concentration is essentially constant during this experiment, so
rate = k′[A] where k′ = k[B]2. For this experiment, the reaction is a pseudo-first-order
reaction in A.
 [A]   3.8 × 10 −3 M 
ln   = −k′t, ln   −1
a.  1.0 × 10 − 2 M  = −k′ × 8.0 s, k′ = 0.12 s
 [ A ]0   
For the reaction: k′ = k[B]2, k = 0.12 s−1/(3.0 mol/L)2 = 1.3 × 10 −2 L2 mol−2 s−1
ln 2 0.693
b. t1/2 = = = 5.8 s
k' 0.12 s −1
 [A]  [A]
c. ln  −2
 = −0.12 s −1 × 13.0 s,
 −2
= e−0.12(13.0) = 0.21
 1 .0 × 10 M  1 . 0 × 10
[A] = 2.1 × 10 −3 M
d. [A] reacted = 0.010 M − 0.0021 M = 0.008 M

2 mol C
[C] reacted = 0.008 M × = 0.016 M ≈ 0.02 M
1 mol A
[C]remaining = 2.0 M − 0.02 M = 2.0 M; as expected, the concentration of C basically
remains constant during this experiment since [C]0 >> [A]0.
Reaction Mechanisms
61. For elementary reactions, the rate law can be written using the coefficients in the balanced
equation to determine orders.
a. Rate = k[CH3NC] b. Rate = k[O3][NO]
c. Rate = k[O3] d. Rate = k[O3][O]
62. From experiment (Exercise 39), we know the rate law is Rate = k[H2O2]. A mechanism
consists of a series of elementary reactions where the rate law for each step can be determined
using the coefficients in the balanced equation for each respective step. For a plausible
mechanism, the rate law derived from a mechanism must agree with the rate law determined
from experiment. To derive the rate law from the mechanism, the rate of the reaction is
assumed to equal the rate of the slowest step in the mechanism.
This mechanism will agree with the experimentally determined rate law only if step 1 is the
slow step (called the rate-determining step). If step 1 is slow, then Rate = k[H2O]2 which agrees
with experiment.
Another important property of a mechanism is that the sum of all steps must give the overall
balanced equation. Summing all steps gives:
H2O2 → 2 OH
H2O2 + OH → H2O + HO2
HO2 + OH → H2O + O2
2 H2O2 → 2 H2O + O2
63. A mechanism consists of a series of elementary reactions in which the rate law for each step
can be determined using the coefficients in the balanced equations. For a plausible mechanism,
the rate law derived from a mechanism must agree with the rate law determined from
experiment. To derive the rate law from the mechanism, the rate of the reaction is assumed to
equal the rate of the slowest step in the mechanism.
Because step 1 is the rate-determining step, the rate law for this mechanism is Rate =
k[C4H9Br]. To get the overall reaction, we sum all the individual steps of the mechanism.
Summing all steps gives:
C4H9Br → C4H9+ + Br−
C4H9+ + H2O → C4H9OH2+
C4H9OH2+ + H2O → C4H9OH + H3O+
C4H9Br + 2 H2O → C4H9OH + Br− + H3O+
Intermediates in a mechanism are species that are neither reactants nor products but that
are formed and consumed during the reaction sequence. The intermediates for this
mechanism are C4H9+ and C4H9OH2+.
64. Because the rate of the slowest elementary step equals the rate of a reaction:
Rate = rate of step 1 = k[NO2]2
The sum of all steps in a plausible mechanism must give the overall balanced reaction.
Summing all steps gives:
NO2 + NO2 → NO3 + NO

NO3 + CO → NO2 + CO2
NO2 + CO → NO + CO2
65. The rate law is Rate = k[NO]2[Cl2]. If we assume the first step is rate-determining, we would
expect the rate law to be Rate = k1[NO][Cl2]. This isn't correct. If we assume the second step
is rate-determining, then Rate = k2[NOCl2][NO]. To see if this agrees with experiment, we
must substitute for the intermediate NOCl2 concentration. Assuming a fast- equilibrium first
step (rate reverse = rate forward):
k1
k-1[NOCl2] = k1[NO][Cl2], [NOCl2] = [NO][Cl2]; substituting into the rate equation:
k −1
k 2 k1 k k
Rate = [NO]2[Cl2] = k[NO]2[Cl2] where k = 2 1
k −1 k −1
This is a possible mechanism with the second step the rate-determining step because the derived
rate law agrees with the experimentally determined rate law.
66. Let's determine the rate law for each mechanism. If the rate law derived from the mechanism
is the same as the experimental rate law, then the mechanism is possible (assuming the sum of
all the steps in the mechanism gives the overall balanced equation). When deriving rate laws
from a mechanism, we must substitute for all intermediate concentrations.
a. Rate = k1[NO][O2]; not possible

k1
b. Rate = k2[NO3][NO] and k1[NO][O2] = k−1[NO3] or [NO3] = [NO][O2]
k −1
k 2 k1
Rate = [NO]2[O2]; possible
k −1
c. Rate = k1[NO]2; not possible
k1 k k
d. Rate = k2[N2O2] and [N2O2] = [NO]2, Rate = 2 1 [NO]2 ; not possible
k −1 k −1
Only the mechanism in b is consistent with the experimentally determined rate law, so only
mechanism b is a possible mechanism for this reaction.
Temperature Dependence of Rate Constants and the Collision Model

67. In the following plot, R = reactants, P = products, Ea = activation energy, and RC = reaction
coordinate, which is the same as reaction progress. Note for this reaction that ΔE is positive
because the products are at a higher energy than the reactants.
E
Ea P
R ∆E
RC
68. When ΔE is positive, the products are at a higher energy relative to reactants, and when ΔE is
negative, the products are at a lower energy relative to reactants. RC = reaction coordinate,
which is the same as reaction progress.
69.
125
kJ/mol
E R
216 Ea, reverse
kJ/mol
P
RC
The activation energy for the reverse reaction is:
Ea, reverse = 216 kJ/mol + 125 kJ/mol = 341 kJ/mol
70.
The activation energy for the reverse reaction is ER in the diagram.
ER = 167 − 28 = 139 kJ/mol
71. The Arrhenius equation is k = A exp(−Ea/RT) or, in logarithmic form, ln k = −Ea/RT + ln A.

Hence a graph of ln k versus 1/T should yield a straight line with a slope equal to −Ea/R since
the logarithmic form of the Arrhenius equation is in the form of a straight-line equation, y = mx
+ b. Note: We carried extra significant figures in the following ln k values in order to reduce
round off error.
T (K) 1/T (K−1) k (s−1) ln k

338 2.96 × 10−3 4.9 × 10−3 −5.32
318 3.14 × 10−3 5.0 × 10−4 −7.60
298 3.36 × 10−3 3.5 × 10−5 −10.26
− 10.76 − (−5.85)
Slope = = −1.2 × 104 K = −Ea/R
3.40 × 10 −3 − 3.00 × 10 −3
8.3145 J
Ea = −slope × R = 1.2 × 104 K × , Ea = 1.0 × 105 J/mol = 1.0 × 102 kJ/mol
K mol
72. From the Arrhenius equation in logarithmic form (ln k = −Ea/RT + ln A), a graph of ln k
versus 1/T should yield a straight line with a slope equal to −Ea/R and a y intercept equal to
ln A.
8.3145 J
a. Slope = −Ea/R, Ea = 1.10 × 104 K × = 9.15 × 104 J/mol = 91.5 kJ/mol
K mol
b. The units for A are the same as the units for k ( s −1 ).
y intercept = ln A, A = e33.5 = 3.54 × 1014 s −1
c. ln k = −Ea/RT + ln A or k = A exp(−Ea/RT)
 − 9.15 × 10 4 J/mol 
14 −1

k = 3.54 × 10 s × exp   = 3.24 × 10 −2 s −1

 8.3145 J/K • mol × 298 K 
− Ea
73. k = A exp(−Ea/RT) or ln k = + ln A (the Arrhenius equation)
RT
k  E 1 1 
For two conditions: ln  2  = a  −  (Assuming A is temperature independent.)
 k1  R  T1 T2 
Let k1 = 3.52 × 10 −7 L/mol•s, T1 = 555 K; k2 = ?, T2 = 645 K; Ea = 186 × 103 J/mol

 k2  1.86 × 10 5 J/mol  1 1 
ln   =  −  = 5.6
 3.52 × 10 −7  8.3145 J/K • mol  555 K
  645 K 
k2
= e5.6 = 270, k2 = 270(3.52 × 10 −7 ) = 9.5 × 10 −5 L/mol•s
3.52 × 10 −7
k  E  1 1 
74. For two conditions: ln  2  = a  −  (Assuming A is temperature independent.)
 k1  R  T1 T2 
 8.1 × 10 −2 s −1  Ea  1 1 
ln  =  
− 2 −1  8.3145 J/K • mol  273 K − 293 K
 4.6 × 10 s   
Ea
0.57 = (2.5 × 10 −4 ), Ea = 1.9 × 104 J/mol = 19 kJ/mol
8.3145
k  E  1 1  k2
75. ln  2  = a  − ; = 7.00, T1 = 295 K, Ea = 54.0 × 103 J/mol
 1
k R  1
T T2  k 1
5.4 × 10 4 J/mol  1 1  1 1
ln(7.00) =  − , − = 3.00 × 10 −4
8.3145 J/K • mol  295 K T2  295 K T2
1
= 3.09 × 10 −3 , T2 = 324 K = 51°C
T2
k  E 1 1 
76. ln  2  = a  − ; because the rate doubles, k2 = 2k1.
 k1  R  T1 T2 
Ea  1 1 
ln(2.00) =  − , Ea = 5.3 × 104 J/mol = 53 kJ/mol
8.3145 J/K • mol  298 K 308 K 
77. H3O+(aq) + OH−(aq) → 2 H2O(l) should have the faster rate. H3O+ and OH− will be electro-
statically attracted to each other; Ce4+ and Hg22+ will repel each other. The activation energy
for the Ce4+ and Hg22+ reaction should be a larger quantity, making it the slower reaction.
78. Carbon cannot form the fifth bond necessary for the transition state because of the small
atomic size of carbon and because carbon doesn’t have low-energy d orbitals available to
expand the octet.
Catalysts
79. a. NO is the catalyst. NO is present in the first step of the mechanism on the reactant side,
but it is not a reactant. NO is regenerated in the second step and does not appear in
overall balanced equation.
b. NO2 is an intermediate. Intermediates also never appear in the overall balanced equation.
In a mechanism, intermediates always appear first on the product side, whereas catalysts
always appear first on the reactant side.
k cat A exp[− E a (cat)/RT]  E (un ) − E a (cat ) 
c. k = A exp(−Ea/RT); = = exp  a 
k un A exp[− E (un)/RT]  RT 
k cat  2100 J/mol 
= exp   = e0.85 = 2.3
k un  8.3145 J/K • mol × 298 K 
The catalyzed reaction is approximately 2.3 times faster than the uncatalyzed reaction at
25°C.
80. The mechanism for the chlorine catalyzed destruction of ozone is:
O3 + Cl → O2 + ClO (slow)
ClO + O → O2 + Cl (fast)
O3 + O → 2 O2
Because the chlorine atom-catalyzed reaction has a lower activation energy, the Cl-catalyzed
rate is faster. Hence Cl is a more effective catalyst. Using the activation energy, we can estimate
the efficiency that Cl atoms destroy ozone compared to NO molecules (see Exercise 79c).
k Cl  − E a (Cl) E ( NO)   (−2100 + 11,900) J/mol  3.96
At 25°C: = exp  + a  = exp   = e = 52
k NO  RT RT   (8.3145 × 298) J/mol 
At 25°C, the Cl-catalyzed reaction is roughly 52 times faster than the NO-catalyzed reaction,
assuming the frequency factor A is the same for each reaction.
81. The reaction at the surface of the catalyst is assumed to follow the steps:
H H DCH 2
D D H C C H D D D CH 2 D D CH 2DCH 2D(g)
metal surface
Thus CH2D‒CH2D should be the product. If the mechanism is possible, then the reaction
must be:
C2H4 + D2 → CH2DCH2D
If we got this product, then we could conclude that this is a possible mechanism. If we got some
other product, for example, CH3CHD2, then we would conclude that the mechanism is wrong.
Even though this mechanism correctly predicts the products of the reaction, we cannot say
conclusively that this is the correct mechanism; we might be able to conceive of other
mechanisms that would give the same products as our proposed one.
82. a. W because it has a lower activation energy than the Os catalyst.
b. kw = Aw exp[−Ea(W)/RT]; kuncat = Auncat exp[−Ea(uncat)/RT]; assume Aw = Auncat.

kw  − E a (W) E (uncat ) 
= exp  + a 
k uncat  RT RT 
kw  − 163,000 J/mol + 335,000 J/mol 

= exp   = 1.41 × 10
30
k uncat  8.3145 J/K • mol × 298 K 
The W-catalyzed reaction is approximately 1030 times faster than the uncatalyzed
reaction.
c. Because [H2] is in the denominator of the rate law, the presence of H2 decreases the rate of
the reaction. For the decomposition to occur, NH3 molecules must be adsorbed on the
surface of the catalyst. If H2 is also adsorbed on the catalyst surface, then there are fewer
sites for NH3 molecules to be adsorbed, and the rate decreases.
83. The rate depends on the number of reactant molecules adsorbed on the surface of the catalyst.
This quantity is proportional to the concentration of reactant. However, when all the catalyst
surface sites are occupied, the rate becomes independent of the concentration of reactant.
84. At high [S], the enzyme is completely saturated with substrate. Once the enzyme is com-pletely
saturated, the rate of decomposition of ES can no longer increase, and the overall rate remains
constant.
85. Assuming the catalyzed and uncatalyzed reactions have the same form and orders, and be-
cause concentrations are assumed equal, the rates will be equal when the k values are equal.
k = A exp(−Ea/RT); kcat = kun when Ea,cat/RTcat = Ea,un/RTun.

4.20 × 10 4 J/mol 7.00 × 10 4 J/mol
= , Tun = 488 K = 215°C
8.3145 J/K • mol × 293 K 8.3145 J/K • mol × Tun
− ∆[A]
86. Rate = = k[A] x
∆t
Assuming the catalyzed and uncatalyzed reaction have the same form and orders, and
because concentrations are assumed equal, rate ∝ 1/∆t, where ∆t = ∆time.
Rate cat Δt 2400 yr rate cat k
= un = and = cat
Rate un Δt cat Δt cat rate un k un
Rate cat k A exp[− E a (cat)/RT]  − E a (cat) + E a (un) 
= cat = = exp  
Rate un k un A exp[− E a (un)/RT]  RT 
k cat  − 5.90 × 10 4 J/mol + 1.84 × 10 5 J/mol 

= exp  = 7.62 × 1010
k un • mol × 600. K

 8.3145 J/K 
Δt un rate cat k 2400 yr
= = cat , = 7.62 × 1010, ∆tcat = 3.15 × 10 −8 yr ≈ 1 s
Δt cat rate un k un Δt cat
Additional Exercises
87. Box a has 8 NO2 molecules. Box b has 4 NO2 molecules, and box c has 2 NO2 molecules. Box
b represents what is present after the first half-life of the reaction, and box c represents what is
present after the second half-life.
a. For first order kinetics, t1/2 = 0.693/k; the half-life for a first order reaction is concen-tration
independent. Therefore, the time for box c, the time it takes to go through two half-lives,
will be 10 + 10 = 20 minutes.
b. For second order kinetics, t1/2 = 1/k[A]0; the half-life for a second order reaction is in-
versely proportional to the initial concentration. So if the first half-life is 10 minutes, the
second half-life will be 20 minutes. For a second order reaction, the time for box c will be
10 + 20 = 30 minutes.
c. For zero order kinetics, t1/2 = [A]0/2k; the half-life for a zero order reaction is directly
related to the initial concentration. So if this reaction was zero order, then the second half-
life would decrease from 10 min to 5 min. The time for box c will be 10 + 5 = 15 minutes
if the reaction is zero order.
88. Rate = k[H 2SeO 3 ] x [H + ] y [I − ] z ; comparing the first and second experiments:
3.33 × 10 −7 k (2.0 × 10 −4 ) x (2.0 × 10 −2 ) y (2.0 × 10 −2 ) z

= , 2.01 = 2.0x, x = 1
1.66 × 10 −7 k (1.0 × 10 − 4 ) x (2.0 × 10 − 2 ) y (2.0 × 10 − 2 ) z
Comparing the first and fourth experiments:

6.66 × 10 −7 k (1.0 × 10 −4 )(4.0 × 10 −2 ) y (2.0 × 10 −2 ) z
−7
= −4 −2 y −2 z
, 4.01 = 2.0y, y = 2
1.66 × 10 k (1.0 × 10 )(2.0 × 10 ) (2.0 × 10 )
Comparing the first and sixth experiments:
13.2 × 10 −7 k (1.0 × 10 −4 )(2.0 × 10 −2 ) 2 (4.0 × 10 −2 ) z

=
1.66 × 10 −7 k (1.0 × 10 − 4 )(2.0 × 10 − 2 ) 2 (2.0 × 10 − 2 ) z
log (7.95)
7.95 = 2.0 z , log(7.95) = z log(2.0), z = = 2.99 ≈ 3
log(2.0)
Rate = k[H2SeO3][H+]2[I−]3
Experiment 1:
2 3
1.66 × 10 −7 mol  1.0 × 10 − 4 mol   2.0 × 10 − 2 mol   2.0 × 10 − 2 mol 
= k  

 
 


Ls  L  L   L 
k = 5.19 × 105 L5/mol5•s = 5.2 × 105 L5/mol5•s = kmean
89. The integrated rate law for each reaction is:
ln[A] = −4.50 × 10−4 s−1(t) + ln[A]0 and ln[B] = −3.70 × 10−3 s−1(t) + ln[B]0
Subtracting the second equation from the first equation (ln[A]0 = ln[B]0):
 [A] 
ln[A] − ln[B] = −4.50 × 10−4(t) + 3.70 × 10−3(t), ln   = 3.25 × 10−3(t)
 [B] 
When [A] = 4.00 [B], ln(4.00) = 3.25 × 10−3(t), t = 427 s.
90. The pressure of a gas is directly proportional to concentration. Therefore, we can use the
pressure data to solve the problem because Rate = −Δ[SO2Cl2]/Δt ∝ − ΔPSO 2Cl 2 /Δt.
Assuming a first order equation, the data and plot follow.
Time (hour) 0.00 1.00 2.00 4.00 8.00 16.00

PSO 2Cl 2 (atm) 4.93 4.26 3.52 2.53 1.30 0.34
ln PSO 2Cl 2 1.595 1.449 1.258 0.928 0.262 −1.08
Because the ln PSO 2Cl 2 versus time plot is linear, the reaction is first order in SO2Cl2.
a. Slope of ln(P) versus t plot: −0.168 hour −1 = −k, k = 0.168 hour −1 = 4.67 × 10 −5 s −1
Because concentration units don’t appear in first-order rate constants, this value of k
determined from the pressure data will be the same as if concentration data in molarity
units were used.
ln 2 0.6931 0.6931
b. t1/2 = = = = 4.13 hour
k k 0.168 h −1
 PSO 2Cl 2   PSO 2Cl 2 

c. ln  = −kt = −0.168 h−1(20.0 h) = −3.36,


 P
 = e −3.36 = 3.47 × 10 −2

 P0   0 
Fraction remaining = 0.0347 = 3.47%
91. From 338 K data, a plot of ln[N2O5] versus t is linear, and the slope = −4.86 × 10 −3 (plot not
included). This tells us the reaction is first order in N2O5 with k = 4.86 × 10 −3 at 338 K.
From 318 K data, the slope of ln[N2O5] versus t plot is equal to −4.98 × 10 −4 , so k = 4.98 ×
10 −4 at 318 K. We now have two values of k at two temperatures, so we can solve for Ea.
k  E  1 1   4.86 × 10 −3  Ea  1 1 
ln  2  = a  − , ln   =  
 −4  8.3145 J/K • mol  318 K − 338 K 
 k1  R  T1 T2   4.98 × 10   
Ea = 1.0 × 105 J/mol = 1.0 × 102 kJ/mol

Hence a graph of ln k versus 1/T should yield a straight line with a slope equal to -Ea/R since
the logarithmic form of the Arrhenius equation is in the form of a straight-line equation, y =
mx + b. Note: We carried one extra significant figure in the following ln k values in order to
reduce round-off error.
T (K) 1/T (K−1) k (L/mol•s) ln k

195 5.13 × 10−3 1.08 × 109 20.80
230. 4.35 × 10−3 2.95 × 109 21.81
260. 3.85 × 10−3 5.42 × 109 22.41
298 3.36 × 10−3 12.0 × 109 23.21
369 2.71 × 10−3 35.5 × 109 24.29
Using a couple of points on the plot:

20.95 − 23.65 − 2.70 − Ea
slope = −3 −3
= −3
= −1.35 × 103 K =
5.00 × 10 − 3.00 × 10 2.00 × 10 R
Ea = 1.35 × 103 K × 8.3145 J/K•mol = 1.12 × 104 J/mol = 11.2 kJ/mol
93. a. t (s) [C4H6] (M) ln[C4H6] 1/[C4H6] (M −1)

0 0.01000 −4.6052 1.000 × 102
1000. 0.00629 −5.069 1.59 × 102
2000. 0.00459 −5.384 2.18 × 102
3000. 0.00361 −5.624 2.77 × 102
The plot of 1/[C4H6] versus t is linear, thus the reaction is second order in butadiene.
From the plot (not included), the integrated rate law is:
1
= (5.90 × 10−2 L/mol•s)t + 100.0 M −1
[C 4 H 6 ]
b. When dimerization is 1.0% complete, 99.0% of C4H6 is left.
1
[C4H6] = 0.990(0.01000) = 0.00990 M; = (5.90 × 10−2)t + 100.0
0.00990
101 = (5.90 × 10−2)t + 100.0, t = 17 s ≈ 20 s
1
c. 10.0% complete, [C4H6] = 0.00900 M; = (5.90 × 10−2)t + 100.0,
0.00900
t = 188 s ≈ 190 s
1 1
d. = kt + ; [C4H6]0 = 0.0200 M; at t = t1/2, [C4H6] = 0.0100 M.
[C 4 H 6 ] [C 4 H 6 ]0
1 1
= (5.90 × 10−2)t1/2 + , t1/2 = 847 s = 850 s
0.0100 0.0200
1 1
Or: t1/2 = = = 847 s
k[A]0 (5.90 × 10 L/mol • s)(2.00 × 10 − 2 M)
−2
e. From Exercise 12.45, k = 1.4 × 10−2 L/mol•s at 500. K. From this problem, k = 5.90 ×
10−2 L/mol•s at 620. K.
k  E  1 1   5.90 × 10 −2  Ea  1 1 
ln  2  = a  − , ln  =  
 1.4 × 10 − 2  8.3145 J/K • mol  500. K − 620. K 
 k1  R  T1 T2     
12 = Ea(3.9 × 10−4), Ea = 3.1 × 104 J/mol = 31 kJ/mol
94. When the pressure decreases from 536 torr to 268 torr, this is a factor of one-half. We need to
determine the half-life of this reaction at 295oC, which requires us to calculate k at 295oC.
k  E  1 1 
For two conditions: ln  2  = a  −  (Assuming A is temperature independent.)
 k1  R  T1 T2 
 1.7 × 10 −2 s −1  Ea  1 1 
ln  − 4 −1
= 
 8.3145 J/K • mol  660. K − 720. K

 7.2 × 10 s   
Ea
3.2 = (1.3 × 10 −4 ), Ea = 2.0 × 105 J/mol
8.3145
Let k1 = 1.7 × 10 −2 s−1, T1 = 720. K; k2 = ?, T2 = 568 K (295oC); Ea = 2.0 × 105 J/mol
   
 = 2.0 × 10 J/mol  1
5
k2 1
ln  −  = −8.9
 1.7 × 10 − 2  8.3145 J/K • mol  720. K
   568 K 
k2
−2
= e−8.9, k2 = 2.3 × 10 −6 s−1
1.7 × 10
ln 2 0.693
For a first order reaction, t1/2 = ; t1/2 = = 3.0 × 105 s = 3.5 days
k 2.3 × 10 −6 s −1
95. To determine the rate of reaction, we need to calculate the value of the rate constant k. The
activation energy data can be manipulated to determine k.
 − 26.2 × 10 3 J/mol 
k = Ae − E a /RT = 0.850 s−1 × exp  = 3.29 × 10−5 s−1

 8.3145 J/K • mol × 310.2 K 
Rate = k[acetycholine receptor-toxin complex]
 0.200 mol 
Rate = 3.29 × 10 −5 s −1   = 6.58 × 10−6 mol/L•s
 L 
96. Rate = k[DNA]x[CH3I]y; comparing the second and third experiments:
1.28 × 10 −3 k (0.200) x (0.200) y

−4
= , 2.00 = 2.00 x , x = 1
6.40 × 10 x
k (0.100) (0.200) y
Comparing the first and second experiments:
6.40 × 10 −4 k (0.100)(0.200) y
= , 2.00 = 2.00 y , y = 1
3.20 × 10 − 4 k (0.100)(0.100) y
The rate law is Rate = k[DNA][CH3I].
Mechanism I is possible because the derived rate law from the mechanism (Rate =
k[DNA][CH3I]) agrees with the experimentally determined rate law. The derived rate law for
Mechanism II will equal the rate of the slowest step. This is step 1 in the mechanism giving a
derived rate law that is Rate = k[CH3I]. Because this rate law does not agree with experiment,
Mechanism II would not be a possible mechanism for the reaction.
97. a. If the interval between flashes is 16.3 s, then the rate is:
1 flash/16.3 s = 6.13 × 10−2 s−1 = k
Interval k T
16.3 s 6.13 × 10−2 s−1 21.0°C (294.2 K)
13.0 s 7.69 × 10−2 s−1 27.8°C (301.0 K)
k  E  1 1 
ln 2  = a  −  ; solving using above data: Ea = 2.5 × 104 J/mol = 25 kJ/mol
 
k 1 R  T1 T2 
 k  2.5 × 10 4 J/mol  1 1 
b. ln −2
 =  
 8.3145 J/K • mol  294.2 K − 303.2 K  = 0.30
 6.13 × 10   
k = e0.30 × (6.13 × 10−2) = 8.3 × 10−2 s−1; interval = 1/k = 12 seconds.
c. T Interval 54-2(Intervals)
21.0°C 16.3 s 21°C

27.8°C 13.0 s 28°C
30.0°C 12 s 30.°C
This rule of thumb gives excellent agreement to two significant figures.
k cat A cat exp (−E a , cat / RT )  − E a , cat + E a , uncat 

98. k = A exp(−Ea/RT); = = exp 

k uncat A uncat exp (−E a , uncat / RT )  RT 
k cat  − E a, cat + 5.00 × 10 4 J/mol 
3
2.50 × 10 = = exp  
k uncat  8.3145 J/K • mol × 310. K 
 
ln(2.50 × 103) × 2.58 × 103 J/mol = −Ea, cat + 5.00 × 104 J/mol
E a , cat = 5.00 × 104 J/mol − 2.02 × 104 J/mol = 2.98 × 104 J/mol = 29.8 kJ/mol
99. Comparing experiments 1 and 2, as the concentration of AB is doubled, the initial rate
increases by a factor of 4. The reaction is second order in AB.
Rate = k[AB]2, 3.20 × 10−3 mol/L•s = k(0.200 M)2
k = 8.00 × 10−2 mol/L•s = kmean
For a second order reaction:

1 1
t1/2 = = −2
= 12.5 s
k[AB]0 8.00 × 10 L/mol • s × 1.00 mol/L
100. Rate = k[A]x[B]y; comparing the first and second experiments:
11.8 k (0.50) x (1.0) y

= x y
, 3.9 = 2.5 x , taking the log of both sides gives :
3.0 k (0.20) (1.0)
log(3.9)
log(3.9) = x log(2.5), x = = 1.5
log(2.5)
Comparing the second and third experiments:
189.5 k (2.0)1.5 (2.0) y
= 1.5 y
, 16.1 = (4)1.5 (2.0) y , y = 1
11.8 k (0.50) (1.0)
The rate law is Rate = k[A]1.5[B].
Rate = k[A]1.5[B], 11.8 mol/L•s = k(0.50 M)1.5(1.0 M), k = kmean = 33 L1.5/mol1.5•s
101. a. Because [A]0 << [B]0 or [C]0, the B and C concentrations remain constant at 1.00 M for
this experiment. Thus Rate = k[A]2[B][C] = k′[A]2, where k′ = k[B][C].
For this pseudo-second-order reaction:

1 1 1 1
= k′t + , −5
= k′(3.00 min) +
[A] [A]0 3.26 × 10 M 1.00 × 10 − 4 M
k′ = 6890 L/mol•min = 115 L/mol•s

k′ 115 L/mol • s
k′ = k[B][C], k = , k = = 115 L3/mol3•s
[B][C] (1.00 M )(1.00 M )
b. For this pseudo-second-order reaction:
1 1
Rate = k′[A]2, t1/2 = = = 87.0 s
k ′ [A]0 115 L/mol • s(1.00 × 10 − 4 mol/L)
1 1 1
c. = k′t + = 115 L/mol•s × 600. s + = 7.90 × 104 L/mol
[A] [A]0 1.00 × 10 − 4 mol/L
[A] = 1/7.90 × 104 L/mol = 1.27 × 10–5 mol/L
From the stoichiometry in the balanced reaction, 1 mol of B reacts with every 3 mol of A.
Amount A reacted = 1.00 × 10–4 M – 1.27 × 10–5 M = 8.7 × 10–5 M

1 mol B
Amount B reacted = 8.7 × 10–5 mol/L × = 2.9 × 10–5 M
3 mol A
[B] = 1.00 M − 2.9 × 10–5 M = 1.00 M
As we mentioned in part a, the concentration of B (and C) remains constant because the

A concentration is so small compared to the B (or C) concentration.
ChemWork Problems
102. The coefficients in the balanced reaction relate the rate of consumption of reactants to the rate
of production of products. From the balanced reaction, the rate of production of I− will be equal
to the rate of consumption of S2O32−. By convention, all rates are given as positive values.
2−
− Δ[S 2 O 3 ] Δ[I − ] − (−7.05 × 10 −3 mol/L)
Rate = = = = 6.41 × 10 −4 mol/L•s
Δt Δt 11.0 s
103. Rate = k[A]x[B]y; using data from experiment 3 and experiment 4:

3.46 × 10 −2 k (0.24) x (0.090) y
= = 8.0x, 8.00 = 8.0x, x = 1
4.32 × 10 −3 x
k (0.030) (0.090) y
From experiments 1 and 4:

3.46 × 10 −2 k (0.24)(0.090) y
= , 1.00 = 2.0 × (1/2)y, 1/2 = (1/2)y, y = 1
3.46 × 10 − 2 k (0.12)(0.18) y
The reaction is first order with respect to both A and B; rate = k[A][B]
3.46 × 10 −2 mol  0.12 mol  0.18 mol 
From the first experiment: = k  ,
Ls  L  L 
k = 1.6 L/mol•s; all four experiments give the same value of k to two significant figures.
104. The integrated rate law for a zero-order reaction is [A] = −kt + [A]0.
0.021 mol  2.50 × 10 −2 mol  0.0800 mol

[A] = −kt + [A]0, = −   ×t +
 , t = 2.36 s
L  Ls  L
105. Because the ln[A] versus time plot is linear, the reaction is first order in A. The slope of
the ln[A] versus time plot equals −k. Therefore, the integrated rate law and the rate constant
value are:
ln[A] = −kt + ln[A]0; k = 7.35 × 10−3 s−1
From the problem, 77.1% A remains: [A] = 0.771(1.00 × 10−2 mol/L) = 7.71 × 10−3 mol/L
 [A]   7.71 × 10 −3 M 
ln  = − kt, ln 
 1.00 × 10 − 2 M  = −(7.35 × 10 s )t
−3 −1
 [A]0  
ln(0.771)
t= = 35.4 s
− 7.35 × 10 −3 s −1
106. Because the 1/[A] versus time plot was linear, the reaction is second order in A. The slope of
the 1/[A] versus time plot equals the rate constant k. Therefore, the rate law, the integrated
rate law, and the rate constant value are:
1 1
Rate = k[A]2; = kt + ; k = 6.90 × 10-2 L/ mol•s
[A] [A]0
1
The half-life expression for a second-order reaction is: t1/2 =
k[A]0
1
For this reaction: t1/2 = −2
= 145 s
6.90 × 10 L/mol • s × 0.100 mol/L
Note: We could have used the integrated rate law to solve for t1/2, where [A] = (0.100/2) M.
Because the half-life for a second-order reaction depends on concentration, we will use the
integrated rate law to solve. For the second half-life, [A] = 0.100/4 = 0.0250 mol/L and [A]0
= 0.0500 mol/L.
1 1 1 6.90 × 10 −2 L 1
= kt + , = × t + , t = 290. s = 2nd half-life
[A] [A]0 0.0250 M mol s 0.0500 M
107. a. False; from the half-life expression for a zero order reaction in Table 12.6 of the text,
there is a direct relationship between concentration and the half-life value. As the reaction
proceeds for a zero order reaction, the half-life value will decrease because concentration
decreases.
b. True; a catalyst does not affect the energy difference ∆E between products and reactants.
c. False; from the half-life expression for a first order reaction in Table 12.6, the half-life
does not depend on concentration.
d. True; the half-life for a second order reaction increases with time because there is an
inverse relationship between concentration and the half-life value.
k  E  1 1 
108. For two conditions: ln  2  = a  −  (Assuming A is temperature independent.)
 k1  R  T1 T2 
 0.891 L/mol • s  Ea  1 1 
ln  =  
−4  8.3145 J/K • mol  575 K − 781 K
 2.45 × 10 L/mol • s   
Ea
8.20 = (4.6 × 10 −4 ), Ea = 1.5 × 105 J/mol = 150 kJ/mol
8.3145
Let k1 = 0.891 L/mol•s, T1 = 781 K; k2 = ?, T2 = 648 K; Ea = 1.5 × 105 J/mol
 k2   
 = 1.5 × 10 J/mol  1 − 1
5
ln   = −4.7
 0.891  8.3145 J/K • mol  781 K
   648 K 
k2
= e−4.7 = 9.1 × 10−3, k2 = 8.1 × 10 −3 L/mol•s
0.891

Hence a graph of ln k versus 1/T should yield a straight line with a slope equal to -Ea/R since
the logarithmic form of the Arrhenius equation is in the form of a straight-line equation, y =
mx + b. Note: We carried one extra significant figure in the following ln k values in order to
reduce round-off error.
T (K) 1/T (K−1) k (min −1) ln k

−3
298.2 3.353 × 10 178 5.182
293.5 3.407 × 10−3 126 4.836
290.5 3.442 × 10−3 100. 4.605
The plot of ln k vs. 1/T gives a straight line. The equation for the straight line is:
ln k = −6.48 × 103(1/T) + 26.9; slope = −6.48 × 103 K = −Ea/R
Ea = 6.48 × 103 K × 8.3145 J/mol•K = 5.39 × 104 J/mol = 53.9 kJ/mol
ln k = −6.48 × 103 (1/280.7) + 26.9 = 3.8, k = e3.8 = 45 min−1
The chirping rate will be about 45 chirps per minute at 7.5oC.
Challenge Problems
[ A ]t
− d[A]
t
d[A]
110.
dt
= k[A]3, ∫ [A]3
= − ∫ k dt
[ A ]0 0
xn +1 1 [ A ]t
1 1
∫ x dx =
n
; so: − = − kt , − + = − kt
n +1 2[A]2 [ A ]0
2
2[A]t 2[A]02
For the half-life equation, [A]t = 1/2[A]0:

1 1 4 1
− + = − kt1/ 2 , − 2
+ = − kt1/ 2
1 
2 2
2[A]0 2[A]0 2[A]02
2 [A]0 
2 
3 3
− = − kt1/ 2 , t1/2 =
2[A]02 2[A]02 k
The first half-life is t1/2 = 40. s and corresponds to going from [A]0 to 1/2 [A]0. The second
half-life corresponds to going from 1/2 [A]0 to 1/4 [A]0 .
3 3 6
First half-life = 2
; second half-life = =
2[A]0 k 1 
2
[A]02 k
2 [A]0  k
2 
3
First half - life 2[A]02 k
= = 3/12 = 1/4
Second half - life 6
[A]02 k
Because the first half-life is 40. s, the second half-life will be four times this, or 160 s.
111. Rate = k[I−]x[OCl−]y[OH−]z; comparing the first and second experiments:
18.7 × 10 −3 k (0.0026) x (0.012) y (0.10) z

= , 2.0 = 2.0x, x = 1
9.4 × 10 −3 k (0.0013) x (0.012) y (0.10) z
Comparing the first and third experiments:
9.4 × 10 −3 k (0.0013)(0.012) y (0.10) z

= , 2.0 = 2.0y, y = 1
4.7 × 10 −3 k (0.0013)(0.0060) y (0.10) z
Comparing the first and sixth experiments:
4.8 × 10 −3 k (0.0013)(0.012)(0.20) z
= , 1/2 = 2.0z, z = −1
9.4 × 10 −3 k (0.0013)(0.012)(0.10) z
k[I − ][OCl − ]
Rate = ; the presence of OH− decreases the rate of the reaction.
[OH − ]
For the first experiment:
9.4 × 10 −3 mol (0.0013 mol/L) (0.012 mol/L)

=k , k = 60.3 s −1 = 60. s −1
Ls (0.10 mol/L)
For all experiments, kmean = 60. s −1 .
1 1 1
112. For second order kinetics: − = kt and t1/2 =
[A] [A]0 k[A]0
1 1 1 1
a. = (0.250 L/mol•s)t + , = 0.250 × 180. s +
[A] [A]0 [A] 1.00 × 10 − 2 M
1
= 145 M −1 , [A] = 6.90 × 10 −3 M
[A]
Amount of A that reacted = 0.0100 − 0.00690 = 0.0031 M.
1
[A2] = (3.1 × 10 −3 M) = 1.6 × 10 −3 M
2
b. After 3.00 minutes (180. s): [A] = 3.00[B], 6.90 × 10 −3 M = 3.00[B], [B] = 2.30 × 10 −3 M
1 1 1 1
= k2t + , −3
= k 2 (180. s) + , k2 = 2.19 L/mol•s
[B] [B]0 2.30 × 10 M 2.50 × 10 − 2 M
1 1
c. t1/2 = = = 4.00 × 102 s
k[A]0 0.250 L/mol • s × 1.00 × 10 − 2 mol/L
113. a. We check for first-order dependence by graphing ln[concentration] versus time for each
set of data. The rate dependence on NO is determined from the first set of data because the
ozone concentration is relatively large compared to the NO concentration, so [O3] is
effectively constant.
Time (ms) [NO] (molecules/cm3) ln[NO]
0 6.0 × 108 20.21
100. 5.0 × 108 20.03
500. 2.4 × 108 19.30
700. 1.7 × 108 18.95
1000. 9.9 × 107 18.41
Because ln[NO] versus t is linear, the reaction is first order with respect to NO.
We follow the same procedure for ozone using the second set of data. The data and
plot are:
Time (ms) [O3] (molecules/cm3) ln[O3]
0 1.0 × 1010 23.03
50. 8.4 × 109 22.85
100. 7.0 × 109 22.67
200. 4.9 × 109 22.31
300. 3.4 × 109 21.95
The plot of ln[O3] versus t is linear. Hence the reaction is first order with respect to
ozone.
b. Rate = k[NO][O3] is the overall rate law.
c. For NO experiment, Rate = k′[NO] and k′ = − (slope from graph of ln[NO] versus t).
18.41 − 20.21
k′ = −slope = − = 1.8 s −1
(1000. − 0) × 10 −3 s
For ozone experiment, Rate = k′′[O3] and k′′ = − (slope from ln[O3] versus t plot).
(21.95 − 23.03)
k′′ = −slope = − = 3.6 s −1
(300. − 0) × 10 −3 s
d. From the NO experiment, Rate = k[NO][O3] = k′ [NO] where k′ = k[O3].
k′ = 1.8 s −1 = k(1.0 × 1014 molecules/cm3), k = 1.8 × 10 −14 cm3/molecules•s
We can check this from the ozone data. Rate = k′′ [O3] = k[NO][O3], where k′′ = k[NO].
k′′ = 3.6 s −1 = k(2.0 × 1014 molecules/cm3), k = 1.8 × 10 −14 cm3/molecules•s
Both values of k agree.
114. Rate = k3[Br−][H2BrO3+]; we must substitute for the intermediate concentration. Because
steps 1 and 2 are fast-equilibrium steps, rate forward reaction = rate reverse reaction.
k2[HBrO3][H+] = k-2[H2BrO3+]; k1[BrO3−][H+] = k-1[HBrO3]

k1 k k 2 k1
[HBrO3] = [BrO3−][H+]; [H2BrO3+] = 2 [HBrO3][H+] = [BrO3−][H+]2
k −1 k −2 k − 2 k −1
k 3 k 2 k1
Rate = [Br−][BrO3−][H+]2 = k[Br−][BrO3−][H+]2
k − 2 k −1
115. a. Rate = k3[COCl][Cl2]; from the fast-equilibrium reactions 1 and 2:

[COCl] k k
= 2 , [COCl] = 2 [CO][Cl]
[Cl][CO] k −2 k −2
1/ 2
[Cl]2 k  k 
= 1 , [Cl] =  1 [Cl 2 ] 
[Cl 2 ] k −1  k −1 
1/ 2
k 2  k1 
Thus [COCl] =   [CO][Cl2]1/2; Substituting into rate law:
k − 2  k −1 
1/ 2
k  k 
Rate = k 3 2  1  [CO][Cl2]3/2 = k[CO][Cl2]3/2
k − 2  k −1 
b. Cl and COCl are intermediates.

116. On the energy profile to the right, R =

reactants, P = products, Ea =
activation energy, ΔE = overall
energy change for the reaction, I =
intermediate, and RC = reaction
coordinate, which is the same as
reaction progress.
a-d. See plot to the right.
e. This is a two-step reaction since an intermediate plateau appears between the reactant and
the products. This plateau represents the energy of the intermediate. The general reaction
mechanism for this reaction is:
R→I
I→P
R→P
In a mechanism, the rate of the slowest step determines the rate of the reaction. The
activation energy for the slowest step will be the largest energy barrier that the reaction
must overcome. Since the second hump in the diagram is at the highest energy, the second
step has the largest activation energy and will be the rate-determining step (the slow step).
k  E  1 1  rate 2 k
117. ln  2  = a  −  ; assuming = 2 = 40.0 :
 k1  R  T1 T2  rate1 k1
Ea  1 1 
ln(40.0) =  −  , Ea = 1.55 × 105 J/mol = 155 kJ/mol
8.3145 J/K • mol  308 K 328 K 
(carrying an extra sig. fig.)
Note that the activation energy is close to the F2 bond energy. Therefore, the rate-
determining step probably involves breaking the F2 bond.
H2(g) + F2(g) → 2 HF(g); for every 2 moles of HF produced, only 1 mole of the reactant is
used up. Therefore, to convert the data to Preactant versus time, Preactant = 1.00 atm – (1/2)PHF.
Preactant Time
1.000 atm 0 min
0.850 atm 30.0 min
0.700 atm 65.8 min
0.550 atm 110.4 min
0.400 atm 169.1 min
0.250 atm 255.9 min
The plot of ln Preactant versus time (plot not included) is linear with negative slope, so the
reaction is first order with respect to the limiting reagent.
For the reactant in excess, because the values of the rate constant are the same for both
experiments, one can conclude that the reaction is zero order in the excess reactant.
a. For a three-step reaction with the first step limiting, the energy-level diagram could be:
R
P
Reaction coordinate
Note that the heights of the second and third humps must be lower than the first-step acti-
vation energy. However, the height of the third hump could be higher than the second
hump. One cannot determine this absolutely from the information in the problem.
b. We know the reaction has a slow first step, and the calculated activation energy indicates
that the rate-determining step involves breaking the F2 bond. The reaction is also first order
in one of the reactants and zero order in the other reactant. All this points to F2 being the
limiting reagent. The reaction is first order in F2, and the rate-determining step in the
mechanism is F2 → 2 F. Possible second and third steps to complete the mechanism follow.
F2 → 2 F slow
F + H2 → HF + H fast
H + F → HF fast
F2 + H2 → 2 HF
c. F2 was the limiting reactant.
k  E  1 1 
118. We need the value of k at 500. K; ln 2  = a  − 
 k1  R  T1 T2 
 k2  1.11 × 10 5 J/mol  1 1 
ln  =  −  = 22.2
−12 
 2.3 × 10 L/mol • s  8.3145 J/K • mol  273 K 500 K 
k2
= e22.2, k2 = 1.0 × 10−2 L/mol•s
2.3 × 10 −12
Because the decomposition reaction is an elementary reaction, the rate law can be written using
the coefficients in the balanced equation. For this reaction, Rate = k[NO2]2. To solve for the
time, we must use the integrated rate law for second-order kinetics. The major problem now
is converting units so they match. Rearranging the ideal gas law gives n/V = P/RT. Substituting
P/RT for concentration units in the second-order integrated rate equation:
1 1 1 1 RT RT RT  P0 − P 
= kt + , = kt + , − = kt , t =  
[ NO 2 ] [ NO 2 ]0 P / RT P0 / RT P P0 k  P × P0 
(0.08206 L atm/K • mol)(500. K)  2.5 atm − 1.5 atm 

t= −2
×   = 1.1 × 103 s
1.0 × 10 L/mol • s  1.5 atm × 2.5 atm 
119. a. [B] >> [A], so [B] can be considered constant over the experiments. This gives us a
pseudo-order rate-law equation.
b. Note that in each case the half-life doubles as time increases (in experiment 1, the first half-
life is 40. s, the second half-life is 80. s; in experiment 2, the first half- life is 20. s, the
second half-life is 40. s). This occurs only for a second-order reaction, so the reaction is
second order in [A]. Between expt. 1 and expt. 2, we double [B] and the reaction rate
doubles, thus it is first order in [B]. The overall rate-law equation is rate = k[A]2[B].
1 1
Using t1/2 = , we get k = = 0.25 L/mol•s; but this is actually k′
k[A]0 (40.)(10.0 × 10 − 2 )
where Rate = k′[A]2 and k′ = k[B].
k′ 0.25
k= = = 0.050 L2/ mol2•s
[B] 5.0
c. i. This mechanism gives the wrong stoichiometry, so it can’t be correct.
ii. Rate = k[E][A]

k 1 [A][B] k k1
k1[A][B] = k-1[E]; [E] = ; Rate = [A]2 [B]
k −1 k −1
This mechanism gives the correct stoichiometry and gives the correct rate law. This
is a possible mechanism for this reaction.
iii. Rate = k[A]2
This mechanism gives the wrong derived rate law, so it can’t be correct. Only
mechanism ii is possible.
120. a. Rate = k[A]x[B]y; looking at the data in experiment 2, notice that the concentration of A is
cut in half every 10. s. Only first-order reactions have a half-life that is independent of
concentration. The reaction is first order in A. In the data for experiment 1, notice that the
half-life is 40. s. This indicates that in going from experiment 1 to experiment 2, where the
B concentration doubled, the rate of reaction increased by a factor of four. This tells us that
the reaction is second order in B.
Rate = k[A][B]2
b. This reaction in each experiment is pseudo-first order in [A] because the concentration of
B is so large, it is basically constant.
Rate = k[B]2[A] = k′ [A], where k′ = k[B]2
For a first-order reaction, the integrated rate law is:

 [A] 
ln  = − k′t
 [A]0 
Use any set of data you want to calculate kΝ. For example, in experiment 1, from 0 to
20. s the concentration of A decreased from 0.010 M to 0.0071 M:
 0.0071  −2 −1
ln  = − k′ (20. s), k′ = 1.7 × 10 s
 0.010 
k′ = k[B]2, 1.7 × 10 −2 s −1 = k(10.0 mol/L)2
k = 1.7 × 10 −4 L2/mol2•s
We get similar values for k using other data from either experiment 1 or experiment 2.
 [A] 
c. ln  = − k′t = − (1.7 × 10 −2 L2/mol2•s) × 30. s, [A] = 6.0 × 10 −3 M
 0.010 M 
121. Rate = k[A]x[B]y[C]z; during the course of experiment 1, [A] and [C] are essentially constant,
and Rate = k′[B]y , where k′ = k[A]0x [C]0z .
[B] (M) Time (s) ln[B] 1/[B] (M -1)

1.0 × 10 −3 0 −6.91 1.0 × 103
2.7 × 10 −4 1.0 × 105 −8.22 3.7 × 103
1.6 × 10 −4 2.0 × 105 −8.74 6.3 × 103
1.1 × 10 −4 3.0 × 105 −9.12 9.1 × 103
8.5 × 10 −5 4.0 × 105 −9.37 12 × 103
6.9 × 10 −5 5.0 × 105 −9.58 14 × 103
5.8 × 10 −5 6.0 × 105 −9.76 17 × 103
A plot of 1/[B] versus t is linear (plot not included), so the reaction is second order in B, and
the integrated rate equation is:
1/[B] = (2.7 × 10 −2 L/mol•s)t + 1.0 × 103 L/mol; k′ = 2.7 × 10 −2 L/mol•s
For experiment 2, [B] and [C] are essentially constant, and Rate = k′′[A]x, where k′′ =
k[B]0y [C]0z = k[B]02 [C]0z .
[A] (M) Time (s) ln[A] 1/[A] (M−1)

1.0 × 10 −2 0 −4.61 1.0 × 102
8.9 × 10 −3 1.0 −4.95 140
5.5 × 10 −3 5.0 −5.20 180
3.8 × 10 −3 8.0 −5.57 260
2.9 × 10 −3 10.0 −5.84 340
2.0 × 10 −3 13.0 −6.21 5.0 × 102
A plot of ln[A] versus t is linear, so the reaction is first order in A, and the integrated rate law
is:
ln[A] = −(0.123 s−1)t − 4.61; k′′ = 0.123 s −1
Note: We will carry an extra significant figure in k′′.
Experiment 3: [A] and [B] are constant; Rate = k′′′[C]z
The plot of [C] versus t is linear. Thus z = 0.
The overall rate law is Rate = k[A][B]2.
From Experiment 1 (to determine k):
k′ = 2.7 × 10 −2 L/mol•s = k[A]0x [C]0z = k[A]0 = k(2.0 M), k = 1.4 × 10 −2 L2/mol2•s

0.123 s −1
From Experiment 2: k′′= 0.123 s −1 = k[B] 02 , k = = 1.4 × 10 −2 L2/mol2•s
(3.0 M ) 2
Thus Rate = k[A][B]2 and k = 1.4 × 10−2 L2/mol2•s.
122. a. Rate = (k1 + k2[H+])[I−]m[H2O2]n

In all the experiments, the concentration of H2O2 is small compared to the concentrations
of I− and H+. Therefore, the concentrations of I− and H+ are effectively constant, and the
rate law reduces to:
Rate = kobs[H2O2]n, where kobs = (k1 + k2[H+])[I−]m
Because all plots of ln[H2O2] versus time are linear, the reaction is first order with respect
to H2O2 (n = 1). The slopes of the ln[H2O2] versus time plots equal −kobs, which equals
−(k1 + k2[H+])[I−]m. To determine the order of I−, compare the slopes of two experiments
in which I− changes and H+ is constant. Comparing the first two experiments:
slope (exp . 2) − 0.360 − [k1 + k 2 (0.0400 M )] (0.3000 M ) m
= =
slope (exp . 1) − 0.120 − [k1 + k 2 (0.0400 M )] (0.1000 M ) m
m
 0.3000 M 
3.00 =   = (3.000)m, m = 1
 0.1000 M 
The reaction is also first order with respect to I-.
b. The slope equation has two unknowns, k1 and k2. To solve for k1 and k2, we must have
two equations. We need to take one of the first set of three experiments and one of the
second set of three experiments to generate the two equations in k1 and k2.
Experiment 1: Slope = −(k1 + k2[H+])[I−]
−0.120 min−1 = −[k1 + k2(0.0400 M)](0.1000 M) or 1.20 = k1 + k2(0.0400)

Experiment 4:
−0.0760 min−1 = −[k1 + k2(0.0200 M)](0.0750 M) or 1.01 = k1 + k2(0.0200)
Subtracting 4 from 1:
1.20 = k1 + k2(0.0400)
−1.01 = −k1 − k2(0.0200)
0.19 = k2(0.0200), k2 = 9.5 L2/mol2•min
1.20 = k1 + 9.5(0.0400), k1 = 0.82 L/mol•min
c. There are two pathways, one involving H+ with Rate = k2[H+][I−][H2O2] and another not
involving H+ with Rate = k1[I−][H2O2]. The overall rate of reaction depends on which of
these two pathways dominates, and this depends on the H+ concentration.
Integrative Problems
3600 s ln 2 ln 2
123. 8.75 h × = 3.15 × 104 s; k = = = 2.20 × 10 −5 s −1
h t1/2 3.15 × 10 s
4
The partial pressure of a gas is directly related to the concentration in mol/L. So, instead of
using mol/L as the concentration units in the integrated first-order rate law, we can use partial
pressures of SO2Cl2.
P  P  3600 s
ln  = −kt, ln  = − (2.20 × 10 −5 s −1 ) × 12.5 h ×
 0
P  791 torr  h
1 atm
PSO 2Cl 2 = 294 torr × = 0.387 atm
760 torr
PV 0.387 atm × 1.25 L
n= = = 9.94 × 10 −3 mol SO2Cl2
RT 0.08206 L atm
× 593 K
K mol
6.022 × 10 23 molecules
9.94 × 10 −3 mol × = 5.99 × 1021 molecules SO2Cl2
mol
ln 2 ln 2
124. k= = = 1.04 × 10 −3 s −1
t1/ 2 667 s
1 mol InCl 1 mol In +

2.38 g InCl × ×
150.3 g mol InCl
[In+]0 = = 0.0317 mol/L
0.500 L
 [In + ]   [In + ]  3600 s

ln +  = − kt , ln  = − (1.04 × 10 −3 s −1 ) × 1.25 h ×

 [In ]0   0.0317 M  h
Solving: [In+] = 2.94 × 10 −4 mol/L
The balanced equation for the reaction is: 3 In+(aq) → 2 In(s) + In3+(aq)
0.0317 mol 2.94 × 10 −4 mol

Mol In+ reacted = 0.500 L × − 0.500 L ×
L L
= 1.57 × 10 −2 mol In+
2 mol In 114.8 g In
1.57 × 10 −2 mol In+ × +
× = 1.20 g In
3 mol In mol In
k  E 1 1   1.7 × 10 −2 s −1  Ea  1 1 
125. ln 2  = a  −  ; ln  =  − 
 k1  R  T1 T2   − 4 −1 
 7.2 × 10 s  8.3145 J/K • mol  660. K 720. K 
Solving: Ea = 2.1 × 105 J/mol
For k at 325°C (598 K):

 1.7 × 10 −2 s −1 
 = 2.1 × 10 J/mol  1 − 1 
5
ln   , k = 1.3 × 10 −5 s −1
 
 k  8.3145 J/K • mol  598 K 720. K 
For three half-lives, we go from 100% → 50% → 25% → 12.5%. After three half-lives,
12.5% of the original amount of C2H5I remains. Partial pressures are directly related to gas
concentrations in mol/L:
PC 2 H 5 I = 894 torr × 0.125 = 112 torr after 3 half-lives
Marathon Problem
126. a. Rate = k[CH3X]x[Y]y; for experiment 1, [Y] is in large excess, so its concentration will
be constant. Rate = k′[CH3X]x, where k′ = k(3.0 M)y.
A plot (not included) of ln[CH3X] versus t is linear (x = 1). The integrated rate law is:
ln[CH3X] = −(0.93)t − 3.99; k′ = 0.93 h−1
For experiment 2, [Y] is again constant, with Rate = k′′ [CH3X]x, where k′′ = k(4.5 M)y.
The natural log plot is linear again with an integrated rate law:
ln[CH3X] = −(0.93)t − 5.40; k′′ = 0.93 h−1
k' 0.93 k (3.0) y

Dividing the rate-constant values: = = , 1.0 = (0.67)y, y = 0
k" 0.93 k (4.5) y
The reaction is first order in CH3X and zero order in Y. The overall rate law is:
Rate = k[CH3X], where k = 0.93 h−1 at 25°C

b. t1/2 = (ln 2)/k = 0.6931/(7.88 × 108 h−1) = 8.80 × 10−10 hour
k  E  1 1   7.88 × 10 8  Ea  1 1 
ln 2  = a  −  , ln  =  
c.   8.3145 J/K • mol  298 K − 358 K 
 k1  R  T1 T2   0.93   
Ea = 3.0 × 105 J/mol = 3.0 × 102 kJ/mol
d. From part a, the reaction is first order in CH3X and zero order in Y. From part c, the acti-
vation energy is close to the C-X bond energy. A plausible mechanism that explains the
results in parts a and c is:
CH3X → CH3 + X (slow)

CH3 + Y → CH3Y (fast)
CH3X + Y → CH3Y + X
Note: This is a plausible mechanism because the derived rate law is the same as the
experimental rate law (and the sum of the steps gives the overall balanced equation).

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CHAPTER 12

15. In a unimolecular reaction, a single reactant molecule decomposes to products. In a bimolecular

19. Two reasons are:

b. ∆E1 represents the activation energy for the uncatalyzed pathway.

− ∆[PH 3 ] − (−0.048 mol/2.0 L)

− ∆[H 2 O 2 ] − (0.500 M − 1.000 M)

From the coefficients in the balanced equation:

Rate Laws from Experimental Data: Initial Rates Method

12.5 × 10 −6 k (0.080) x (0.040) y

12.5 × 10 −6 mol  0.080 mol  0.040 mol 

33. a. Rate = k[NOCl]n; using experiments two and three:

2.26 × 10−3 = k(0.190)x and 8.90 × 10−4 = k(0.0750)x

7.91 × 10 −2 k (0.12) x (0.18) y

7.91 × 10 −2 mol  0.12 mol  0.18 mol 

2.00 × 1016 molecules/cm3•s = k(1.00 × 1018 molecules/cm3)2

k = 2.00 × 10−38 cm6/molecules2•s = kmean

37. a. Rate = k[Hb]x[CO]y

c. From the first experiment:

0.619 µmol/L•s = k(2.21 µmol/L)(1.00 µmol/L), k = 0.280 L/µmol•s

38. a. Rate = k[ClO2]x[OH−]y; from the first two experiments:

2.30 × 10−1 = k(0.100)x(0.100)y and 5.75 × 10−2 = k(0.0500)x(0.100)y

2.30 × 10−1 = k(0.100)(0.100)y and 1.15 × 10−1 = k(0.100)(0.0500)y

The rate law is Rate = k[ClO2]2[OH−].

Integrated Rate Laws

Time [H2O2] ln[H2O2]

Rate = k[A]; ln[A] = −kt + ln[A]0; k = 2.97 × 10−2 min−1

b. The half-life expression for a first order rate law is:

100% → 50.0% → 25.0% → 12.5%; t = 3 × t1/2 = 3 × 23.3 min = 69.9 min

Or we can use the integrated rate law:

Time (s) [NO2] (M) ln[NO2] 1/[NO2] ( M −1 )

1.43 × 103 − 357 = (3.60 × 10−2)t, t = 2.98 × 104 s

b. The half-life expression for a zero-order reaction is t1/2 = [A]0/2k.

c. [C2H5OH] = −kt + [C2H5OH]0 , 0 mol/L = −(4.00 × 10−5 mol/L•s)t +

Time 195 604 1246 2180 6210 s

t (s) [O] (atoms/cm3) ln[O]

b. The overall rate law is Rate = k[NO2][O].

k′ = k[NO2], 1.0 × 102 s−1 = k(1.0 × 1013 molecules/cm3)

k = 1.0 × 10−11 cm3/molecules•s

Third half-life ([A]0 is now 0.025 M): t1/2 = 1/(10 × 0.025) = 4 s

[A] = −(5.0 × 10−2 mol/L•s)t + 1.00 × 10−3 mol/L

[A] = 7.5 × 10−4 mol/L

[B]produced = [A]reacted = 2.5 × 10−4 M

57. Successive half-lives double as concentration is decreased by one-half. This is consistent

[A] = 0.25(0.10 M) = 0.025 M

Rate = k[AV][V] = k′[AV], where k′ = k[V]0

The slope of the ln[AV] versus time plot is equal to −k′.

d. [A] reacted = 0.010 M − 0.0021 M = 0.008 M

a. Rate = k[CH3NC] b. Rate = k[O3][NO]

c. Rate = k[O3] d. Rate = k[O3][O]

Rate = rate of step 1 = k[NO2]2

NO2 + NO2 → NO3 + NO

a. Rate = k1[NO][O2]; not possible

Temperature Dependence of Rate Constants and the Collision Model

The activation energy for the reverse reaction is:

Ea, reverse = 216 kJ/mol + 125 kJ/mol = 341 kJ/mol

The activation energy for the reverse reaction is ER in the diagram.

ER = 167 − 28 = 139 kJ/mol