CHEM 102/105 Dr. M.

Gedik

Problem Set #2: Kinetics Part II and Equilibrium (warm-up)

DISCLAIMER: Questions marked with asterisk (*) are meant to be challenging and test your ability to
apply concepts learned in class to the problem.

1. For the reaction A ® products successive half-lives are obtained to be 10.0, 20.0 and 40.0 min
for an experiment in which [A]o = 0.10 M. Calculate the concentration of A after 25 min.
HINT: Think about what order the reaction should be based on the given information.

For questions where you need to calculate concentration after a certain time, you want first to
determine the order and use the appropriate integrated rate law for that order.
t1/2 changes Þ can’t be 1st order
[A]o
Try zero order First t1/2 =
2k
[A]o
2 [A]o
Second t1/2 = = < first t1/2
2k 4k
So successive half-lives for zero order decrease contrary to given data Þ can’t be zero order
1
Try second order First t1/2 =
k[A]o
1 2
Second t1/2 = = > first t1/2
[A]o k[A]o
k
2
So successive half-lives for second order increase agreeing with given data Þ 2nd order
Alternatively, recall that half-lives for second order reactions increase, while half-lives for zero order
reactions decrease(Handout 6). We discussed how to determine this by “inspection of the half-life
formulas” in lecture.

1 1
k= = = 1 M–1 min–1
t1/2 [A]o 10 min x 0.1 M

1 1 1
= + kt = + 1 M–1 min–1 x 25 min = 35 M–1
[A] [A]o 0.1 M

1
[A] = = 2.86 x 10–2 M
35 M–1
2. A reaction is carried out at 25 °C. When the temperature is increased by 15°C, the rate doubles.
(a) What is the activation energy of the reaction?
(b) Given that the enthalpy of the reaction is +23 kJ mol-1, sketch the reaction profile. Your diagram
should include axis labels, units, the value of Ea (both directions) and DH.

(a) Use the form of the Arrhenius equation which relates temperatures and rate constants. If the rate is
doubling, the rate constant will also double (you only need the ratio of rate constants).

k2 Ea 1 1
ln ! " = ! – "
k1 R T1 T2
2 Ea 1 1
ln ! " = ! – "
1 8.314 J/mol K 298.15 K 313.15 K

Ea = 36 kJ/mol

TS
(b)

Ea (forward) = 36 kJ Ea (reverse) = 13 kJ
Potential Energy (kJ)

Products

Reactants DH = + 23 kJ

Reaction Progress à

3. For a given reaction, the rate constant, k, was measured at two different temperatures. The two data
points determined in this experiment are as follows:
(1) 25 °C, 1.1 x 10–5 min–1 and (2) 225 °C, 2.4 x 10-2 min–1
The student who performed the experiment then plotted the logarithmic (linearized) form of the
Arrhenius equation.

(a) What value of Ea did the student get from the experimental data?
(b) What is the value of A?
(c) What is the order of this reaction?
 (a) From the linearized form of the Arrhenius equation:
Ea 1
ln k = ! " + ln 𝐴
R T

slope = -Ea/R for the plot of ln k vs 1/T.

Recall that ln k will represent the y values whereas 1/T represents the x values.
The slope of the line can be determined as follows:

ln k2 − ln k1 ln 2.4×10-2 − ln 1.1×10-5
slope = = = − 5.71×103 K
1/T2 − 1/T1 1 1
/498.15 K − 298.15 K0

Ea = −slope x R = −(−5.71´103 K)(8.314 J/mol K) = 4.7 ´104 J/mol = 47 kJ/mol

(b) Use the Arrhenius equation to solve for A, subbing in the value of Ea from above.
Ea
k = A 𝑒 "#RT$
4.7 ´104 J/mol
#% &
-2 -1 (8.314 J/mol K)(498.15 K)
2.4×10 min = 𝐴 e

A = 2.0 x 103 min-1 or 1.9 x 103 min-1 if you use the other data set.

(c) Based on the units of the rate constant (or A), the order of this reaction is 1.

4. Even when a mechanism is consistent with the rate law, later work may show it to be incorrect. For
example, the reaction between hydrogen and iodine has this rate law: rate = k[H2][I2]. The long
accepted mechanism had a single bimolecular step, that is, the overall reaction was thought to be

elementary: H2 (g) + I2 (g) ® 2 HI (g)

In the 1960s, however, spectroscopic evidence showed the presence of free I atoms during the reaction.
Kineticists have since proposed a three-step mechanism:
®
(1) I2 (g) ¬ 2 I (g) fast
®
(2) H2 (g) + I (g) ¬ H2I (g) fast

(3) H2I (g) + I (g) ® 2 HI (g) slow

Show that this mechanism is consistent with the rate law.
Derive the rate law starting with the rate determining step (step 3)
rate = k3 [H2I][I] intermediate [H2I] can’t be left in rate equation
k–2 [H2I] = k2 [H2][I] step 2 fast equilibrium
 k2
Rearrange: [H2I] = [H2][I]
k–2
k2
Insert into rate law: rate = k3 [H2][I]2 [I] needs to be replaced
k–2
k–1 [I]2 = k1 [I2] step 1 fast equilibrium
k1
Rearrange [I]2 =
[I ]
k–1 2
k2 k1
Insert into rate law rate = k3 [H2][I2]
k–2 k–1
k2 k1
Consistent with observed rate law, where kobserved = k3
k–2 k–1

5. The following three step mechanism has been proposed for the reaction of chlorine and chloroform.
k1
®
(1) Cl2 (g) ¬ 2 Cl (g)
k –1
k2
(2) Cl (g) + CHCl3 (g) ¾® HCl (g) + CCl3 (g)
k3
(3) CCl3 (g) + Cl (g) ¾® CCl4 (g)

The numerical values of the rates for these steps are: k1 = 4.8 x 103, k –1 = 3.6 x 103, k2 = 1.3 x 10–2,
k3 = 2.7 x 102. Derive the rate law and the magnitude of k for the overall reaction.
Note the units for each step is different and are not given, but I expect you to be able to find them if
needed. (Same approach as Q#2 of Problem Set 1)
k2 is much smaller than the other rate constants. \ Second step is RDS

Rate = k2 [Cl][CHCl3] can’t leave intermediate Cl in expression

From step 1 k1 [Cl2] = k –1 [Cl]2
k1
[Cl] = [Cl2]1/2
k –1
k1
Rate = k2 [Cl][CHCl3] = k2 [Cl2]1/2 [CHCl3] 1.5 order
k –1

k1 4.8 x 103
koverall = k2 = 1.3 x 10–2 = 0.015
k –1 3.6 x 103
M M
Determine the units of k: = k M1/2 M = k M3/2 à k= = M–1/2 s–1
s M3/2 s

\ k = 0.015 M–1/2 s–1

 [O3]2
*6. A simplified rate law for the reaction 2 O3 (g) ® 3 O2 (g) is rate = k .
[O2]

For this reaction, propose a two step mechanism that consists of a fast, reversible first step, followed
by a slow second step.

1st step is a fast reversible step in which an intermediate must be formed and later react in step 2.
®
If we use (similar to the previous problem) O3 ¬ 3 O we will not obtain a rate depending on O2.

®
So try Step 1 O3 ¬ O2 + O with rate constants k1 and k –1 respectively

In the second step we need O3 to react with the intermediate O.

Step 2 O3 + O ® 2 O2 with rate constant k2 (slow, so RDS)

®
Net: step 1 + step 2 2 O3 ¬ 3 O2 OK

Check rate based on proposed mechanism:

Rate = k2 [O3][O] (2nd step RDS) but can’t leave intermediate [O] in expression

k1 [O3]
First step k1 [O3] = k –1 [O2][O] or [O] =
k –1 [O2]

k1 [O3] k1 [O3]2 [O3]2

Replace in rate rate = k2 [O3] = k2 = kobserved
k –1 [O2] k –1 [O2] [O2]

k1
Agreement with observed rate law (kobserved = k2 ) Þ plausible mechanism
k –1
Here’s an alternative mechanism that yields the same rate law.
®
Step 1 2 O3 ¬ O2 + O4 fast

Step 2 O4 ® 2 O2 slow (RDS)

RateRDS = k2 [O4]
From the fast step 1 k1 [O3]2 = k –1 [O2][O4]
k1 [O3]2
[O4] =
k –1 [O2]
k1 [O3]2
Insert into rate of RDS rateRDS = k2 [O4] = k2
k –1 [O2]
®
Net: step 1 + step 2 2 O3 ¬ 3 O2 OK
Both proposed mechanisms are acceptable.
7. The following mechanism is proposed for the reaction of gaseous nitric oxide and bromine to form
nitrosyl bromide.
k1
®
NO (g) + Br2 (g) ¬ NOBr2 (g)
k –1

k2
NOBr2 (g) + NO (g) ¾® 2 NOBr (g)

Derive a theoretical rate law for the above mechanism.

HINT: You need to use the steady state approximation for this since you have no information on the
rates of reactions.

No information regarding relative rates Þ use steady state approximation

Rate = k2 [NOBr2][NO] use the step that produces the products (often last step)

Can’t leave intermediate [NOBr2] in expression

Write steady state equation: rate formation intermediate = rate disappearance intermediate

k1 [NO] [Br2] = k –1 [NOBr2] + k2 [NOBr2][NO]

k1 [NO] [Br2]
[NOBr2] =
k –1 + k2 [NO]

k1 [NO]2 [Br2]
Replace in rate: rate = k2 [NOBr2][NO]= k2
k –1 + k2 [NO]

The order from the derived rate law is not well defined as the denominator is an addition term.
However, we can narrow it down by looking at the two extreme conditions.

* Consider only the terms in the denominator. Set one term to be much larger than the other, to obtain
these extreme conditions:

i) k –1 >> k2 [NO] This is equivalent to step 1 being fast and step 2 being slow.

k1 [NO]2 [Br2] k1 [NO]2 [Br2]

Rate = k2 » k2 3rd order overall
k –1 + k2 [NO] k –1
 ii) k –1 << k2 [NO] This is equivalent to step 1 being slow and step 2 being fast.

k1 [NO]2 [Br2] k1 [NO]2 [Br2]

Rate = k2 » k2 = k1 [NO] [Br2] 2nd order overall
k –1 + k2 [NO] k2 [NO]

So the order is somewhere between 2nd order and 3rd order overall.

---------------------------------------------MIDTERM CUTOFF--------------------------------------------------

8. Write the equilibrium expression for the following reactions:

Using pressures rather than concentrations for gases, although concentrations are also valid.
®
a) Br2 (l) ¬ Br2 (g) K = PBr2 (g)

®
b) H2O (s) ¬ H2O (g) K = PH2O (g)

® [H3O+][F–]
c) HF (aq) + H2O (l) ¬ H3O+ (aq) + F– (aq) K=
[HF]

® [HCOOH][OH–]
d) HCOO– (aq) + H2O (l) ¬ HCOOH (aq) + OH– (aq) K=
[HCOO–]

®
e) Na2SO4×10H2O (s) ¬ Na2SO4 (s) + 10 H2O (g) K = PH2O10

®
f) BaF2 (s) ¬ Ba2+ (aq) + 2 F– (aq) K = [Ba2+][F–]2

®
PO2 (g)
g) O2 (aq) ¬ O2 (g) K=
[O2 (aq)]

® [I2 (aq)]
h) I2 (in CCl4) ¬ I2 (aq) K=
[I2 (CCl4)]

® [Cu(NH3)4 2+]
i) Cu2+ (aq) + 4 NH3 (aq) ¬ [Cu(NH3)4]2+ (aq) K=
[Cu2+][NH3]4