Problem Set #2 key

1. Phosgene gas can be produced by the reaction

CO(g) + Cl2 (g) –> COCl2
The rate law for the reaction is found to be rate=k [Cl2]3/2[CO]
A postulated mechanism is:
k1
Step1 Cl2<=> 2Cl
k-1
k2
Step 2 Cl + CO <=> COCl
k-2
k3
Step 3 COCl + Cl2 ==> COCl2 + Cl

(a) if this mechanism is correct, which step is rate-determining?

(b) Using the response to (a), determine the value of rate constant k in terms
of the individual k’s (k1, k-1, k2,…etc)

To answer (a), write what the rate law would be if each step were rate limiting:
For step 1, rate=k1 [Cl2], so clearly this step is not rate-determining.
For step 2, rate = k2 [Cl][CO] , but Cl is an intermediate and cannot show up
in the rate law. But we know from step 1 that k-1[Cl]2=k1[Cl2] (assuming a fast
equilibrium step), thus
[Cl]2 = k1[Cl2]/k-1 and [Cl]= (k1[Cl2]/k-1)1/2
substituting back into the rate expression gives:
rate = k2 [Cl][CO] = k2 (k1[Cl2]/k-1)1/2 [CO] = k [Cl2]1/2 [CO], so this step is not
rate-determining.
For step 3, rate= k3 [COCl][Cl2] but COCl is an intermediate.
We know that k-2[COCl] = k2 [Cl][CO]; [COCl] =k2[Cl][CO]/k-2 ] (assuming
a fast equilibrium step
Thus rate = k3 [COCl][Cl2] = k3(k2[Cl][CO]/k-2)[Cl2] =k [Cl][CO][Cl2]
We know that [Cl]= (k1[Cl2]/k-1)1/2 from above,

Thus rate = k (k1[Cl2]/k-1)1/2 [CO][Cl2] = k [Cl2]3/2[CO]

So third step is rate determining.
(b) since we collected all the rate constants into k for solving part (a), we just
go back and include all these rate constants in the final expression:
rate = k3 [COCl][Cl2] = k3(k2[Cl][CO]/k-2)[Cl2] = (k3k2/k-2) [Cl][CO][Cl2]
rate=(k3k2/k-2)[CO][Cl2](k1[Cl2]/k-1)1/2 = (k3k2k11/2/k-2k-11/2)[Cl2]3/2[CO]
kobs= k3k2 (k1)1/2/k-2 (k-1)1/2

2. The rate constant for a reaction at 40°C is exactly 3.00 times the rate constant
at 20°C. Calculate the Arrhenius energy of activation for the reaction
assuming a temperature-independent pre-exponential factor A.
since k=Ae-Ea/RT , k40°C/k20°C=3= Ae-Ea/RT2/ Ae-Ea/RT1 (the A’s cancel)
T2=273+40 = 313K
T1=273+20 = 293K
ln 3 = -Ea/R(1/T2-1/T1)= 1.09 = -Ea/R (1/313K – 1/293K)
Ea=41.5 kJ/mol (activation energies are always positive)

3. The reaction
A ==> B + C
Is second order in A. When [A]o=0.100M, the reaction is 20% complete in 40
minutes
(a) Calculate the value of the rate constant (in L/min mol)
(b) Calculate the half-life of the reaction
(a) For a second-order reaction:
1/[A]t = kt + 1/[A]o
[A]t=0.8 [A]o=.08M
Thus, (1/0.08M)- (1/0.10M) = k (40 minutes)
k=0.0625M-1m-1
-1 -1
(c) t1/2 = 1/k[A]o; 1/(0.0625M m )(0.1M) = 160 minutes = t1/2

4. 4. Two mechanisms have been proposed for the overall reaction:

2 NO(g) + H2(g) ==> N2O (g) + H2O (g)

Mechanism 1
NO + H2 <=> NOH2 fast
NOH2 + NO ==> N2O + H2O slow

Rate = k2[NOH2][NO], but [NOH2] is an intermediate

Consider first step as a fast equilibrium, then

k1[NO][H2]=k-1[NOH2]; [NOH2]=k1[NO][H2]/k-1

substituting: rate = k2[NO](k1[NO][H2]/k-1)=(k2k1/k-1)[NO]2[H2]=kobs[NO]2[H2]

Mechanism 2
2NO <=> N2O2 slow
N2O2 + H2 ==> N2O + H2O fast

Rate = k1 [NO][NO] = k1 [NO]2

To distinguish: mechanism 1 has a first-order dependence on [H2], the second

mechanism has a zero order dependence on [H2]