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Problem Set #3 AY2016-2017

1. A certain substance is mixed with equal quantities of


substances B & C. At the end of 1000 seconds half of A
has reacted. How much is left unreacted at the end of
2000 seconds if the reaction with respect to A is (a) first-
order, (b) second-order in which equal amounts of A & B
reacts, (c) third-order in which equal amounts of A, B & C
react & (d) zero-order.
2. The reaction CH 3CH 2 NO2 + OH - � H 2O + CH 3CHNO2 is
second-order and k at 0⁰C is 39.1 li/mole.min. An
aqueous solution is made from 0.004M nitroethane and
0.005M NaOH. How long will it take for 90% of
nitroethane to react at 25ᵒC?
3. If a first-order reaction has an activation energy of
E
25,000 cal/mol and for the k = k0e - RT , ko has a value of 5
x 103 per second, at what temperature will the reaction
have a half-life of 1 min?
4. The reaction A + 2B → R is first-order with respect to
each reactant. If equimolar amounts of A & B are
introduced into a constant-volume reactor and 80% of A
remains after 3 mins., how much will remain after 6
mins?
5. For the reaction A → R, second-order kinetics and CAO =
1 mol/li, we get 50% conversion after an hour in a batch
reactor. What will the conversion be and the
concentration of A after 1 hr if CAO = 10 mol/li? If R has an
initial concentration of 0.2 mol/li, how much R is present
after 1 hr?
6. Hydrogen peroxide reacts with the thiosulfate ion in a
slightly acidic solution as follows:
H 2O2 + 2 S2O3-2 + 2 H + � 2 H 2O + S 4O6-2

The reaction rate is independent of the hydrogen


concentration in the pH range 4-6. The following
empirical data were obtained at 25⁰C @ pH = 5.0. Initial
concentrations are: H2O2 = 0.03680 M;S2O3-2 = 0.02040 M
t, min 16 36 43 52
[S2O3-2] x 103 M 10.30 5.18 4.16 3.13
Determine the rate law that fits the given empirical data.
7. The empirical data for a liquid-phase reaction A→ B are
as follows:
% conversion 25 60 75 85 95
t, min 20 100 200 300 500
What is the rate law for this reaction?
8. An aqueous solution of ethyl acetate is to be
saponified with sodium hydroxide. The initial
concentration of ethyl acetate is 5.0 g/li and that of
caustic soda is 0.10N, values of the second-order rate
constant in li/mole.min are k = 23.5 @ 0⁰C & k = 92.4 @
20⁰C. The reaction is essentially irreversible, the time
required to saponify 95% of ether at 40⁰C.

CH3COOC2H5 + NaOH → CH3COO-Na+ + C2H5OH

9. Two hundred ml of 1M HCHO is added to 100 ml of 2M


H2O2 and allowed to react. After 2 hrs the concentration
of HCOOH is 0.114M. When will the reaction be 90%
complete? What will be the concentration of HCOOH be
then? Assume an elementary reaction.

HCHO + H2O2 → HCOOH + H2O


10. Happert & Mack give the following data for the vapor-
phase decomposition of ethylene oxide into methane and
carbon monoxide at 414.5 ⁰C:

time, min 0 5 7 9 12 18
∏, mm Hg 116.51 122.56 125.72 128.74 133.23 141.37

Show that the decomposition follows a first-order


reaction, and calculate the specific rate constant.

C2H4O → CH4 + CO