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CHEMISTRY II (FAC0025)

TUTORIAL 2

1. Consider the reaction


4NO2 (g) + O2 (g)

2N2O5 (g)

Suppose that, at a particular moment during the reaction, molecular oxygen is


reacting at the rate of 0.024 M/s.
(a) At what rate is N2O5 being formed?
(b) At what rate is NO2 reacting?
Answer:
(a) From the rate expression we have

(b) Here we have:

= -0.096 M/s

2. The data shown below were obtained from the following reaction:
BF3(g) + NH3(g) F3BNH3(g)
Exp
1
2
3
4
5

[BF3]initial
(M)
0.250
0.250
0.200
0.350
0.175

[NH3]initial
(M)
0.250
0.125
0.100
0.100
0.100

Initial Rate of Reaction


(Ms-1)
0.2130
0.1065
0.0682
0.1193
0.0596

a. Determine the rate law for the reaction.


b. Calculate the value of the rate constant, k, for the reaction.
c. At 25oC, it takes 2.22 hours for the concentration of BF3 to drop from 1.80 M to 0.90 M.
How many hours are required for the concentration of BF3 to drop from 0.80 M to 0.025
M at 25C?
Answer:
a)

Rate k BF3 NH3


m

Rate1 k 0.250M 0.250M


0.2130Ms 1

Rate 2 k 0.250Mm 0.125Mn 0.1065Ms 1


m

2n 2
n 1
Rate 4 k 0.350M 0.100M
0.1193Ms 1

m
n
Rate 5
0.0596Ms 1
k 0.175 0.100M
m

2m 2
m 1
Rate = k [BF3] [NH3]
b) From experiment 1

M
s
k
3.41M1s 1
0.250M0.250M
0.2130

c) t1/2 = 2.22 hours.


0.80 M 0.40 M 0.20 M 0.10 0.050 M 0.025 M
t = 5 x t1/2 = 11.10 hours

3. Cyclopentadiene (C5H6) reacts with itself to form dicyclopentadiene (C10H12). A 0.0400 M


solution of C5H6 was monitored as a function of time as the reaction
2C5H6 C10H12
proceeded. The following data were collected:
Time (s)
0.0
50.0
100.0
150.0
200.0

[C5H6], M
0.0400
0.0300
0.0240
0.0200
0.0174

What is the order of the reaction? What is the value of rate constant?

Answer:
Time

[C5H6]

ln [C5H6]

1/[C5H6]

0.0400

-3.219

25.0

50

0.0300

-3.507

33.3

100

0.0240

-3.730

41.7

150

0.0200

-3.912

50.0

200

0.0174

-4.051

57.5

Reaction is second order;


Slope = k = 0.163 M-1s-1

4. At 500oC, cyclopropane (C3H6) rearranges to propene (CH3-CH=CH2). The reaction is first order,
and the rate constant is 6.7 10-4 s-1. if the initial concentration of C3H6 is 0.0500 M:
a) What is the molarity of C3H6 after 30 min?
b) How long does it takes for the cyclopropane concentration to drop to 0.0100 M?
c) How many minutes does it take for the 26% of the C3H6 to react?

Answer:
a) First order reaction;

lnC 3H6 t kt lnC 3H6 O

C 3H6 t

exp 6.7 10 4 30 60 ln0.0500


0.0150 M

b)

lnC 3H6 t kt lnC 3H6 O


t

c)

ln0.0100 ln0.0500
2402 s 40 minutes
6.7 10 4

if 26% react 74% remainsin the end 74% 0.0500 M 0.0370 M


lnC 3H6 t kt lnC 3H6 O
t

5.

ln0.0370 ln0.0500
449 s 7.50 minutes
6.7 10 4

Iodine atoms combine to form molecular iodine in the gas phase

I(g) + I(g)

I2(g)

This reaction follows second-order kinetics and has the high rate constant 7.0109/M.s at 23oC.
(a) If the initial concentration of I was 0.086 M, calculate the concentration after 2.0 min.
(b) Calculate the half-life of the reaction if the initial concentration of I is 0.60 M and if it is 0.42
M.
Answer:
(a) To calculate the concentration of a species at a later time of a second order reaction, we need
the initial concentration and the rate constant.
Applying the following Equation:

1
1
kt
[ A]t
[ A]o
7.0 x10 9
1
60s
1

2.0 min x

[ A]t M .s
1min 0.086M
[ A]t 1.2 x10 12 M

(b) For [I]0 = 0.60 M

t1
2

1
[ A]o

1
10

2.4 x10 s
9
7.09 x10 0.6M
M .s

For [I]0 = 0.42 M

t1
2

1
[ A]o

1
10

3.4 x10 s
9
7.09 x10 0.42 M
M .s

6.

The reaction between ethyl iodide and hydroxide ion in ethanol (C2H5OH) solution:
C2H5I (alc) + OH- (alc) C2H5OH (l) + I- (alc)
has an activation energy, Ea of 86.8 kJ/mol and a frequency factor, A of 2.10 1011 M-1s-1.
a) Predict the rate constant for the reaction at 35oC.
b) A solution of KOH in ethanol is made up by dissolving 0.335 g KOH in ethanol to form 250.0 ml
of solution. Similarly, 1.453 g of C2H5I is dissolved in ethanol to form 250.0 ml of solution. Equal
volumes of the two solutions are mixed. Assuming the reaction is first order in each reactant,
what is the initial rate at 35oC?
c) Which reagent in the reaction is limiting, assuming the reaction proceeds to completion?
Answer:
a)

Ea
lnA
RT
E a 86.8 kJ/mol 8.68 10 4 J/mol

ln k -

T 35 273 308K
A 2.10 1011 M 1s 1
8.68 10 4 J/mol mol K
ln 2.10 1011 M 1s 1 7.8264
ln k

308K
8.314
J

4
1 1
k 3.99 10 M s

b)

0.335 g

56.1 g/mol

M 1 ( KOH )
0.02389 M KOH
0.250 L
1.453 g

156.0g/mol

M 1(C2 H 5 I )
0.0373 M C 2 H 5 I
0.250 L
If equal volumes of the solutions are mixed, the new concentrations:

M 2V2 M 1V1

Use :

M 2 ( KOH )
M 2 ( C2 H 5 I )

where

0.02389M V1
2V1

0.0373M V1
2V1

V2 2V1

0.011945 M KOH
0.01863 M C 2 H 5 I

Assuming the reaction is first order in each reactant:


Rate

= k [C2H5I] [OH-]
= (3.99 10-4 M-1s-1)(0.011945 M)(0.01863 M)
= 8.88 10-8 M/s

c) Since C2H5I and OH- react in a 1:1 mole ratio, and equal volumes of the solution are mixed, the
reactant with smaller concentration, KOH, is the limiting reactant.

7.

The rate constant of a first-order reaction is 3.46 X 10-2 s-1 at 298 K. What is the rate constant at
350 K if the activation energy for the reaction is 50.2 kJ/mol?

Answer:
The data are:
k1 = 3.46 X 10-2 s-1
T1 = 298 K

k2= ?
T2 = 350 K

Ea = 50.2 kJ/mol

Substituting in Equation:

3.46 x10 2 s 1 50.2 x10 3 J / mol 298K 350 K


-3.01
ln
k2

8.314 J / mol.K 298K 350 K )


3.46 x10 2 s 1

e 3.01 0.0493
k2

k 2 0.702s 1