CHEREKN PROBLEM SET 2

MULTIPLE REACTIONS

1. For the reaction A  R k = 3/sec

A  S k = 0.5/sec
Calculate the concentration of R and S produced per mole of A fed if conversion of A is 95%.

2. For the reaction A  R -rA = k1CA

A  2S -rA = k2CA
After a reaction time of 50 minutes, 90% of A has decomposed and the product is found to contain 9.1
mol of R per mole of S. Neither R nor S is present initially in the reaction vessel. Evaluate k1 and k2.

3. An experimental investigation of the liquid phase hydrochlorination of octyl and dodecyl alcohols in a
batch reactor revealed the following stoichiometry:
R1OH + HCl  R1Cl + H2O
R2OH + HCl  R2Cl + H2O
Where R1OH and R1Cl are used to represent octyl alcohol and octyl chloride, respectively, while R2OH
and R2Cl are used to represent dodecyl alcohol and dodecyl chloride, respectively. Initial concentrations
are as follows:
C(HCl)o = 1.3 C(R1OH)o = C(R2OH)o = 2.21
Calculate the moles of dodecyl; chloride and octyl chloride produced when 20% of the octyl alcohol has
been consumed. Also calculate the percentage of HCl reacted when 20% of the octyl alcohol has reacted
k1 = 1.6x10-3 li/mol-min
k2 = 1.92x10-3

4. A(g) is decomposed into R(g) and S(g) by two possible competing paths:
A  R k1
A  S k2
Under atmospheric pressure in an isothermal batch reactor maintained at 600 oC. Initially, the partial
pressure of A, R, and S are 600, 100, and 60 mm Hg, respectively. When all A has been reacted, the
molar ratio of R to S inside the reactor becomes 2 to 1. If the partial pressure of A inside the reactor is
reduced to 50 mm Hg in 5 minutes, what will be the expected molar ratio of the three gases after 2
minutes of operation?

5. For the reaction A + X  V k1

B + X  W k2
k1/k2 = 0.44. If the conversion of A is 10%, what is the conversion of B? Assume CAo = CBo.

6. The series reaction A  R  S has been studied and the constants k1 and k2 were found to be
equal. Half-life of A is 15 minutes with CAo = 2.0, CRo = 0.2 and CSo = 0.1 gmol/li. Determine the
following:
a. CRmax
b. If the reaction is conducted in a batch reactor containing CRmax in the product with tc = 10
minutes, estimate the number of batches that can be made in one day. Assume 24-h operation.

7. The reaction A  B  C k1 = 0.01/sec, k2 = 0.003/sec

B  D k3 = 0.002/sec.
is carried out in a batch reactor in which pure A is present initially with a concentration of 0.2mol/cc.
Derive an expression that gives the concentration of B as a function of time. Find CA, CB, CC and CD at t
= 2 min.

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 k1
8. For the reaction A R, k1 = 0.24/min and k2 = 0.12/min. Find the
k2
Concentration of A and R after 8 minutes if CAo = 1mol/li and CRo = 0. What is the conversion at
equilibrium?

9. The following data refer to a reaction that is believed to be of second order in the forward direction and
first order in the reverse direction. Initial concentrations of the two reactants are each 1.2 lbmol/ft 3 and
there was no product present initially.
k1
A + B C
k2
lbmoles A converted/ft3 rate, lbmoles/ft3-min
0 2.16
0.8 0.00
a. What is the equilibrium constant?
b. Find the specific reaction rates.
c. How long does it take to convert 50% of the reactants?

10. For the irreversible reaction at constant volume and temperature

k1
A R
k2
k1 = 0.36/h and k2 = 0.12/h. Starting with pure A, at what time will A and R be equal? What will be the
ratio of R to A after 1.5 hours?
k1 k2
11. The reaction A B C
k3
k3 = 0.12/min, k1 = k2 = 0.24/min. Find the concentration of B and C after 8 minutes if the initial
concentration of A is 3mols/li.

12. For the homogeneous-catalyzed reaction 2A  R, the data below show the concentration of A after 1
hour for two catalyst concentrations. Solve for the specific rate of reaction for the catalyzed and
uncatalyzed reactions if the rate of reaction is first order with respect to the catalyst.
CA
t CC = 0.1mol/li CC = 0.2mol/li
0 5 5
1 3 2.5

13. The reaction below is elementary and the product R has catalytic effect
A + B  R + S CAo = CBo = 2mols/li, CRo = 0.1mol/li
At t = 10 minutes, XA = 0.4. Determine
a. specific rate of reaction
b. concentration of A when the reaction velocity is maximum
c. time when the reaction velocity is maximum

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VARIABLE VOLUME SYSTEM

14. Find the second order rate constant for the disappearance of A in the gaseous phase reaction: A  5B
if the volume of the reaction mixture starting with 80% A increases by 80% in 10 minutes. The total
pressure within the system stays constant at 2.5 atm at 25oC.

15. The decomposition of acetaldehyde: 2CH3CHO  2CH4 + 2CO2 is an elementary reaction. At

518oC pure acetaldehyde at 363 mmHg was placed in a constant volume reactor and after 665 sec, the
pressure of acetaldehyde drops by 224 mmHg. If the same reaction were to be placed in a constant
pressure system (variable volume) with the same feed composition and condition, at what time will the
conversion be 60%?

16. A first order homogeneous gas phase reaction: A  3.8R takes place in a constant pressure system.
Starting with pure A, the volume increases by 60% of the original in 5 minutes. For the same reaction,
starting with 80% A, in how many minutes will the pressure of A be equal to 0.2 atm if the feed is
introduced at 1 atm.

17. The reaction 2A  B is second order with respect to A and the volume decreases by 40% in 4 minutes.
What is the conversion achieved? The same reaction is conducted in a constant volume system and
pressure of A becomes 0.2 in 4 minutes. What is the initial pressure of A?

18. The following data were obtained from the reaction: A  2B.

t 18 100 200 450 1680

V/Vo 1.25 1.60 1.75 1.85 1.95
Find the rate equation.

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NON-ELEMENTARY REACTIONS

19. The formation of C2H4 can be represented by the following mechanism

k
C H  1 2CH*
2 6 3
k
CH*  C H  2  CH  C H*
3 2 6 4 2 5
k
C H*5  3 C H  H*
2 2 4
k
H*  C H  4  H  C H*
2 6 2 2 5
k
H*  C H*5  5 c H
2 2 6

Show that the rate of formation of C2H4 is first order.

20. Given the following mechanism

Cl  O 3  k1 ClO  ClO
2 2
k
ClO  O 3   2  ClO  O
k 
1/ 2
2
Cl2 1/ 2 O3 3/ 2
3
2
Show that :  rO3  2k3  1 
k  k4 
ClO 3  O 3 3 ClO  2O
2 2
k
ClO 3  ClO 3  4  Cl  3O
2 2

21. The formation of hydrogen bromide may be represented by the following scheme

k
Br  1 2Br
2
k
Br  H  2  HBr  H
2
k
H  Br  3 HBr  Br
2
k
H  HBr  4  H  Br
2
k
Br  Br 
5 Br
2
1/ 2
k 
2k 2  1  H 2 Br2 
1/ 2

  k5 
k HBr 
Show that rHBr
1 4
k 3 Br2 

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22. The thermal decomposition of acetaldehyde is shown in the following mechanism

CH 3CHO k1 CH  CHo

3
k
CH  CH 3CHO  2  CH  CH CO
4
3 3
k
CH CO  3 CH  CO
3 3
k
2CH   4C H
3 2 6

1/ 2
k 
Show that rCH4  k 2  1  CH 3CHO3 / 2
 k4 

23. The decomposition of ozone into oxygen follows the mechanism:

k1
O3 O O
k2 2
k 3 2O
O  O  2
3

2k1k3 O3 
2
 rO3 
k 2 O2   O3 
Show that