Centeno, Robenjoy C.

ChE 416 Problem Set

1. A steam of pure gaseous reactant A (CAo=660 mol/liter) enters a plug flow reactor at a flow rate
of FAo=540 mmol/min and polymerizes there as follows 3A↔R, -rA=54mmol/liter/min
How large a reactor is needed to lower the concentration of A in the exit stream to CA=330
mmol/liter?

Sol’n:

𝑛𝑥−1 − 𝑛𝑥−0 1 − 3 2
𝜀𝐴 = = =−
𝑛𝑥−0 3 3
𝐶𝐴𝑜 (1 − 𝑋𝐴 )
𝐶𝐴 =
(1 + 𝜀𝐴 𝑋𝐴 )
660𝑚𝑚𝑜𝑙
330𝑚𝑚𝑜𝑙 ( 𝑙
)(1 − 𝑋𝐴 )
=
𝑙 2
[1 + (− 3)(𝑋𝐴 )]
𝑋𝐴 = 0.75

0.75
𝑑𝑥𝐴
𝜏 = 𝐶𝐴𝑜 ∫
0 −𝑟𝐴
660𝑚𝑚𝑜𝑙 0.75 𝑑𝑥𝐴
𝜏=( )∫
𝑙 0
𝑚𝑚𝑜𝑙
54 /𝑚𝑖𝑛
𝑙

660𝑚𝑚𝑜𝑙/𝑙
𝜏= [𝑋𝐴 ]|0.75
0
54𝑚𝑚𝑜𝑙
/𝑚𝑖𝑛
𝑙
𝜏 = 9.17 𝑚𝑖𝑛

𝑉 = 𝜏𝑉1
540
𝑉 = 9.17 min ( ) 𝑙/𝑚𝑖𝑛
660
V=7.503L

2. Acetone is produced from 2-propanol in the presence of dioxygen and the photocatalyst Ti02
when the reactor is irradiated with ultraviolet light. For a reaction carried out at room temperature
in 1.0 mol of liquid 2-propano1 containing 0.125 g of catalyst, the following product
concentrations were measured as a function of irradiation time (J. D. Lee, M.S. Thesis, Univ. of
Virginia, 1993.)
Reaction time(min) 20 40 60 80 100 120 140 160 180
Acetone produced 1.9 3.9 5.0 6.2 8.2 10 11.5 13.2 14.0
(gacetone/g2-propanol)× 104
 Calculate the first-order rate constant.
16
14
y = 0.0776x + 0.4528
12
10

Conc. 8
6
4
2
0
0 50 100 150 200
time

k = 0.0776 min-1

3. A first-order homogeneous reaction of A going to 3B is carried out in a constant pressure batch

reactor. It is found that starting with pure A the volume after 12 min is increased by 70 percent at
a pressure of 1.8 atm. If the same reaction is to be carried out in a constant volume reactor and the
initial pressure is 1.8 atm, calculate the time required to bring the pressure to 2.5 atm.

Sol’n:
𝐴 → 3𝐵
Volume increased by 70%:

Final Volume (V) = 0.7 Initial Volume (V0)

Variable volume system, 𝑉 = 𝑉0 (1 + 𝜉𝐴 𝜒𝐴 )

t =? 2𝜒𝐴 = 0.7
𝜒𝐴 = 0.35
𝜒𝐴
𝑑𝜒𝐴
𝑡 = 𝑁𝐴0 ∫ Time taken increase in volume,
(−𝑟𝐴 )𝑉
0 T=12min, and 𝜒𝐴 = 0.35
1−𝜒𝐴
(−𝑟𝐴 )𝑉 = 𝑘𝐶𝐴0 ( ) 𝑉0 (1 + 𝜉𝐴 𝜒𝐴 )
1+𝜉𝐴 𝜒𝐴
𝜒 𝑑𝜒𝐴
𝑉𝜒 −1 − 𝑉𝜒𝐴 −0 3 − 1 𝑡 = 𝑁𝐴0 ∫0 𝐴 1−𝜒𝐴
𝜉𝐴 = 𝐴 = =2 𝑘𝐶𝐴0 ( )𝑉 (1+𝜉𝐴 𝜒𝐴 )
1+𝜉𝐴 𝜒𝐴 0
𝑉𝜒𝐴 −0 1 𝜒𝐴
𝑁𝐴 1 𝑑𝜒𝐴
= 0× ∫
Calculate 𝜒𝐴 𝑉0 𝑘𝐶𝐴0 (−𝛾𝐴 )𝑉
0

1.7𝑉0 = 𝑉0 (1 + 2𝜒𝐴 )
1 + 2𝜒𝐴 = 1.7
 𝜒𝐴
@Constant Temperature: k =0.036 min-1
1 𝑑𝜒𝐴
= ∫
𝑘 (−𝛾𝐴 )𝑉
0 Therefore,
1 𝜒 1 1
= [ln (1 − 𝜒𝐴 )]0 𝐴 𝑡 = [𝑙𝑛 ]
𝑘 𝑘 (1 − 𝜒𝐴 )
1 1
= [𝑙𝑛 ]
𝑘 (1 − 𝜒𝐴 ) @P= 2.5 atm, 𝜒𝐴 = 0.1935
1 1
𝑘 = [𝑙𝑛 ]
𝑡 (1 − 𝜒𝐴 ) 1 1
𝑡 = 0.036 [𝑙𝑛 (1−0.1935)] = 5.97 𝑚𝑖𝑛
1 1
= [𝑙𝑛 ]
12 (1 − 0.35)
= 0.036 𝑚𝑖𝑛−1

@Constant Volume: P0 = 1.8 atm

 4. Consider the reversible, elementary, gas phase reaction shown below that occurs at 300 K in a
constant volume reactor of 1.0 L.

a. For an initial charge to the reactor of 1.0 mol of A, 2.0 mol of B, and no C, find the
equilibrium conversion of A and the final pressure of the system. Plot the composition in
the reactor as a function of time.
b. Consider the reversible, elementary, gas phase reaction of A and B to form C occurring
at 300 K in a variable volume (constant pressure) reactor with an initial volume of 1.0 L.
For a reactant charge to the reactor of 1.0 mol of A, 2.0 mol of B, and no C, find the
equilibrium conversion of A. Plot the composition in the reactor and the reactor volume
as a function of time.
c. Consider the effect of adding an inert gas, I, to the reacting mixture. For a reactant charge
to the reactor of 1.0 mol of A, 2.0 mol of B, no C, and 3.0 mol of I, find the equilibrium
conversion of A. Plot the composition in the reactor and the reactor volume as a function
of time.

Sol’n:

a. Reversible elementary gas phase reaction

Temperature (T) = 300K
Volume of Reactor (V) = 1L
k1=6.0 L/mol h
k2=3.0 L/mol h

𝑑𝐶𝐴 𝑑𝑥𝐴
− = 𝐶𝐴𝑜 = 𝑘1 𝐶𝐴 𝐶𝐵 − 𝑘𝐶𝐶
𝑑𝑡 𝑑𝑡
𝑑𝑥𝐴
𝐶𝐴𝑜 = 𝑘1 𝐶𝐴𝑜 (1 − 𝑥)(𝐶𝐵𝑜 − 𝐶𝐵𝑜 𝑥𝐵 ) − 𝑘2 𝐶𝐶
𝑑𝑡
For equilibrium conversion,
𝑑𝑥𝐴
=0
𝑑𝑡

𝑘1 𝐶𝐴𝑜 (1 − 𝑥𝑒 )(𝐶𝐵𝑜 − 𝐶𝐵𝑜 𝑥𝐵 ) − 𝑘2 𝐶𝐶 = 0

𝑘1 𝐶𝐴𝑜 (1 − 𝑥𝑒 )(𝐶𝐵𝑜 − 𝐶𝐴𝑜 𝑥𝑒 ) − 𝑘2 (𝐶𝐶𝑜 + 𝐶𝐴𝑜 + 𝑥𝑒 ) = 0

Here Cc=0
𝑘1 𝐶𝐴𝑜 (1 − 𝑥𝑒 )(𝐶𝐵𝑜 − 𝐶𝐴𝑜 𝑥𝐵 ) = 𝑘2 𝐶𝐴𝑜 𝑥𝑒
𝑘1 (1 − 𝑥𝑒 )(𝐶𝐵𝑜 − 𝐶𝐴𝑜 𝑥𝑒 ) = 𝑘2 𝑥𝑒
(6)(1 − 𝑥𝑒 )(2 − 𝑥𝑒 ) = 𝑘2 𝑥𝑒
(6)(2 − 𝑥𝑒 − 2𝑥𝑒 + 𝑥𝑒 2 ) = 3𝑥𝑒
2𝑥𝑒 2 − 7𝑥𝑒 + 4 = 0
On solving the equation, 𝑥𝑒 = 0.719
 So product contains,
𝑛𝐴𝑜
𝐶𝐴 = 𝐶𝐴𝑜 (1 − 𝑥) = (1 − 𝑥) = 1 − 0.719 = 0.281 𝑚𝑜𝑙/ℎ
𝑉
𝐶𝐵 = 𝐶𝐵𝑜 (1 − 𝑥) = (2)(1 − 0.719) = 0.562 𝑚𝑜𝑙/ℎ
𝐶𝐶 = 0.719 𝑚𝑜𝑙/ℎ
Total= 0.281+0.562+0.719= 1.562 mol/h

Final pressure is
𝑛𝑅𝑇
𝑃= = 𝐶𝑅𝑇 = (1.562)(8.314)(300) × 103 = 3895.94 𝑘𝑃𝑎
𝑉

b. Variable Volume reactor

Feed to the reactor:
NAo= 1mol Equilibrium conversion (Xeq)=?
NBo= 2mol
NCo= 0mol
Xeq can be calculated by:

[𝐶𝐶𝑒 ]
𝐾𝐶 = @ 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚
[𝐶𝐴𝑒 ][𝐶𝐵𝑒 ]
𝑁𝐶 𝑁𝐴𝑜 𝑋
𝐶𝐶𝑒 = =
𝑉 𝑉
𝑁𝐴 𝑁𝐴𝑜 (1 − 𝑋)
𝐶𝐴𝑒 = =
𝑉 𝑉
𝑁𝐵 𝑁𝐵𝑜 (1 − 𝑋)
𝐶𝐵𝑒 = =
𝑉 𝑉

𝑁 𝑋
[ 𝐴𝑜
𝑉 ]
𝐾𝐶 =
𝑁 (1 − 𝑋) 𝑁𝐵𝑜 (1 − 𝑋)
[ 𝐴𝑜 𝑉 ][ 𝑉 ]
𝑋 𝑉
𝐾𝐶 = ( )( ) → 𝑒𝑞. 1
1 − 𝑋 𝑁𝐵𝑜 (1 − 𝑋)
Substituting the values in eq.1 we get
𝑋 1
2=( )( )
1 − 𝑋 2(1 − 𝑋)
 𝑋
4=
(1 − 𝑋)2
4 + 4𝑋 2 − 8𝑋 = 𝑋
4𝑋 2 − 9𝑋 + 4 = 0
X= 1.64 X= 0.6096
Since conversion cannot be greater than 1, therefore we neglect the root, X= 1.64

∴ The conversion attained X= 0.6096 ≈ 60.96%

c. Adding inert
Feed (in moles)
A= 1mol, B= 2mol, C= 0, Inert= 3mol
𝐴+𝐵 ⇌𝐶
@equilibrium
[𝐶𝐶𝑒 ]
𝐾𝐶 =
[𝐶𝐴𝑒 ][𝐶𝐵𝑒 ]
𝑁𝐶 𝑁𝐴𝑜 𝑋
𝐶𝐶𝑒 = =
𝑉 𝑉
𝑁𝐴 𝑁𝐴𝑜 (1 − 𝑋)
𝐶𝐴𝑒 = =
𝑉 𝑉
𝑁𝐵 𝑁𝐵𝑜 (1 − 𝑋)
𝐶𝐵𝑒 = =
𝑉 𝑉
But inert is added,
𝑉 = 𝑉𝑜 (1 + 𝜖𝑋)
𝜖 = fractional change in conversion
4−3
𝜖 = 3 = 1⁄3

[𝐶𝐶𝑒 ]
𝐾𝐶 =
[𝐶𝐴𝑒 ][𝐶𝐵𝑒 ]
𝑁𝐴𝑜 𝑋
( )
𝑉𝑜 (1 + 𝜖𝑋)
=
𝑁 (1 − 𝑋) 𝑁𝐵𝑜 (1 − 𝑋)
( 𝐴𝑜 )( )
𝑉𝑜 (1 + 𝜖𝑋) 𝑉𝑜 (1 + 𝜖𝑋)
𝑘1 𝑋 𝑉𝑜 (1 + 𝜖𝑋)
𝐾𝐶 = = [( ) ]
𝑘2 1 − 𝑋 𝑁𝐵𝑜 (1 − 𝑋)
6 𝑋 1(1 + 1⁄3 𝑋)
= = [( ) ]
3 1−𝑋 2(1 − 𝑋)
𝑋(1 + 1⁄3 𝑋)
2=
2(1 − 𝑋)2
4(1 − 𝑋)2 = 𝑋(1 + 1⁄3 𝑋)
4(1 + 𝑋 2 − 2𝑋) = 𝑋 + 1⁄3 𝑋 2
4 + 4𝑋 2 − 8𝑋 = 𝑋 + 1⁄3 𝑋 2
 1
(4 − ) 𝑋 2 − 9𝑋 + 4 = 0
3
11 2
𝑋 − 9𝑋 + 4 = 0
3
11𝑋 2 − 27𝑋 + 12 = 0
𝑋 = 1.87 𝑋 = 0.5824
Since the conversion cannot be greater than 1, we reject the value of X=1.87
Hence, conversion at equilibrium: X=0.5824 ≈ 58.24%

5. The irreversible reaction 2A → B takes place in the gas phase in a constant temperature plug flow
reactor. Reactant A and diluent gas are fed in equimolar ratio, and the conversion of A is 85
percent. If the molar feed rate of A is doubled, what is the conversion of A assuming the feed rate
of diluent is unchanged?

Solution:

2A → B

𝑋𝐴 = 0.85 = 85%

For first order reaction

For PFR:

𝑉 𝜏 𝑋𝐴
= =
𝐹𝐴𝑜 𝐶𝐴𝑜 −𝑟𝐴

𝑉 𝜏 𝑋𝐴
= =
𝐹𝐴𝑜 𝐶𝐴𝑜 𝑘𝐶𝐴𝑜 (1 − 𝑋𝐴 )

𝑉 𝑋𝐴
= 𝜏𝑘 =
𝐹𝐴𝑜 1 − 𝑋𝐴

For 1st order reaction:

𝑉
−𝑙𝑛(1 − 𝑋𝐴 ) = 𝑘𝜏 =
𝐹𝐴𝑜

−𝑙𝑛(1 − 𝑋𝐴1 ) 𝐹𝐴2

=
−𝑙𝑛(1 − 𝑋𝐴2 ) 𝐹𝐴1

𝐹𝐴2 = 2𝐹𝐴1
−𝑙𝑛(1−0.85)
−𝑙𝑛(1−𝑋𝐴2 )
=2 −𝑙𝑛(1 − 𝑋𝐴2 ) = 0.9485

1 − 𝑋𝐴2 = 0.3873

𝑋𝐴2 = 0.6127
 6. Titanium dioxide particles are used to brighten paints. They are produced by gas-phase oxidation
of TiCl4 vapor in a hydrocarbon flame. The dominant reaction is hydrolysis,
𝑇𝑖𝐶𝑙4 + 2𝐻2 𝑂 ⇒ 𝑇𝑖𝑂2 (𝑠) + 4𝐻𝐶𝑙
The reaction rate is first-order in TiC14 and zero-order in H20. The rate constant for the reaction
is:
88000𝐽/𝑚𝑜𝑙 −1
𝑘 = 8.0 × 104 𝑒𝑥𝑝 [− ]𝑠
𝑅𝑔 𝑇
The reaction takes place at 1200 K in a constant pressure flow reactor at 1 atm pressure (1.01 X
105 Pa). The gas composition at the entrance to the reactor is:
CO2 8%
H2O 8%
O2 5%
TiCl4 3%
N2 Remainder
a. What space time is required to achieve 99 percent conversion of the TiC14 to TiO2?
b. The reactor is 0.2 m diameter and 1.5 m long. Assuming that the reactor operates 80 percent of
the time, how many kilograms of TiO2 can be produced per year? (The molecular weight of TiO2
is 80 g/mol.) Rg = 8.3144 J/mol/K

Given:

TiCl4 gas phase oxidation of TiCl4 vapor in hydrocarbon flow

𝑇𝑖𝐶𝑙4 + 2 𝐻2 𝑂 ⇒ 𝑇𝑖𝑂2 (𝑠) + 4 𝐻𝐶𝑙

The reaction rate is first order in TiCl4 and zero order in H2O.
88000𝐽
The reaction constant 𝑘 = 8 × 104 exp (𝑚𝑜𝑙(8.314)𝑇)

Reaction Temperature (T) =1200K @ constant pressure flow reactor at P = 1atm (8 × 104 𝑃𝑎)

The gas composition at entrance to the reactor:

CO2 -8% H2O -8% O2 -5% TiCl4 -3% N2 -76%

Other data given:

Reactor diameter (d) = 0.2 m, length (L)= 1.5 m, gas constant (R)= 8.3144 J/ mole –K

Reactor operates 80% time

Mol.wt of TiO2= 80 g/mol

 a) Solution:
88000
Rate constant (k) =8 × 104 exp (8.314(1200)) = 8 × 104 exp(8.82)

log 𝑘 = log(8 × 104 ) + log(8.82) = log(8) + log(104 ) + log(8.82)

log 𝑘 = 0.9032 + 4 + 0.9455 ; ∴ 𝑘 = 706412𝑠 −1

Atomic wt. of Ti = 48 g/atom

Mol.wt of TiCl4=48 +35.5 (4)= 190 g/mole

8(44) 8(18) 5(32) 3(190) 76(28)
The average molecular wt. of the gas mixture = + + + + = 33.54𝑔/𝑚𝑜𝑙
100 100 100 100 100

Only 3% of TiCl4 is available in the reaction,

99 3
And 99% of 3% of TiCl4= 100 (100) = 0.0297𝑔 𝑜𝑓 𝑇𝑖𝐶𝑙4 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑖𝑛 𝑡ℎ𝑒 𝑟𝑥𝑛 𝑡𝑜 𝑡𝑎𝑘𝑒 𝑝𝑎𝑟𝑡

𝜋𝑑 2 22 0.2 2
Volume of the reactor (V)= 2
𝐿 = 7
( 2 ) (1.5) = 0.0471𝑚3 = 47.1 𝑙𝑖𝑡𝑒𝑟𝑠

For the first order reaction:

𝑑𝐶
Reaction rate (rA) = = 𝑘𝐶𝑎 𝑓
𝑑𝑡

For this reaction, separating and integrating ,we get

𝑑𝐶𝑎
−(𝐶𝑎 − 𝐶𝑎𝑜 ( ) = 𝑘 ∫ 𝑡 − 0𝑑𝑡
𝐶𝑎

𝐶𝑎
− ln = 𝑘𝑡 → 𝑒𝑞. 1
𝐶𝑎𝑜

𝑃𝑉 = 𝑛𝑅𝑇

𝑛 𝑃 105
= 𝐶𝑎 = = = 10.02
𝑉 𝑅𝑇 (8.314)(1200)
𝑑𝑋𝐴
Or, 𝑑𝑡
= 𝑘(1 − 𝑋𝐴 )

ln(1 − 𝑋𝐴 ) = 𝑘𝑡

ln(1 − 0.0297) = (706412)𝑡

0.030 = (706412)𝑡 ; ∴ 𝑡 = 21192.36 𝑠𝑒𝑐

For Zero order reaction:

 𝐶𝑎𝑜 0.031
𝑡= = = 21192.36 𝑠𝑒𝑐
𝑘 706412
𝑉𝐶𝑎𝑜 𝑋𝐴 𝑓−𝑋𝐴𝑖 0.0297
Space time (𝜏) = 𝐹𝑎𝑜
= 𝐶𝑎𝑖 −𝑟𝐴
= 10.023 ( 0.03
) = 9.93 𝑠𝑒𝑐

b) Solution:
Production of TiO2= 9.93 = 47.1(1 − 𝑋𝐴 )
9.93
47.1
= (1 − 𝑋𝐴 )

0.21 = (1 − 𝑋𝐴 )

𝑋𝐴 = 0.79(80) = 63.2𝑔/𝑠
63.2𝑔 1993075200𝑔
𝑋𝐴 = 3600𝑠 24ℎ 365 𝑑𝑎𝑦𝑠 = 𝑦𝑟
= 1993𝑡𝑜𝑛/𝑦𝑟
𝑠( )( )( )
1ℎ 1𝑑𝑎𝑦 1𝑦𝑟