CHEMICAL REACTION ENGINEERING

HOMEWORK 01
JUAN SEBASTIAN SUAREZ OSPINA
GUSTAVO ALBERTO BARRERA SERNA

EXERCISE 1
The irreversible gas phase nonelementary reaction:

𝐴 + 2𝐵 → 𝐶

is to be carried out isothermally in a constant pressure Batch reactor. The feed is at a temperature of 227°C,
a pressure of 1013kPa, and its composition is 33.3% A and 66.7% B. Laboratory data taken under identical
conditions are as follows:

-rA (mol/dm3.seg)*103 0.010 0.005 0.002 0.001

X 0.0 0.2 0.4 0.6

SOLUTION:

Sketch:

Assumptions:
 The temperature and pressure are constant during the process.
 The A specie is the limiting reactant.
 The gas phase is ideal.
 The inlet molar flow is constant.

The inlet concentration is given by the ideal gas equation:

𝑃𝑖 𝑉 = 𝑛𝑖 𝑅𝑇

In concentration terms:
𝑛𝑖 𝑃𝑖 𝑦𝑖 𝑃
𝐶𝑖 = = =
𝑉 𝑅𝑇 𝑅𝑇
Substituting:
0,333 ∗ 1013𝑘𝑃𝑎 𝑚𝑜𝑙
𝐶𝐴0 = 3 = 0,081
8,314𝑘𝑃𝑎.𝑑𝑚
𝑚𝑜𝑙.𝐾
∗ 500𝐾 𝐿

0,667 ∗ 1013𝑘𝑃𝑎 𝑚𝑜𝑙

𝐶𝐵0 = 3 = 0,163
8,314𝑘𝑃𝑎.𝑑𝑚
𝑚𝑜𝑙.𝐾
∗ 500𝐾 𝐿

a. Estimate the volume of a plug flow reactor required to achieve 30% conversion of A for an entering
volumetric flow rate of 2.0m3/min.
The rate law data are:

-rA (mol/dm3.seg)*103 0.010 0.005 0.002 0.001

X 0.0 0.2 0.4 0.6

Now, shall calculate de reciprocal rate data and then plot versus conversion.

1/-rA (dm3.seg/mol)*105 1.0 2.0 5.0 10.0

The plot is shown in the follow figure:

RECIPROCAL RATE
1.20E+06

1.00E+06
1/-rA (dm3.seg/mol)

8.00E+05

6.00E+05

4.00E+05

2.00E+05

0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6
X

The moles balance for a Plug Flow Reactor is given by:

𝑋
𝐹𝐴0
𝑉𝑃𝐹𝑅 = ∫ 𝑑𝑋
0 −𝑟𝐴

If the molar flow of the specie A is constant, it can leave the integral sign as follows:

𝑋
1
𝑉𝑃𝐹𝑅 = 𝐹𝐴0 ∫ (
) 𝑑𝑋
0 −𝑟 𝐴
The volume for a PFR is the area under curve. To realize de operation is useful to use a Simpson´s Rule. In
this case for seven points:
𝑛−2
𝑛−1 2
𝑥𝑛
𝑥𝑛 − 𝑥0 𝑓(𝑥0 ) + 𝑓(𝑥𝑛 )
∫ 𝑓(𝑥) 𝑑𝑥 = ( ) + 2 ∑ 𝑓(𝑥𝑖 ) + 2 ∑ 𝑓(𝑥2𝑖+1 )
𝑥0 3𝑛 2
1 0
[ ]
The data to calculate the volume are shown in the follow table:

1/-rA (dm3.seg/mol)*105 1.00 1.27 1.52 1.77 2.00 2.80 3.51

X 0.00 0.05 0.10 0.15 0.20 0.25 0.30

Substituting these values on a Simpson´s Rule:

5 2
0.3
1 𝑋6 − 𝑋0 𝑓(𝑋0 ) + 𝑓(𝑋6 )
∫ ( ) 𝑑𝑋 = [( ) + 2 ∑ 𝑓(𝑋𝑖 ) + 2 ∑ 𝑓(𝑋2𝑖+1 )]
0.0 −𝑟𝐴 3∗6 2
1 0

0.3
1 0.3 − 0.0 1.00 + 3.60
∫ ( ) 𝑑𝑋 = [( ) + 2 ∗ (1.27 + ⋯ + 2.80) + 2 ∗ (1.27 + 1.77 + 2.80)] ∗ 105
0.0 −𝑟𝐴 18 2

0.3
1 𝑑𝑚3 𝑠𝑒𝑔
∫ ( ) 𝑑𝑋 = 54500.00 𝑚𝑜𝑙
0.0 −𝑟𝐴
The PFR volume is:

𝑋 𝑋
1 1
𝑉𝑃𝐹𝑅 = 𝐹𝐴0 ∫ ( ) 𝑑𝑋 = 𝐶𝐴0 𝑣0 ∫ ( ) 𝑑𝑋
0 −𝑟𝐴 0 −𝑟𝐴

Substituting the values:

𝑚𝑜𝑙 𝑚3 1𝑚𝑖𝑛 1000𝐿 𝑑𝑚3 𝑠𝑒𝑔

𝑉𝑃𝐹𝑅 = 0,081 ∗ 2𝑚𝑖𝑛 ∗ ∗ ∗ 54500 𝑚𝑜𝑙
𝐿 60𝑠𝑒𝑔 1𝑚3

𝑉𝑃𝐹𝑅 = 147150𝑑𝑚3

b. Estimate the volume of a CSTR required to take the effluent from the PFR above and achieve 50% total
conversion.

For a CSTR, the moles balance is:

𝐹𝐴0 (𝑋2 − 𝑋1 ) 1
𝑉𝐶𝑆𝑇𝑅 = = 𝐹𝐴0 ( ) (𝑋2 − 𝑋1 )
−𝑟𝐴2 −𝑟𝐴2

This volume is the area of the rectangle, this has a height: the reciprocal rate and the conversion difference
its base.
1
𝑉𝐶𝑆𝑇𝑅 = 𝐶𝐴0 𝑣0 ( ) (𝑋2 − 𝑋1 )
−𝑟𝐴2

𝑚𝑜𝑙 𝑚3 1𝑚𝑖𝑛 1000𝐿 𝑑𝑚3 𝑠𝑒𝑔

𝑉𝐶𝑆𝑇𝑅 = 0,081 ∗ 2𝑚𝑖𝑛 ∗ ∗ ∗ 7.5 ∗ 105 𝑚𝑜𝑙 ∗ (0.5 − 0.3)
𝐿 60𝑠𝑒𝑔 1𝑚 3

𝑉𝐶𝑆𝑇𝑅 = 405000𝑑𝑚3
The plot of the situation is show in the follow figure:

RECIPROCAL RATE
1.20E+06

1.00E+06
1/-rA (dm3.seg/mol)

8.00E+05

6.00E+05

4.00E+05

2.00E+05

0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6
X

c. What is the total volume of the two reactors?

The total volume is the sum of the PFR and CSTR volume:

𝑉 = 𝑉𝑃𝐹𝑅 + 𝑉𝐶𝑆𝑇𝑅 = 147150𝑑𝑚3 + 405000𝑑𝑚3

𝑉 = 552150𝑑𝑚3

d. What is the volume of a single plug flow reactor necessary to achieve 60% conversion? 80% conversion?

For a PFR the moles balance is:

𝑋
1
𝑉𝑃𝐹𝑅 = 𝐹𝐴0 ∫ (
) 𝑑𝑋
0 −𝑟𝐴
The calculate procedure is similar at the (a) item. In this case is necessary to use more data and then apply
the Simpson´s Rule. The data are shown in the follow table:

1/-rA (dm3.seg/mol)*105 1.00 1.27 1.52 1.77 2.00 2.80 3.51

X 0.00 0.05 0.10 0.15 0.20 0.25 0.30
1/-rA (dm3.seg/mol)*105 4.25 5.00 6.30 7.50 8.76 10.0 ---
X 0.35 0.40 0.45 0.50 0.55 0.60 ---
 RECIPROCAL RATE
1.20E+06

1/-rA (dm3.seg/mol) 1.00E+06

8.00E+05

6.00E+05

4.00E+05

2.00E+05

0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6
X

For thirteen points the Simpson´s Rule is:

11 5
0.6
1 𝑋12 − 𝑋0 𝑓(𝑋0 ) + 𝑓(𝑋12 )
∫ ( ) 𝑑𝑋 = [( ) + 2 ∑ 𝑓(𝑋𝑖 ) + 2 ∑ 𝑓(𝑋2𝑖+1 )]
0.0 −𝑟𝐴 3 ∗ 12 2
1 0

Replacing the values:

11 5
0.6
1 0.6 − 0.0 1.0 + 10
∫ ( ) 𝑑𝑋 = [( ) + 2 ∑(1.27 + ⋯ + 8.76) + 2 ∑(1.27 + 1.77 + ⋯ + 8.76)] ∗ 105
0.0 −𝑟𝐴 3 ∗ 12 2
1 0

0.6
1 𝑑𝑚3 𝑠𝑒𝑔
∫ ( ) 𝑑𝑋 = 241933.33 𝑚𝑜𝑙
0.0 −𝑟𝐴
Then, the volume is:
𝑚𝑜𝑙 𝑚3 1𝑚𝑖𝑛 1000𝐿 𝑑𝑚3 𝑠𝑒𝑔
𝑉𝑃𝐹𝑅 = 0,081 ∗ 2𝑚𝑖𝑛 ∗ ∗ ∗ 241933.33
𝐿 60𝑠𝑒𝑔 1𝑚3 𝑚𝑜𝑙

𝑉𝑃𝐹𝑅 = 653220𝑑𝑚3

e. What is the volume of a single CSTR necessary to achieve 50% conversion?

For a CSTR:

𝐹𝐴0 𝑋1 1
𝑉𝐶𝑆𝑇𝑅1 = = 𝐶𝐴0 𝑣0 ( )𝑋
−𝑟𝐴1 −𝑟𝐴1 1
In a CSTR the rate reaction is the exit value. The volume of a CSTR is the area of a rectangle. The plot
necessary to obtain the volume is shown in the follow figure. Then:

𝑚𝑜𝑙 𝑚3 1𝑚𝑖𝑛 1000𝐿 𝑑𝑚3 𝑠𝑒𝑔

𝑉𝐶𝑆𝑇𝑅1 = 0,081 ∗ 2𝑚𝑖𝑛 ∗ ∗ ∗ 7.5 ∗ 105 𝑚𝑜𝑙 ∗ 0.5
𝐿 60𝑠𝑒𝑔 1𝑚 3

𝑉𝐶𝑆𝑇𝑅1 = 1 012500𝑑𝑚3

f. What is the volume of a second CSTR to raise the conversion from 50% to 60%?

The procedure is the same that (e) item. In the plot are both situations 50 and 60% of conversion.

Now, for a 60% conversion in a second CSTR:

𝐹𝐴0 (𝑋2 − 𝑋1 ) 1
𝑉𝐶𝑆𝑇𝑅2 = = 𝐶𝐴0 𝑣0 ( ) (𝑋2 − 𝑋1 )
−𝑟𝐴2 −𝑟𝐴2

1
𝑉𝐶𝑆𝑇𝑅2 = 𝐶𝐴0 𝑣0 ( ) (𝑋2 − 𝑋1 )
−𝑟𝐴2

𝑚𝑜𝑙 𝑚3 1𝑚𝑖𝑛 1000𝐿 𝑑𝑚3 𝑠𝑒𝑔

𝑉𝐶𝑆𝑇𝑅2 = 0,081 ∗ 2𝑚𝑖𝑛 ∗ ∗ ∗ 1.0 ∗ 106 𝑚𝑜𝑙 ∗ (0.6 − 0.5)
𝐿 60𝑠𝑒𝑔 1𝑚3

𝑉𝐶𝑆𝑇𝑅2 = 270000𝑑𝑚3

RECIPROCAL RATE
1.20E+06

1.00E+06
1/-rA (dm3.seg/mol)

8.00E+05

6.00E+05

4.00E+05

2.00E+05

0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6
X
g. Plot the rate of reaction and conversion as a function of PFR volume.

The mole balance for a PFR is given by:

𝑋
1
𝑉𝑃𝐹𝑅 = 𝐹𝐴0 ∫ ( ) 𝑑𝑋
0 −𝑟𝐴

The integral sign shall calculate by Simpson’s Rule. For example, when conversion is 0.1:

1 0
0.1
1 𝑋2 − 𝑋0 𝑓(𝑋0 ) + 𝑓(𝑋2 )
∫ ( ) 𝑑𝑋 = [( ) + 2 ∑ 𝑓(𝑋𝑖 ) + 2 ∑ 𝑓(𝑋2𝑖+1 )]
0 −𝑟𝐴 3∗2 2
1 0

0.1
1 0.1 − 0.0 1.0 + 1.52
∫ ( ) 𝑑𝑋 = [( ) + 2(1.27) + 2(1.27)] ∗ 105
0 −𝑟𝐴 3∗2 2

0.1
1 𝑑𝑚3 𝑠𝑒𝑔
∫ ( ) 𝑑𝑋 = 10566.67 𝑚𝑜𝑙
0 −𝑟𝐴

The volume is:

𝑚𝑜𝑙 𝑚3 1𝑚𝑖𝑛 1000𝐿 𝑑𝑚3 𝑠𝑒𝑔
𝑉𝑃𝐹𝑅 = 0,081 ∗ 2𝑚𝑖𝑛 ∗ ∗ ∗ 10566.67 𝑚𝑜𝑙
𝐿 60𝑠𝑒𝑔 1𝑚 3

𝑉𝑃𝐹𝑅 = 28530𝑑𝑚3

RECIPROCAL RATE
1.20E+06

1.00E+06
1/-rA (dm3.seg/mol)

8.00E+05

6.00E+05

4.00E+05

2.00E+05

0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6
X

X 0.0 0.1 0.2 0.3 0.4 0.5 0.6

1/-rA(dm3.seg/mol)*105 1.00 1.52 2.00 3.51 5.00 7.50 10.00
-rA(mol /dm3.seg)*10-5 1.00 0.66 0.50 0.29 0.20 0.13 0.10
V (dm3) 0 28530 75150 147150 258390 422415 653220
The reaction rate and conversion as a function of volume are shown in the follows figures:

RATE OF REACTION
1.00E-05

8.00E-06
-rA (mol/dm3.seg)

6.00E-06

4.00E-06

2.00E-06

0.00E+00
0 100000 200000 300000 400000 500000 600000 700000
V (dm3)

CONVERSION
0.6

0.5

0.4

0.3
X

0.2

0.1

0
0 100000 200000 300000 400000 500000 600000 700000
V (dm3)

The plots show us opposites behaviors, the rate of reaction and volume are variables inversely proportional
while the conversion and volume are directly proportional. If want to achieve longer conversion the volume
reactor increases until a constant value. The reactor size is longer with the decrease of the rate of reaction
because the reactants stay more times no reacting.

h. Give a critique of the answers to this problem.

The use of Simpson´s Rule is important and useful in the PFR because the polynomial fit isn’t an easy work.
This method was applied in the items (a, d, g). For CSTR the principle is calculating the rectangle area
resulting of the conversion vs reciprocal rate plot as was made in the (b, e, f) items.
Because the method used the answers are logical, the CSTR volume is longer than a PFR because for it the
volume is given by the area under curve while a CSTR is the rectangle area.

Find the volume of the PFR necessary to achieve an 80% conversion can be complicated, because don’t have
rate of reaction data for a range 60-80%; besides interpolate can be dangerous because can’t assure that
rate of reaction will have the same behavior.

The volume of the CSTR2 is smaller than CSTR1, is logic, because the conversion range for the CSTR1 is 0,5
while for the CSTR2 is 0,1. Analyzing the design equation for a CSTR’s in series the volume is a function of the
conversion difference.

EXERCISE 2
Pure A is fed at a volume flow rate of 1000dm3/h and at a concentration of 0,005lbmol/ft3 to an existing a
CSTR, which is connected in series to an existing tubular reactor. If the volume of the CSTR is 1200dm 3 and
the tubular reactor volume is 600dm3, what are the intermediate and final conversions that can be achieved
with the existing system? The reciprocal rate is plotted in figure as a function of conversion for the
conditions at which the reaction is to be carried out.

SOLUTION:

Moles balance for a CSTR:

𝐹𝐴0 𝑋1 𝐹𝐴0
𝑉𝐶𝑆𝑇𝑅 = =( )𝑋
−𝑟𝐴 −𝑟𝐴 1

To obtain the conversion achieved in the CSTR shall develop an iterative procedure. The first step is to
suppose conversion values and then calculate FA0/-rA.
The second step is read at the same conversion value this ratio and compares these. If the ratios are the
same, this value is correct else suppose a new conversion value. The plot given can be better seem in follow
figure:
 4000

3000
FA0/-rA (dm)

2000

1000

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
X

Now:
𝐹𝐴0 𝑉𝐶𝑆𝑇𝑅
=
−𝑟𝐴 𝑋1

The table and plot necessaries to find X1 value are:

X1 supp. FA0/-rA calc. FA0/-rA read. Difference

0.2 6000 1100 4900
0.4 3000 1400 1600
0.6 2000 2100 -100
0.5 2400 1700 700
0.58 2069 2000 69
The range of conversion is small, and then can interpolate these values to obtain a difference equal to zero.
So the conversion is:
𝑋1 = 0.588

The PFR volume is given by:

𝑋2 𝑋2
𝑑𝑋 𝐹𝐴0
𝑉𝑃𝐹𝑅 = 𝐹𝐴0 ∫ =∫ ( ) 𝑑𝑋
𝑋1 −𝑟𝐴 𝑋1 −𝑟𝐴

This expression means that the PFR volume is the area under curve. In this case the area is a trapezoid, so
the conversion achieved in the device shall be calculated iterating the area and compare with the volume
given.

The trapezoid area is given by:

(𝐵 + 𝑏)
𝑉𝑃𝐹𝑅 = 𝐴 = ∗ℎ
2
Where: B and b are the major and minor bases respectively and h is the height. In this situation b is a
constant value and, B and h are variables.

Suppose that PFR conversion is 0.7, so:

ℎ = 𝑋2𝑠𝑢𝑝𝑝𝑜𝑠𝑒𝑑 − 𝑋1 = 0.7 − 0.588

ℎ = 0.112

Then, need to read FA0/-rA at this conversion value:

𝐹𝐴0
𝐵=( )
−𝑟𝐴 𝑋
2 𝑠𝑢𝑝𝑝𝑜𝑠𝑒𝑑

𝐵 = 3000𝑑𝑚3

The area is:

(3000 + 2040)𝑑𝑚3
𝑉𝑃𝐹𝑅 = 𝐴 = ∗ 0.112
2
𝑉𝑃𝐹𝑅 = 𝐴 = 282.24𝑑𝑚3

The iterative procedure values and plot are shown to follow:

X2 supp. h B (dm3) Atrapezoid difference

0.7 0.112 3000 282.24 317.76
0.76 0.172 3600 485.04 114.96
0.78 0.192 3800 560.64 39.36
0.79 0.202 3900 599.94 0.06

Then, the conversion achieved in the PFR is:

𝑋2 = 0.790

The plot is shown in the next page.

EXERCISE 3
According to you, what are the most important equations that were shown in chapters one and two?
Describe the restrictions and conditions of their use.

SOLUTION:

The most important equations are the continuous flow: CSTR and PFR design equations, because those
reactors achieve higher conversion than Batch reactors.

PFR
The design equation is given by:

𝑋 𝑋
𝐹𝐴0 1
𝑉𝑃𝐹𝑅 = ∫ 𝑑𝑋 = ∫ 𝐹𝐴0 ( ) 𝑑𝑋
0 −𝑟𝐴 0 −𝑟𝐴

- This reactor operates to steady state.

- The conversion depends of the position.

CSTR
The design equation is given by:

𝐹𝐴0 𝑋 1
𝑉𝐶𝑆𝑇𝑅 = = 𝐹𝐴0 ( )𝑋
−𝑟𝐴 −𝑟𝐴

- This reactor is a dispositive that operates to steady state.

- Shall guarantee the perfect mixed condition, to achieve those characteristics inside the tank can be the
same in the outlet.
- A good agitation to do the temperature and concentration constants, then rate of reaction also.
- It’s commonly used to liquid phase reaction.