Department of Chemical Engineering

University of San Carlos Technological Center

Nasipit, Talamban, Cebu City

ChE 512L
Chemical Engineering Laboratory 2

Reaction Rate Kinetics, Temperature Effects, and Performance of a Plug Flow Reactor
( Tubular Flow Reactor )

An Initial Laboratory Report Submitted To

Engr. May V. Tampus
Instructor, ChE 512L

By
Group 4
Aaron, James Glerry J.
Chia, Bernadette A.
Saladaga, Jesha Helery R.

July 30, 2014

2. Objectives
2.1 Determine the reaction order and the rate constant for the ethyl actetate-NaOH reaction
system using plug flow reactor data.
2.2 Determine the variation of conversion with respect to the residence time.
2.3 Verify the temperature dependence of the reaction rate constant.

4.

Results and Discussion

4.1 Determination of Reaction Order and the Rate Constant

0.04
0.03
0.03
0.02

0.00 1.00 2.00 3.00 4.00

-3.3000
f(x) = - 0x + 0.03
R = 0.98

-3.4000
-3.5000

f(x) = - 0.12x - 3.38

ln CNaOH,f -3.6000

CNaOH,f 0.02

-3.7000

0.01

R = 0.98

-3.8000

0.01

-3.9000

0.00
0.00 1.00 2.00 3.00 4.00

-4.0000

, min

, min

(a)

(b)

60.0000
50.0000
40.0000

1/ CNaOH,f (L/mol)

f(x) = 4.99x + 28.12

R = 0.98

30.0000
average

20.0000

Linear (average)

10.0000
0.0000
0.00

5.00

, min

(c)
Figures 4.1.1 Plots of the average of the two trials in (a) zero order, (b) first order, and (c) second
order reaction kinetics.

Table 4.1.1. Summary of Reaction Order and Rate Constant Determination

Reaction Order,

Rate

n
0

Kinetics
-rA=k

1
2

Rate Constant, k

Unit

0.9775
0.9790

333.7041
8.1728

mol/L.min
1/min

0.9800

0.2005

L/mol.min

Plot

R2

-rA=kCA

CA vs
ln(CA) vs

-rA=kCA2

1/CA vs

The integral method was used to determine the order and rate constant of the ethyl acetateNaOH reaction. Figure 4.1.1 shows the best fit lines for every plot of an order. It can be seen
that the best fit line with the highest regression coefficient, R 2, is the n=2. This means that the
reaction between ethyl acetate and NaOH is second order. This is in accordance with the
hypothesis that the reaction is second order based on its stoichiometry. The reaction depends
on both the concentration of ethyl acetate and NaOH, and may possibly follow an elementary
rection.

4.2 Conversion as a Function of Residence Time

0.90
0.80
0.70
0.60
0.50
xNaOH 0.40
0.30
0.20
0.10
0.00
0.0000

1.0000

2.0000

3.0000

4.0000

5.0000

Residence time, min

Figure 4.2 Variation of conversion with residence time.

Data plotted are the average of the two trials.

Figure 4.2 shows that for a certain residence time ( = 0 to = 1 min), the conversion of
NaOH increases. But after = 1 min, the slope of the curve changes. The conversion of NaOH
still increases with the residence time, but in a lesser rise as compared to the first part. This is
because at the beginning of the reaction, there are still higher concentrations of the reactants
giving way to more reaction. However, as time increases, there is a decrease in the reactant
concentrations and little conversion is going on. As time increases, more products are formed,
more reactants are consumed, and conversion increases.

4.3 Determination of Temperature Dependence of Reaction Rate

4.0000
3.5000

f(x) = - 3917.01x + 15.83

R = 0.99

3.0000
2.5000
ln kave

2.0000
1.5000
1.0000
0.5000
0.0000
3.00E-03

3.20E-03

3.40E-03

1/Tave ,K-1

Figure 4.3 Variation of Rate Constant with Temperature Based on Average Values

Figure 4.3 shows the Arrhenius plot of the reaction between ethyl acetate and NaOH; table
4.3 shows the calculated frequency factor (k0) and activation energy (E) from the experiment.
Because the plot (figure 4.3) gives off an R 2 = 0.9933, the reaction follows Arrhenius law which
states that the energy activation energy is constant for a reaction at the same concentration but
different temperatures. The temperature dependency of a reaction is found in the rate constant
which is affected by the activation energy and the temperature of the system. The higher the
temperature, the higher the rate constant is because high temperatures signify higher kinetic
energy of the molecules. This will lead to more collisions between the reactants and the reaction
occurring between them.
The average activation energy calculated is 131777.4 J/mol and the k 0 is 7466971. The high
value of the activation energy means that the ethyl acetate-NaOH reaction is greatly affected by
the temperature, or that it is a temperature-sensitive reaction.

Table 4.3 Temperature Dependence of Trials 1 and 2, and Average

Average
Trial 1
Trial 2

ko

E (J/mol)

7.47E+06
1.31E+06
4.22E+07

131577.4
28653.37
36478.51

References:

Geankoplis, C. J. (2003). Transport Processes and Unit Operations / C.J. Geankoplis.

Englewood Cliffs, EUA : Prentice-Hall.

Levenspiel, O. (1967). Chemical reaction engineering. New York: Wiley.

7. Appendices
Table 7.1. Determination of Initial Concentration of NaOH Solution

Volume of

Initial Buret

Final Buret

NaOH (mL)

Reading (mL)

Reading (mL)

10.00
10.00

0.00
9.50

9.50
19.60

Trial 1
Trial 2

Volume of 0.1N
HCl used in
titration (mL)
9.50
10.10
Average CNaOH
(mol/L)

CNaOH
(mol/L)
0.095
0.101
0.098

Table 7.2. Determination of initial concentration of EtOAc solution

Trial 1
Trial 2

Volume

Volume of

Volume of

of EtOAc

0.1N NaOH

0.1 N HCl

(mL)

added (mL)

added (mL)

5.00
5.00

10.00
10.00

10.00
10.00

Initial

Final

Volume of

Buret

Buret

NaOH used

CEtOAc

Reading

Reading

in titration

(mol/L)

(mL)
20.00
33.00

(mL)
25.20
38.10

(mL)
5.20
5.10
Average

0.098
0.096

EtOAc

0.097

(mol/L)

Table 7.3. Relevant Parameters

Reactor Volume
(L)
CNaOH in feed
vessel (mol/L)

0.4

CHCl used (N)

0.1

0.098

CNaOH used in
titration (N)

0.097

Table 7.4. Data for Constructing n=0, n=1, n=2 Graphs

T (0C)

Initial
31.5
31.0
31.0
31.0
40.0
51.5

Final
31.2
31.0
31.0
31.0
41.0
50.8

FNaOH
(cm3/
min)
50
100
150
200
100
100

FEtOAc
(cm3/
min)

v0
(cm3/
min)

50
100
150
200
100
100

100
200
300
400
200
200

(min)

4.00
2.00
1.33
1.00
2.00
2.00

TITRANT (0.097 N NaOH)

Initial Reading Final Reading
VNaOH (mL)
(mL)
(mL)
1
2
1
2
1
2
0.00
8.15
8.15
16.35 8.15 8.20
16.35 23.50
23.50
31.40 7.15 7.90
30.60 37.90
37.90
45.10 7.30 7.20
0.00
7.20
7.20
14.60 7.20 7.40
0.00
7.80
7.80
15.80 7.80 8.00
17.80 26.50
26.50
34.80 8.70 8.30

CNaOH, effluent
(mol/L)
1
0.0209
0.0306
0.0292
0.0302
0.0243
0.0156

xNaOH

2
0.0205
0.0234
0.0302
0.0282
0.0224
0.0195

1
0.7863
0.6873
0.7021
0.6922
0.7516
0.8407

2
0.7912
0.7615
0.6922
0.7120
0.7714
0.8011

Table 7.4. Data for Constructing n=0, n=1, n=2 Graphs (Continued)

, min

4
2
1.3333
1

CNaOH,f

Trial 1
0.020
9
0.030
6
0.029
2
0.030
2

Trial 2
0.020
5
0.023
4
0.030
2
0.028
2

ln CNaOH,f

Ave.

Trial NaOH
1 ,fTrial 2
47.74
48.87
41
59
32.63
42.78
18
99
34.25
33.15
83
65
33.15
35.43
65
59

Trial 1

Trial 2

-0.0428

-3.8659

-3.8893

-0.0307

-3.4853

-0.0262
-0.0268

Average

CNaOH,f (mol/L)

Average

Trial 1

Trial 2

-3.8776

0.0209

0.0205

0.0207

-3.7563

-3.6208

0.0306

0.0234

0.027

-3.5339

-3.5012

-3.5176

0.0292

0.0302

0.0297

-3.5012

-3.5677

-3.5345

0.0302

0.0282

0.0292

Table 7.5. Conversions with Respect to Residence Times

Residence time,
(min)

Average

Trial 1

Trial 2

4.0000
2.0000
1.3333

0.7888
0.7244
0.6972

0.7863
0.6873
0.7021

0.7912
0.7615
0.6922

Ave.
0.7888
0.7244
0.6972
0.7021
0.7615
0.8209

1.0000
0.0000

0.7021
0.0000

0.6922
0.0000

0.7120
0.0000

60.0000

-3.2000

50.0000

-3.4000

f(x) = 5.02x + 26.49

40.0000
R = 0.87
30.0000

1/ CNaOH,f (L/mol)

0.0350
0.0300

f(x) = - 0.12x - 3.34

-3.6000
ln CNaOH,f
R = 0.86

20.0000

-3.8000

10.0000
0.0000
0.00

5.00

0.0250
0.0200

CNaOH,f 0.0150
0.0100

-4.0000
0.00 2.00 4.00 6.00

0.0050
0.0000
0.001.002.003.004.005.00

, min

, min

(a)

f(x) = - 0x + 0.03
R = 0.85

(b)

(c)

60.0000
50.0000
f(x) = 4.96x + 29.74
40.0000
R = 0.86
30.0000

1/ CNaOH,f (L/mol)

20.0000
10.0000
0.0000
0.005.00
, min

(d)

-3.2000

0.0400

-3.4000

0.0300

-3.6000 f(x) = - 0.12x - 3.43

ln CNaOH,f
R = 0.83
-3.8000

CNaOH,f

f(x) = - 0x + 0.03
R = 0.79

0.0200
0.0100

-4.0000
0.00 2.00 4.00 6.00

0.0000
0.00 1.00 2.00 3.00 4.00 5.00

, min

, min

(e)

(f)

Figures 7.1 Plots of the trials 1 (a to c) and 2 (d to f) in second order, first order, and zero order reaction kinetics respectively.

1.00

1.00

0.80

0.80

0.60

0.60

xNaOH 0.40

xNaOH 0.40

0.20

0.20

0.00

0.00
0

0 1 1 2 2 3 3 4 4

Residence time, min

Residence time, min

Figures 7.2 Plots of Conversions versus Residence Time of Trials 1 and 2 respectively.

Table 7.6. Data for Determining Temperature Effects

Average
Temperature, Tave
(oC)
(K)
31
304.15
40
313
50.5
323.5

(1/Tave)
0.003288
0.003195
0.003091

Final cNaOH
(mol/L)
Trial 1
Trial 2

Trial 1

Trial 2

0.098

0.0306

0.0234

0.6873

0.7615

2.00

0.098

0.0243

0.0127

0.7516

0.8704

2.00

0.098

0.0156

0.0098

0.8407

0.9001

2.00

Initial CNaOH
(mol/L)

xNaOH

(min)

Table 7.6. Data for Determining Temperature Effects (Continued)

Trial 1

k=1 /(*Ca)
Trial 2
Average

Average

16.31588

21.39495

18.8554

2.792139

3.063155

2.9276

20.54232

39.37008

29.9562

3.022487

3.673006

3.3477

32.03075

51.07252

41.5516

3.466696

3.933247

3.7000

4
3
ln k

Trial 1

ln k
Trial 2

6.00
f(x) = - 4472.02x + 17.09
R = 0.98

1
0
3.0E-03

3.2E-03

1/Tave ,K-1

3.4E-03

4.00
ln k 2.00
0.00
3.0E-03

f(x) = - 5227.6x + 20.07

R = 0.93
3.2E-03

1/Tave ,K-1

3.4E-03

Figures 7.1 Plots of Temperature Dependence of Trials 1 and 2, respectively

SAMPLE CALCULATIONS