Department of Chemical Engineering University of San Carlos-Technological Center Nasipit, Talamban, Cebu City

ChE 512L Chemical Engineering Laboratory 1

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

Initial Laboratory report submitted to Engr. Ramelito C. Agapay Instructor, ChE 512L

By Cequia, Ma. Aimee Lynn Malinao, Karmela Sheryl

July 12, 2011

1. Objectives: Determine the reaction order and the rate constant for the ethylacetate-NaOH reaction system using plug flow reactor data. Determine the variation of conversion with respect to the residence time. Verify the temperature dependence of the reaction rate constant.

2. Results and Interpretations

0.9600 ln(()/(1NaOH ) ) 0.9400 0.9200 0.9000 0.8800 0.8600 0.8400 0.8200 0.8000 0.00 1.00 2.00 3.00 4.00 5.00 6.00 average Linear (average) y = 0.0306x + 0.7941 R = 0.8744

, min
Figure 1. Plot of against residence time at reaction order n=2.

-3.1400 -3.1600 -3.1800 -3.2000 0.00 1.00 2.00 3.00 4.00 5.00 6.00

y = -0.033x - 3.1498 R = 0.8733 average Linear (average)

ln CNaOH,f

-3.2200 -3.2400 -3.2600 -3.2800 -3.3000 -3.3200

, min

Figure 2. Plot of ln CNaOH,f against residence time at reaction order n=1.

0.0430 0.0420 0.0410 y = -0.0013x + 0.0427 R = 0.8576

CNaOH,f

0.0400 0.0390 0.0380 0.0370 0.0360 0.00 1.00 2.00 3.00 4.00 5.00 6.00 average Linear (average)

, min
Figure 3. Plot of CNaOH,f against residence time at reaction order n=0.

The concentration of sodium hydroxide decreased with increasing residence time as seen in figures 2 and 3 where the slopes are negative. Figure 1 showed that the conversion of sodium hydroxide increased with increasing residence time. Residence time was defined as the length of time the fluid would stay in the reactor. The longer the reactants would stay in the reactor, more products would be formed.
Table 1. Reaction rate constant at different reaction order. reaction order, n 2 1 0 R Trial 1 0.8461 0.845 0.8308
2

reaction rate constant, k Trial 2 0.8872 0.886 0.8693 Trial 1 1.1959 34.0136 909.0909 Trial 2 1.4948 27.3224 714.2857

Average 1.3454 30.6680 811.6883

Unit L/mol.min 1/min mol/L.min

The entries in Table 1 showed the values of the reaction rate constant at different overall reaction order with their corresponding correlation coefficients, R2. Among the three overall reaction orders, n = 2 was selected since it had the correlation coefficient nearest to 1. Thus, the saponification reaction between ethyl acetate and sodium hydroxide was a second-order reaction and this was expected since the reaction was homogeneous and an elementary reaction.

The correlation coefficient describes how the equation best represents the data and the highest attainable correlation coefficient value is 1 (Bluman, 2004). The correlation coefficient obtained for the second order reaction was 0.8872 which was still far from 1. One of the reasons for the large difference of the correlation coefficient was the assumption made in deriving the equation used in plotting the data. The reaction was assumed to occur at an ideal tubular flow reactor which meant that there was no back mixing and that radial mixing only occurred in the reactor. There are two kinds of deviation from the ideal behaviour: 1.) vortices and eddies produces mixing in the longitudinal direction and 2.) when the fluid is in laminar flow, and the molecular-diffusion process is relatively slow, the annular elements of the fluid flow through the reactor only slightly mixed in the radial direction. Another reason for the deviation from ideal reactor is the fluid near the wall will have a longer residence time in the reactor while the fluid near the center will have a shorter residence time compared to ideal reactor and will result to decrease in conversion (Smith, 1970).

0.66 0.65 0.64 xNaOH 0.63 0.62 0.61 0.60 0.59 0.00 1.00 2.00 3.00 4.00 5.00 6.00 Residence time, min Figure 4. Plot of the average conversion of sodium hydroxide versus residence time

Conversion

is the number of moles of A that reacted per mole of A fed to the

system. The conversion is defined with respect to the basis of the calculation and in this case, species A is taken as the basis of the calculation (Fogler, 2006).

The conversion of sodium hydroxide increased with respect to time, as depicted in Figure 4. Figure 4 showed the strong correlation between conversion and the residence time of the fluid in the plug flow reactor. This trend was expected since in the plug flow reactor, the conversion would increase with increasing residence time (defined as the length of time the reactants spend in the reactor).

0.2 0.18 0.16 0.14 0.12 ln k 0.1 0.08 0.06 0.04 0.02 0 3.05E-03 3.10E-03 3.15E-03 3.20E-03 1/Tave Figure 5. Plot of ln k versus (1/Tave) 3.25E-03 3.30E-03 3.35E-03 y = -415.76x + 1.458 R = 0.9098

The temperature dependence of the reaction rate constant was evident in Figure 5 and was in accordance to the Arrhenius law. The correlation coefficient of the Arrhenius plot shown in Figure 5 was 0.909 which indicated that 90.9% of the data was represented by the equation: dependence of ln k with (1/Tave). [Equation 1] From this plot, two parameters could be determined which were as follows: (1) preexponential factor, and (2) activation energy, E. Using the equation 1, the average , respectively. The and also indicated a high linear

and E values were determined to be equal to 4.527 and

value of the activation energy would indicate the minimum energy requirement in order for the reaction to take place. At a temperature range of , the average

activation energy needed for the saponification reaction between ethyl acetate and sodium hydroxide to occur was .

3. Sample Calculations 3.1. Calculation of the initial concentration of NaOH solution

3.2. Calculation of the initial concentration of ethyl acetate solution

) ( ) ) ( (

( ) ) (

3.3. Calculation of the total flow rate of solutions

3.4. Calculation of the residence time of the fluid in the plug flow reactor ( ) ( ) ( )

3.5. Calculation of NaOH concentration in effluent sample ( ( )( ) )( ( ) )( )( )

3.6. Calculation of the conversion of NaOH ( ) ( )

3.7. Calculation of the reaction rate constant, k If n = 2 ( Notations: ) ( )

3.8. Calculation of the pre-exponential factor, ko , and the activation energy of the reaction, E Given: Equation obtained from regression of Solution: ( ) data:

4. References Bluman, A.G. (2004). Elementary Statistics: A Step by Step Approach, 5th Edition. McGraw-Hill, Inc, New York. Fogler, S.H. (2006). Elements of Chemical Reaction Engineering, 4th Edition. New Jersey: Pearson Education, Inc.

Smith, J. M. (1970). Chemical Engineering Kinetics. McGraw-Hill, Inc, New York.

5. Appendix 5.1. Processed data

Table 2. Volume readings and initial concentration of sodium hydroxide solution Volume of Initial Buret Final Buret Volume of 0.1N HCl NaOH (mL) Reading (mL) Reading (mL) used in titration (mL) Trial 1 Trial 2 5.00 5.00 0.00 5.30 5.30 10.60 5.30 5.30 CNaOH (mol/L) 0.106 0.106

Table 3. Volume readings and initial concentration of ethyl acetate solution Volume of Volume of Volume of Initial Final Volume 0.1 N NaOH 0.1 N HCl Buret Buret of EtOAc NaOH used in added Reading Reading (mL) added titration (mL) (mL) (mL) (mL) (mL) Trial 1 5.00 10.00 10.00 26.00 29.00 3.00 Trial 2 5.00 10.00 10.00 29.00 32.00 3.00 Table 4. Flow rate readings and residence time in the plug flow reactor Temperature ( C) Initial 32.0 31.0 30.5 32.0 42.0 50.0 Final 31.5 31.0 31.0 31.0 40.5 50.5 30 60 90 120 90 90
0

CEtOAc (mol/L) 0.600 0.600

Flowrate of 3 NaOH (cm /min)

Flowrate of EtOAc 3 (cm /min) 53 106 159 212 159 159

Total flowrate of solutions, v0 3 (cm /min) 83 166 249 332 249 249

Residence time, (min) 4.82 2.41 1.61 1.20 1.61 1.61

Table 5. Final concentration and conversion of sodium hydroxide solution for different temperature and flow settings VNaOH used in CNaOH,f (mol/L) xNaOH,f Residence Average titration (mL) 0 Temperature ( C) time, (min) Trial 1 Trial 2 Trial 1 Trial 2 Trial 1 Trial 2 31.8 31.0 30.8 31.5 41.3 50.3 4.82 2.41 1.61 1.20 1.61 1.61 6.30 6.05 6.05 5.80 6.25 6.30 6.35 6.10 6.00 5.75 6.30 6.35 0.0370 0.0395 0.0395 0.0420 0.0375 0.0370 0.0365 0.0390 0.0400 0.0425 0.0370 0.0365 0.6509 0.6274 0.6274 0.6038 0.6462 0.6509 0.6557 0.6321 0.6226 0.5991 0.6509 0.6557

Table 6. Reaction rate constant values at different temperature settings Average Temperature, k Tave (1/Tave) o ( C) (K) Trial 1 Trial 2 Average Trial 1 0.0032 1.0934 1.0788 1.08613 0.0893 30.75 303.75 92 54 16 5 42 0.0031 1.1540 1.1697 1.16190 0.1432 41.25 314.25 82 62 56 9 88 0.0030 1.1697 1.1856 1.17771 0.1567 50.25 323.25 94 56 78 7 95

ln k Trial 2 0.0758 65 0.1567 95 0.1703 15 Average 0.082603 0.150041 0.163555

5.2. Figures
0.94 0.92 0.9 0.88 0.86 0.84 0.82 0.8 0.00 2.00 4.00 6.00 residence time, min Figure 6. Plot of
( )

y = 0.0272x + 0.8023 R = 0.8461

Trial 1 Linear (Trial 1)

versus residence time for n=2 (Trial 1)

0.96 0.94 0.92 0.9 0.88 0.86 0.84 0.82 0.8 0.78 0.00 2.00 4.00 6.00 residence time, min Figure 7. Plot of
( )

y = 0.034x + 0.7859 R = 0.8872

Trial 2 Linear (Trial 2)

versus residence time for n=2(Trial 2)

10

-3.16 -3.18 -3.2

ln CNaOH,f

-3.22 -3.24 -3.26 -3.28 -3.3 -3.32 0.00 2.00 4.00 6.00 residence time, min y = -0.0294x - 3.1587 R = 0.845 Trial 1 Linear (Trial 1)

Figure 8. Plot of

versus residence time for n=1 (Trial 1)

-3.14 -3.16 -3.18 -3.2 -3.22 -3.24 -3.26 -3.28 -3.3 -3.32 -3.34 0.00

ln CNaOH,f

Trial 2 Linear (Trial 2) y = -0.0366x - 3.141 R = 0.886 2.00 4.00 6.00

residence time, min Figure 9. Plot of versus residence time for n=1 (Trial 2)

11

0.0430 0.0420 0.0410

CNaOH,f

0.0400 Trial 1 0.0390 0.0380 0.0370 0.0360 0.00 2.00 4.00 6.00 residence time, min y = -0.0011x + 0.0424 R = 0.8308 Linear (Trial 1)

Figure 10. Plot of

versus residence time for n=0 (Trial 1)

0.0430 0.0420 0.0410

CNaOH,f

0.0400 0.0390 0.0380 0.0370 0.0360 0.0350 0.00 2.00 4.00 6.00 residence time, min y = -0.0014x + 0.0431 R = 0.8693 Trial 2 Linear (Trial 2)

Figure 11. Plot of

versus residence time for n=0 (Trial 2)

12

0.66 0.65 0.64 xNaOH 0.63 0.62 0.61 0.60 0.00 1.00 2.00 3.00 4.00 5.00 6.00 Residence time, min Figure 12. Plot of conversion of sodium hydroxide versus residence time (Trial 1)

0.67 0.66 0.65 0.64 xNaOH 0.63 0.62 0.61 0.60 0.59 0.00 1.00 2.00 3.00 4.00 5.00 6.00 Residence time, min Figure 13. Plot of conversion of sodium hydroxide versus residence time (Trial 2)

13

0.18 0.16 0.14 0.12 ln k 0.1 0.08 0.06 0.04 0.02 0 3.1E-03 3.1E-03 3.2E-03 3.2E-03 3.3E-03 3.3E-03 3.4E-03 y = -345.62x + 1.2321 R = 0.9283

Trial 1 Linear (Trial 1)

1/Tave ,K-1
Figure 14. Plot of ln k versus (1/Tave) for Trial 1

0.20 0.18 0.16 0.14 0.12 ln k 0.10 0.08 0.06 0.04 0.02 0.00 3.1E-03 3.1E-03 3.2E-03 3.2E-03 3.3E-03 3.3E-03 3.4E-03 y = -485.89x + 1.684 R = 0.8958 Trial 2 Linear (Trial 2)

1/Tave ,K-1
Figure 15. Plot of ln k versus (1/Tave) for Trial 2

14