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

ChE 512L Chemical Engineering Laboratory 1

Tubular Flow Reactor

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

By Gabutina, Maria Camille Navida, Marjon Obiedo, Elena

June 28, 2012

1. Objectives: Determine the reaction order and the rate constant for the ethyactetate-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 Discussion 2.1 Reaction Order and Rate Constant Determination The reaction order for the ethyl acetate-NaOH reaction system was determined by a trial and error method. It was assumed that the reaction system follows an elementary reaction. For elementary reactions, the rate equation corresponds to the stoichiometric equation. For ethyl acetate-NaOH reaction given by the stoichiometric equation C2H5O2CCH3 + Na-OH CH3CO2Na + H3C-CH2-OH, the rate equation is -rA=kCACB. So in theory, it is expected that the reaction order is 2. The experiment was carried at a constant temperature of 31C and flow rates were varied. Table 1 below shows the different reaction orders and the corresponding coefficient of variation (r2).

Table 1. Different reaction orders with corresponding coefficient of variation (r2). Order Zero First Second(CAOCBO) Rate Kinetics -rA=k -rA=kCA -rA=kCACB Plot CA vs t ln(CA/CAO) vs t ln(M-Xa)/M(1-Xa) vs t Coefficient of variation (r2) 0.9200 0.9256 0.9277

Note: Refer to Appendix A for the plots of the different rate kinetics.

The correlation coefficient describes how the equation best represents the data and the highest attainable correlation coefficient value is 1 (Bluman, 2004). From table 1, it can be observed that the reaction order is 2 since it has the highest coefficient of variation which is 0.9277. The experimental results agrees with the theory justified by the highest coefficient of variation of the rate equation -rA=kCACB in which (CAOCBO).

2.2 Variation of Conversion with respect to the residence time Figure 1 below shows the variation of conversion of NaOH (Xa) as calculated from the initial and final concentrations plotted against residence time (t).

0.505 0.5 0.495 0.49 0.485 Xa 0.48 0.475 0.47 0.465 0.46 0.455 0.00 50.00 100.00 t(sec) Figure 1. Plot of NaOH conversion (Xa) versus residence time (t) 150.00 200.00 250.00

From figure 1, it can be observed that the conversion of NaoH increases with increasing residence time. It is because, as residence time is increased, reactants are made to stay longer in the reactor, allowing more time for interaction leading to increased formation of the product or increased conversion. It can be explained by the equation xa = 1- (Ca/Cao).

2.3 Verification of Temperature Dependency on Rate Constant The temperature dependence of the reaction rate constant was investigated by varying the reaction temperature while setting the flow rates of the NaOH and ethyl acetate constant. A plot of ln k against 1/T was also constructed to obtain the value of the activation energy of the reaction.

Table 2. Values of the reaction rate constant at different temperatures. Temperature (C) 31.0 41.0 55.0 k (L/mol-s) 0.077637 0.095094 0.113978

From table 2, it can be observed that the reaction rate constant (k) is increased with increasing temperature. It is because, as the temperature is increased, the kinetic energy of the molecules is also increased allowing frequent collision between reactant molecules, thus the rate of reaction is also increased which is just directly proportional to the reaction rate constant at constant concentrations.
2.5 2 1.5 ln k 1 0.5 0 0.003 y = -1522.2x + 6.5871 R = 0.9937

0.00305

0.0031

0.00315

0.0032

0.00325

0.0033

0.00335

1/Tave Figure 2. Variation of rate constant with temperature

Based on figure 2, it can be seen that lnk is inversely proportional with 1/T which is in accordance with the Arrhenius Law. With different temperatures but same concentration, Arrhenius Law states that

( )

( *

provided that the activation energy (E) stays constant. From the equation of the trendline, the slope which corresponds to E/R was used to calculate the activation energy. The activation energy obtained was 12,655.57 J/mol.

3. Appendices Appendix A. Raw Data:

Table A. 1: Standardization of NaOH Volume NaOH = 10 mL

Standardization of NaOH mKHP(g) MW CKHP(mol/L) 0.5028 204.22 0.02462 1 2 VKHP,i(mL) 2.50 1.50 VKHP,f(mL) 37.95 36.10 VKHP,used(mL) 35.45 34.60 average CNaOH(mol/L) 0.08728 0.08519 0.08623

Table A. 2: Standardization of HCl Volume HCl = 10 mL

VNaOH,i(mL) 5.40 VNaOH,f(mL) 11.40 VNaOH,used(mL) 6.00 CHCl(mol/L) 0.05174

Table A. 3 Standardizaion of EtOAc Volume EtOAc = 10 mL

Standardization of EtOAc VEtOAc(mL) VNaOH,excess(mL) VHCL added(mL) 10.00 20.00 15.00 1 2 VHCl,i(mL) 4.80 8.80 VHCl,f(mL) 8.80 12.40 VHCl,used(mL) 4.00 3.60 average CEtOAC(mol/L) 0.15177 0.15384 0.15281

Table A.4 Data at constant T and varying flowrates (C1) and constant flowrates with different T (C2)
Tf(C) Tf (K) NaOH (mL/min) EtOAc (mL/min) (L/sec) t(sec) 0 Trial 1 Trial 2 Trial 3 Trial 4 31 30 31 30 304.15 303.15 304.15 303.15 70 130 190 250 40 74 109 143 0.00183 0.00340 0.00498 0.00655 218.18 117.65 80.27 61.07 11.40 15.40 6.00 11.00 16.00 19.70 3.00 6.70 10.20 14.30 18.60 17.50 15.40 19.40 9.90 14.80 19.70 23.40 6.70 10.20 14.30 18.60 23.60 22.00 4.00 4.00 3.90 3.80 3.70 3.70 3.70 3.50 4.10 4.30 5.00 4.50 0.04312 0.04312 0.04398 0.04484 0.04570 0.04570 0.04570 0.04743 0.04225 0.04053 0.03449 0.03880 VNaOH,I (mL) VNaOH,f (mL) VNaOH,used (mL) CNaOH,eff (mol/L) CNaOH,ave (mol/L) 0.08623 0.04312 0.04441 0.04570 0.04657

Trial 1 Trial 2

41 55

314.15 250 328.15 143 0.00655 61.07

0.04139 0.03665

Appendix B. Tables and Figures:

Table B.1 Data for the different rate kinetics:

t(sec) 218.18 117.65 80.27 61.07

CNaOH,ave(mol/L) 0.04312 0.04441 0.04570 0.04657

ln(Ca/Cao) -0.6931 -0.6636 -0.6349 -0.6162

ln(M-Xa/M(1-Xa)) 0.3616 0.3438 0.3267 0.3156

For the zero order: Plot of Ca vs. t

0.04700 0.04650 0.04600 0.04550 Ca(mol/L) 0.04500 0.04450 0.04400 0.04350 0.04300 0.04250 0.0000 50.0000 100.0000 150.0000 200.0000 250.0000 t(sec) . y = -2E-05x + 0.0474 R = 0.92

For the first order: Plot of ln Ca/Cao vs t

-0.61 0.0000 -0.62 -0.63 -0.64 -0.65 -0.66 -0.67 -0.68 -0.69 -0.7 -0.71

50.0000

100.0000

150.0000

200.0000

250.0000

ln(Ca/Cao)

y = -0.0005x - 0.5967 R = 0.9256 t(sec)

For the second order

Plot of ln (M-Xa)/M(1-Xa)

0.37 0.36 y = 0.0003x + 0.3039 R = 0.9277

lnM-Xa/M(1-Xa)

0.35 0.34 0.33 0.32 0.31 0.00 50.00 100.00 t(sec) 150.00 200.00 250.00

Table B.2 Data for the different conversions

Tf(C) NaOH (mL/min) EtOAc(mL/min) Xa

Trial 1 Trial 2 Trial 3 Trial 4 Trial 1 Trial 2

31 30 31 30 41

70 130 190 250

40 74 109 143

0.5 0.485 0.47 0.46 0.52

250 55

143 0.575

B.3 Verification of Temperature Dependency on Rate Constant Table B.3 Data for the calculation of activation energy
Tf(C) 30 41 55 1/Tave 0.003299 0.003183 0.003047 ln k -2.55571 -2.35289 -2.17175

Appendix C. Sample Calculations: C. 1 Calculation of initial concentration of NaOH solution (using KHP) ( * ( * ( * ( ) ( * ( *

) (

) (

) (

) (

C. 2 Calculation of concentration of HCl solution(using NaOH) ( ) ( ) ( ) ( ) ( ) ( )

C. 3 Calculation of initial concentration of EtOAc solution ( ) [ ]

) * ( ) (

( ) ) ( )

)(

)+

*(

) (

) (

)+

C. 4 Calculation of the NaOH concentration in the effluent ( )( ) ( ) ) ( )( )

C. 5 Calculation of reaction rate constant For n=2:

m=slope=0.0003=(CEtOAc,i-CNaOH,i)k ( ) ( )

C. 6 Calculation of frequency factor and the activation energy

) (