Evidence for Reaction Controlled Kinetics during Acid Catalyzed Hydrolysis of Ethyl Acetate using Steady State Packed

Bed Plug Flow Reactor (120)

Abstract: A kinetic analysis was performed to determine the Arrhenius and activation enery constants associtated with the catylytic hydrolysis of ethyl acetate. The anlysis was implemented on a packed bed reactor containing cation exchange resin. The hydrolysis reaction produces acetic acid and ethanol, compounds much less volatile than acetic acid. The values of the desired constants were established by varying the reaction temperatures and flow rate and determining the corresponding outlet concentration of ethyl acetate through titration with a sodium hydroxide solution. The resulting conversion data allowed calculation of a set of kinetic rate constants, which were plotted versus temperature to graphically determine the Arrhenius and activation energy values. The termperature range was 30 to 50 C. At each temperature the flow rate was varied from 75 to 140, as read from the rotameter (actual flow rates were calculated by recording the amount of time required to collect a given volume.) Three samples were collected at each set of process conditions to reduce error in the results. An ethyl acetate solution with a concentration of .406M was fed through the packed bed reactor(PBR). The PBR contains an ion exchange resin that is used as a catalyst for the hydrolysis reaction of ethyl acetate. Samples were collected at three different flow rates at each of three different temperatures. To detemine the rate at which the reaction occurred, the final concentration of each sample was measured by NaOH titration. Once the rate constants were determined, they were used to solve for the Arrhenius and activation energy constants. A first-order reaction depends on the concentration of only one reactant (a unimolecular reaction). Other reactants can be present, but each will be zero-order. The rate law for an elementary reaction that is first order with respect to a reactant A is: =

k is the first order rate constant, which has units of 1/s.

[] Section 1.1: Theoretical Background This experiment focuses on the hydrolysis of ethyl acetate with an acid-charged ion exchange resin catalyst. The reaction yields a mixture of acetic acid and ethanol as shown in Equation #. CH3COOCH2CH3 + H2O -> CH3CH2OH + CH3COOH

Reaction Kinetics A packed bed reactor containing ion exchange resin will be utilized to determine the rate of the reaction. The reaction takes place on the surface of the catalyst. Therefore, the rate of the reaction is based on the mass or surface area of the catalyst. The design equation reflects this dependence as shown in equation #. = =

The differential form of the steady state mole balance for a PFR is:

For the purposes of this lab, the reactor will be modeled as a plug flow with an infinite number of smaller reactors of differential volume. A generalized mole balance can be done on the reactor as in Equation #. In Out + Generation = Accumulation , ,(+) + = =

Assuming steady state conditions (no accumulation), Equation # can be simplified to a differential form as seen in Equation #.

The reaction will be assumed to be first order and take the form of Equation #.

Assuming all samples are analyzed at steady state Equation # and # can be combined and reduced to form Equation (#). =

Separate variables by rearrangement:

Intergrate Equation (#) from the initial to final concentration of ethyl acetate and from V=0 to the total volume of the reactor as shown in Equations (#). 0
, , = = =0

Rearrange variables so that k is isolated:

, 0 ln = , k = ln , 0 ,

The unknown rate constant, k, can be determined by plugging in values for the given variables in equation #. Once k is known, the Arrhenius constant and activation energy can be determined from a plot of the ln(k) vs. 1/T. ln() = ln() 1

equal to

A plot of ln(K) versus 1/T will produce a straight line with ln(A) being the y-intercept and slope

. 0.5 2.62 , = 1.5 [] = [ ] 1000

Wilke-Hougen correlation:

Titration Analysis:

The coefficient of variation is a ratio of standard deviation to the population average value. It allows for a comparison of error relative to the magnitude of the measured value. Expressed as a

percentage, the typical acceptable value for coefficient of variation for a measured population is 1% or less. 1 % = 100 / = ( ( )/)^2
=1 =1

Section 1.2: Experimental Apparatus

Section 1.3: Experimental Procedure Emergency Shutoff Procedure 1. Turn off the main power supply. 2. Close the effluent valve. 3. Notify colleagues of the problem. 4. Evacuate the lab if necessary. Operating "Procedure 1. Insure that all valves are closed. 2. Disconnect the feed bucket from the system. 3. Prepare 5 gallons of a 0.04% aqueous ethyl acetate solution in the feed bucket. 4. Return the feed bucket to its original position and reconnect the system. 5. Check the water level in the heating water reservoir (should be about an inch) 6. Check to ensure that the effluent stream valve from the reactor column is open. (The valve must be open for the second controller to function. 7. Turn on the main power. 8. Set the water temperature to the desired temperature. 9. Turn on the water heater. 10. Let the system reach the desired temperature. 11. Place a graduated cylinder under the product collection valve. 12. Open the collection valve and achieve desired flow rate. 13. Allow the system to reach steady state by collecting 1 liter of product.

14. Replace the graduated cylinder with a 100ml volumetric flask. 15. Allow the flask to fill to at least the 50mL mark. 16. Replace the sample flask with another empty 100mL volumetric flask. 17. Repeat steps 16 through 19 until three samples have been collected. 18. Titrate each sample with 0.1M Sodium Hydroxide. 19. Calculate the concentration of ethyl acetate in each sample-record the average of the 3. 20. Properly clean glassware and dispose of waste. 21. Repeat this process for each desired flow rate and temperature. Shutdown Procedure 1. Turn off the main power. 2. Neutralize any unused titration solution and properly dispose of waste 3. Disconnect the feed tank from the system 4. Fill the feed bucket and flush the system using DI water. 5. Run the system to wash any residual material from the reactor. Section 1.4: Safety/Environmental Factors 1. Ethyl Acetate is a highly flammable, volatile organic liquid. 2. Proper ventilation of the work environment is essential for employee safety. 3. Keep feed reservoir covered at all times to reduce the amount of Ethyl Acetate in the air. 4. Describe any safety factors related to the operation of the experimental apparatus (see attachment 11 for further details). 5. Describe any special personnel protection equipment you are required to wear for the experiment. 5.1. If there are no special requirements, include a statement indicating this. 6. Describe any environmental impacts from this experiment. 6.1. Consider gaseous, aqueous, and solid discharges. 6.2. If there are no special impacts, include a statement indicating this.

SECTION 2: RESULTS

The data collected in this experiment was used to determine the if the system was limited by transport effects or reaction kinetics, to determine the activation energy for the hydrolysis of ethyl acetate and to attempt to verify the Wilke-Hougen Correlation. Three sets of flow rate data were collected for each of three operating temperatures. Plots of ln() vs. 1/ were constructed for each flow rate. From the first plot, the Arrhenius constant was determined from the value of the y intercept. The slope was expected to be negative and that the absolute value of the slope is equal to E/R. The R^2-value was used as a measure of linearity. The Activation Energy was calculated for each plot and averaged to produce a final result of 64.0 kJ/mol.

In order to ascertain if the system was rate limited by diffusion or by reaction kinetics the values of each of the rate constants were calculated. Using the modified Wilke-Hougen correlation from equation #, the rate constant for diffusion was determined to be 0.51/s. Using equation #, the average rate constant for the system was determined to be 8.5E-04/s. Comparing the values of the two rates constants we see that the rate for transport effects is much greater than the rate for the reaction. From this we can conclude that the system is limited by the kinetics of the reaction and not by the transport effects.

Figure 3.0 - Runs at same flow rate ln(k) vs 1/T SECTION 3: ANALYSIS & DISCUSSION OF RESULTS The literature value for the Activation Energy of hydrolysis of ethyl acetate was listed as 67.6kJ/mol. The average experimentally determined value for the hydrolysis of ethyl acetate was 64.0 kJ/mol, a difference of 5% from the accepted literature value. This value was determined by taking the average of each of the three Activation Values derived from the slope of ln(k) vs 1/T for each of the three flow rates.
Nominal Activation Flow Rate (mL/s) Energy 2.1 63,770 2.5 65,189 3.5 63,184 Average 64,048 %CV 1.61

Table 2.0 Activation Energy for each flow rate.

The following sources of error were identified quality of the data: 1. One source of error in our analysis is the limitation of the human eye in detecting the titration end point. The sample replicates for each titration were compared against each other and the percent coefficient of variation(%CV) was determined. The %CV for each replicate set was shown to be less than 1% and it was concluded based on this that the value for each titration was consistent and repeatable. Excluding human error, there are still fundamental limitations to what a human eye can detect. For a more accurate analysis with a higher degree of reproducible results, a potentiometric titration using an autotitrator to perform the titrations should be conducted. 2. Another potential source of error in our analysis is the volume of the volumetric pipet used for measuring the amount of sample used for titration. 3. Another source of error in our analysis is the molarity of the sodium hydroxide used during the titration. 4. The most substantial source of error in our analysis was likely the poor temperature control function utilized in the system used. To maintain relatively constant temperature it was necessary to oscillate between reservoir temperature control and column temperature control. Unfortunately this resulted in a variance in temperature with an average standard deviation of 0.3 degrees for each of the three temperature ranges measured.

In our analysis we were unable to gather sufficient historical data to confirm the Wilke-Hougen Correlation.

SECTION 4: CONCLUSIONS AND RECOMMENDATIONS

1. Provide conclusions to address the objectives of the experiment. 2. Provide conclusions concerning the accuracy of your results. 3. Provide conclusions concerning the sources of error. 4. You may include conclusions for other factors as appropriate. 5. Include recommendations to improve the experiment. 6. Include recommendations for future work. 6.1. Future work may focus on improving the quality of the results. 6.2. Future work may focus on extending the work to achieve new objectives.

SECTION 5: NOMENCLATURE 1. k rate constant 3. Activation Energy 2. A Arrhenius constant 5. T temperature (K)

4. R Gas constant(J/mol*K) 6. 0 - volumetric flow rate (mL/s)

7. - reactor volume(cm^3)

12. reaction rate of ethyl acetate (mol/kg*s) 11. W mass of the catalyst

9. , concentration of ethyl acetate in reactor effluent stream 10. molar flow rate of ethyl acetate (mol/s)

8. , concentration of ethyl acetate in reactor feed stream

SECTION 6: REFERENCES 1. Jones, M.J. Organic Chemistry W.W Norton & Co., 1997, pp.992, 1022-1023. 2. Kunin, R. Ion Exchange Resins 2nd ed. Wiley, New York, 1958, pp- 225-259 3. Anon: Dowex: Ion Exchange , Dow Chemical Co., Midland, MI, 1958, pp.5. 4. Fogler, H.S. Elements of Chemical Reaction Engineering, 4th ed, Pearson Education, Inc, 2006, pp. 91. 5. Introduction to SAS. UCLA: Academic Technology Services, Statistical Consulting Group from http://www.ats.ucla.edu/stat/sas/notes2/ (accessed November 24, 2007). 6.

Appendix A : Raw Experimental Data Table 1.0 Raw Sample Data

Appendix B: Sample Calculations

In Out + Generation = Accumulation =

, ,(+) + = = =

, 0 = , 0 ,

, 0 ln = , k = ln , 0 ,

= = =0

0 =

ln() = ln()

= 0

% = 100 / = ( ( )/)^
= =

[] = [ ] 1000