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FILE: KINETICS.DOC CHEG 239W CHEMICAL ENGINEERING LABORATORY Department of Chemical Engineering University of Connecticut Reaction Kinetics Saponification of Isopropyl Acetate with Sodium Hydroxide Objective: The purpose of this experiment is to examine and determine the reaction kinetics of a simple homogenous liquid-phase system and to model this reaction for either a tubular flow (column) reactor or for a stirred-tank reactor. Simple batch (flask) reactions will be run initially to determine initial rate data from concentration versus time profiles before using the continuous reactor. Equipment: Lauda RM 20 refrigeration water bath with both heating and cooling capabilities Lauda MT water bath for heating 250-mL Erlenmeyer flasks for initial reactions and titrations 1000-mL volumetric flasks 4-L plastic bottles for caustic solutions 1-gal glass bottles for acid solutions 50-mL burettes for titration with support clamps and stands Lead donuts for holding flasks Hampden H6250 Stirred-Tank Kinetics Reactor Hampden H6260 Tubular Kinetics Reactor (Column, or Plug Flow) 1% Phenolphthalein indicator in ethanol (colorless pH 8.2 - pH 10.2 red) Sodium hydroxide reagent pellets Hydrochloric acid reagent (in hood) Isopropyl acetate reagent Stopwatches Background Theory: For the reaction A + B C + D, where ester plus caustic gives the acid and alcohol, one expects second-order kinetics. The reaction (saponification, or its reverse, esterification) can be reversible or irreversible. For the irreversible case, the rate equation for a batch reactor may be written: r = -d[A]/dt = k[A][B] where k is the second order rate constant and [A] and [B] are the concentrations of the reactants in g-moles/L. If strictly equimolar concentrations of reactants are used, the rate equation can be simplified to a general nth-order reaction. r = kn [A]n where n 2.. With good

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experimental data, this model allows the determination of the reaction order for an irreversible reaction. More general cases are covered in the references. The effect of temperature on the rate constant can be compared with that predicted by the Arrhenius expression: k = Ae-E/RT where A is the frequency factor, E is the activation energy of the reaction, R is the gas constant, and T is the absolute temperature. Rate data at various temperatures can be used to determine the frequency factor and activation energy of the reaction. Note that the Arrhenius expression can be written in the form ln k = ln k0 E(1/T - 1/T0)/R, where T0 is an arbitrary temperature and k0 is the rate constant at T0 . For the reversible case, the simple design equation (material balance) for a batch reactor at a known temperature may be written: d[A]/dt = - k{[A][B] - [C][D]/Kc} . The corresponding equation for a tubular flow reactor is identical except that d[A]/d is equated to the right hand expression, where = V/V0 and V0 is the volumetric flow rate and V is the volume of the tube. The notation follows that employed by Fogler [2].

I.

Initial Kinetics Experiment:

For preliminary determination of the kinetic parameters, run batch reactions in flasks immersed in a thermostatted water bath. Check the temperatures with an accurate laboratory thermometer. It is good practice to cover as wide a temperature range as practical, given the equipment. Preparation of Reagents: N/10 NaOH: weigh 16.0 g of reagent pellets in a beaker, mix with distilled water in the hood and transfer into a 4-L plastic bottle, fill, and mix thoroughly. The exact volume isnt critical. See note below. N/10 HCl: dilute 36.0 mL of concentrated hydrochloric acid with distilled water in a gallon glass jug and mix thoroughly. This solution should be slightly stronger than the NaOH; that is, 10.0 mL of alkali should titrate with slightly less than 10.0 mL of HCl. For the highest accuracy, the solutions can be standardized (calibrated) as outlined in the Gas Absorption Experiment handout. N/10 Isopropyl Acetate: Weigh 10.2 g of the IPOAc liquid on the pan balance in a tared beaker and quantitatively transfer it to a 1000-mL volumetric flask. Fill half way with deionized water and mix until dissolved. It dissolves slowly. Finally dilute to the mark and mix well.

Initial Reaction Procedure: To determine the extent of reaction (conversion) with time, preheat for 10 min l00.0 mL of ester and alkali at the test temperature in separate stoppered 250-mL Erlenmeyer flasks with lead donuts for support during immersion. At zero-time mix
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together and stopper. At timed intervals, swirl the flask and transfer a 10.0-mL sample with a volumetric pipette, to an Erlenmeyer flask containing 5.0 mL of N/10 HCl. The HCl should be precooled in an ice bath. Rapidly titrate with N/10 NaOH to a pink end point with one drop of phenolphthalein indicator. As the ester breaks down with time during the reaction, more acetic acid is generated and is easily monitored by the increasing NaOH titer. Plot the reaction curve in your notebook as you do the experiment. If the reaction rate is too fast or slow, rerun with improved time intervals for sampling. Continue sampling until the reaction is substantially complete. One way of estimating the zero-time data point is by inverse addition of the reagents. Mix 5.0 mL HCl with 5.0 mL NaOH. Add 5.0 mL of ester solution, mix, cool, and titrate with NaOH. See Appendix A for a more sophisticated method of handling this aspect of the experiment.

Calculations: In principle at t = 0, only isopropyl acetate and sodium hydroxide are present. Adding a slight excess of HCl over the alkali gives: ester +NaCl + water + HCl excess. Back titration with NaOH gives the HCl excess, V1 . At times t > 0 the solution contains unreacted ester, NaOH, NaOAc, and isopropyl alcohol. The same quantity of HCL added as above will react with NaOH and NaOAc generating free acetic acid and leaving the same excess of HCl. Back titration with NaOH gives the two acids, V2. The amount of acetic acid liberated from the ester at any time is then proportional to V2 - V1 and the reaction progress is thereby followed directly. Determine the experimental order of reaction. Assuming second-order kinetics, use a numerical or graphical method to estimate the reaction rate constant. Repeat at various temperatures, and compare the observed effect of temperature on the rate constant with the predictions of the Arrhenius theory. Report the derived frequency factor and activation energy. Compare with data available in the literature.

Questions: 1. 2. 3. 4. 5.

Somewhere in your report you should address the following:

Why is it necessary to titrate cold samples? Why should titration end points be reached rapidly? What would you expect to be the effect of alcohol chain length on reaction rate? Is there any significant indication that the reaction is not second order? Does your data contradict the hypothesis that the reaction is irreversible?

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II.

Reactor Analysis and Design:

Using your understanding of the saponification reaction, design a set of experiments to examine the continuous reactor assigned. Make up only the amounts of solutions you will need for the day. Use water for preliminary study of the pumping speeds, heating, etc. Refer to the sheet in the Appendix on using the LFE Controller. Consider the following guidelines: The rate constant and the equilibrium constant (if the latter affects the reaction) should be experimentally determined beforehand as a function of temperature and compared to any available values from the literature and/or calculations based on the chemical structure of the ester. Use this kinetic information to design the runs for the continuous reactor, e.g., one set of conditions must result in conversion of the limiting component to at least 80%. Within the temperature chosen for this conversion, you also must be able to vary the flow rates over a sufficient range to check thoroughly your model for the reactor. Conditions (especially temperature) should be standardized, monitored and controlled so that accurate and precise process data are determined. As suggested above, the group results should be compared with a mathematical model of the continuous reactor to demonstrate that you have successfully modeled the reactor and the reaction system. Possible approaches are to: (1) predict the performance of the continuous reactor from the batch data alone, and then compare the observed performance against this prediction; or (2) derive kinetic information from the continuousreactor data alone, and compare these results (e.g., order, rate constants, frequency factor and activation energy) against those found for the batch reactions. You may also wish to use literature rate constants, providing appropriate citations. Using the continuous reactor, ambitious groups can try to model and experimentally verify startup conditions, reagent imbalance, temperature changes, etc. as an alternative to or in addition to the standard steady-state conditions.

II-A. Stirred Tank Reactor H6250 The stirred tank reactor can be run as a constant-volume CFSTR where the reaction mixture flows continuously out the side arm, or in a transient mode with a variable volume as one or both reagents are continuously added. (The case of two reagents rapidly added and the flow then stopped is a simple batch reaction similar to the flask reactions, and not of any interest.) Determine the volume of the reactor, and use your batch kinetic data to find the flows needed to give appropriate conversions. Make runs at different temperatures, and determine the kinetic constants from the reaction data. Develop models for all the types of reactions run. Solve these models and compare to the actual data. Consider runs that simulate real-world types of operations and think in terms of very large equipment where filling delays and general operation problems, such as stirring, are more significant. For example, suppose the reactor was full of water before the reagent streams were started; could this be simulated?

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II-B. Tubular Reactor H6260 The available tubular reactor, also known as a plug-flow or column reactor, can be sampled only at the outlet of the reactor. The reactants pass through the entire fixed length and exit out the top. For given conditions of temperature and concentration, the flow can be varied to change the percent conversion at the exit stream. A plot of conversion versus flow rate will give a maximum at low flows and a downward sloping curve at higher flows. To study the performance of the reactor, one must push well into both regimes. Consider carefully for this reactor the nature of the fluid flow in the tube. Transient data can also be obtained for the tubular reactor, e.g., after a sharp change in flow rate.

General questions: 1. How would CFSTR data be treated to determine kinetic parameters? 2. Derive a design equation for this reaction in a plug-flow reactor using two streams (reactants A and B) of equal molar feed rate. Express your answer in terms of (a) volume, (b) flow rate, (c) initial concentration, and (d) the reaction rate constant. 3. What assumptions are necessary to solve the model equations analytically? 4. Discuss the principal differences between the plug-flow and back-mix (CFSTR) reactors. What might happen if the stirrer were stopped in the CFSTR? 5. How often should data points be taken during an experiment? Should you take more data points at the beginning or the end of the experiment? 6. When is steady state established in the CFSTR and the Tubular Reactor? 7. How is the equilibrium constant of a reaction related to temperature? 8. Compare the kinetic parameters determined from the flask reactions with those determined from the continuous reactor. Can you explain any differences? 9. Which reactor is easiest to run? To model? 10. On a volume basis, which continuous reactor is more efficient for the reaction studied? What are the practical advantages and shortcomings of each? References: 1. C. H. Bamford and C. F. H. Tipper, eds., Comprehensive Chemical Kinetics, vol. 10, "Ester Formation and Hydrolysis," Elsevier, New York, NY, 1972 2. Fogler, H. S., Elements of Chemical Reaction Engineering, Prentice-Hall, Inc., Englewood Cliffs, NJ, 2nd Edition , 1992 3. International Critical Tables, 7,129 (1930) 4. Levenspiel, O., Chemical Reaction Engineering, Wiley, New York, NY, 1967 5. Moore, W. J., Physical Chemistry, Prentice-Hall, Englewood Cliffs, NJ, 1964 6. Smith, J. M., Chemical Engineering Kinetics, McGraw-Hill, New York, NY, 1970

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