Rate Constant Determination for Saponification in Batch & CSTR

February 17, 2005

Presentation by Trevor Binney

Group Members

Jay Berndt
Operations Manager

Me

Eric Houchin
Safety Coordinator

Team Leader

Presentation Plan
Familiarize audience with saponification Discuss the project objectives Overview of process and equipment used Batch and CSTR kinetic data results Difficulties encountered during lab work Give recommendations for future work Answer any questions the audience have

Nomenclature
CSTREtAcNaAcEtOHPPESolnXaConcCaContinuous Stirred Tank Reactor Ethyl Acetate Sodium Acetate Ethyl Alcohol (Ethanol) Personal Protective Equipment Solution Extent of Reaction of NaOH Concentration in mol/L mol/L NaOH

What is Saponification, and what is it used for?

http://www.dictionary.com/ defines saponification as: A reaction in which an ester is heated with an alkali, such as sodium hydroxide, producing a free alcohol and an acid salt, especially alkaline hydrolysis of a fat or oil to make soap.

EtAc

NaOH

NaAc

EtOH

CH3COOC2H5 + NaOH CH3COONa + C2H5OH

Saponification is primarily used for the production of soaps.

Project Objectives
Our team was asked to meet several goals while running saponification experiments
1. Develop conductivity calibration curves for the reactants used in the process. (NaOH & EtAc) 2. Verify feed concentration through standardization using titration 3. Determine the true rate constant for reaction in a batch reactor 4. Obtain reaction rate data for the CSTR as a function of the solution residence time

Safety Considerations
NaOH- Corrosive EtOH & EtAc- Flammable EtAc will corrode various plastics Standard PPE worn, as well as face shield and rubber gloves for handling dangerous chemicals. Clean up spills and broken glass immediately Be aware of where other people in the lab are Open windows for ventilation and work under the fume hood when mixing solutions

Assumptions
Conductivities EtAc & EtOH negligible Solution inside the CSTR is well mixed Solution inside batch reactor well mixed Ethyl acetate bottle wasnt contaminated Liquid pulled from the 1 M EtAc is 1 M The CTSR flow meters were accurate Conductivity linearly proportional to Conc

Conductivity Probe Calibration

Conductivity Probe Calibration

NaOH Conductivity vs Concentration
60

50

y = 214.03x

Conductivity (mho)

40

30

Literature Data Calibration Linear (Literature Data)

0 0.05 0.1 0.15 0.2 0.25 0.3

20

10

Molarity NaOH

Xa & Conc Solved w/ Conductivity

NaOH conductivity: 214*(conc NaOH) mS/m NaAc conductivity: 78*(conc NaAc) mS/m EtAc & EtOH conductivity: negligible Overall conductivity: Ca0*(214-136*Xa) Where Xa = (Ca0 Ca) / Ca0

Continuous Stirred Tank Reactor

CSTR procedure
1. 2. 3. 4. 5. 6. 7. 8. Enter setpoint temperatures using set point 2 Drain reactant tanks as much as possible Prepare three liters of reactant solutions Fill tanks equally and heat to set temp Make sure the bottom reactor drain is closed Turn on the CSTR stirring device Open the flow valves to equal levels Wait until SS reached and record conductivity using a calibrated conductivity probe

Batch Reactor and Heating Bath

Batch Procedure
1. Preheat bath to desired reaction temp 2. Prepare the NaOH and ethyl acetate solutions 3. Fill two erlenmeyer flasks, one with NaOH and the other with EtAc 4. Allow reactants to heat to desired temp 5. Pour one flask into the other submerged flask 6. Using the conductivity probe, record conductivities of the solution every 15 seconds 7. Record data until the conductivity stabilizes

Equations Used for Data Analysis

Arrhenius law: k = k0e-E/RT
ln(k2/k1)=E/R*(1/T1 1/T2)

Ca0*(214-136*Xa) Xa = (Ca0 Ca)/Ca0 Ca = (Cond/Ca0 214)*Ca0/136 + Ca0

Results and Conclusions

Results and Conclusions

Results and Conclusions

(k) Determined rate constant for saponification Experimental k = 0.178 L/mol*sec @ 30 C Experimental k = 0.192 L/mol*sec @ 45 C

As listed in in the Bulletin of the Chemical Society of Japan k = 0.112 L/mol*sec

According to this source, the rate constant we determined was about 59% too large A possible reason for this is that the EtAc solution concentration was higher than predicted

CSTR Results and Conclusions

Data recorded was very inconsistent
For equal feed concentrations, we had runs that yielded conductivities of 6-7 mS and also 3 mS/m, with no results falling in between
Reagent bottle contamination? Inability to completely drain feed tanks Difficulty in maintaining stirring speed

CSTR operations were abandoned for the final lab period to focus on Batch data

Temperature Dependence Results

Multiple trials were run at both 30 & 45 C Arrhenius law: k = k0e-E/RT Rewritten: ln(k2/k1)=E/R*(1/T1 1/T2) R = 8.314 J/mol*K E = Activation energy of this reaction
We were unable to find the value for E in literature

k30 = 0.178 L/mol*sec < k45 =0.192 L/mol*sec Experimental E = 4040 J/mol

Overall Conclusions
Saponification rxn is a 2nd order reversible reaction (1/Ca vs time linear at low time)

-Ra = k*Ca*Cb Considerable error comparing experimental rate constant to that in literature Batch data fairly reproducible and precise CSTR data and operation inconsistent

Difficulties Encountered During Lab

Creation and mixing of ethyl acetate solns
Attempted creation of 1 M stock solution
Attempted to dissolve 9.6 g EtAc/100 mL Max Solubility of EtAc in water is 8 g/100 mL

Possible reagent bottle contamination

Evident through formation of unknown precipitate

CSTR temperature reading inconsistency Inability to completely drain CSTR tanks

Recommendations For Future Work

Do research before entering the lab Become familiar with analytical equipment Begin trials with CSTR as early as possible Split up tasks for each person to do during lab prior to running the labs Make an in depth Design of Experiment before entering the lab

References
Levenspiel, Octave. Chemical Reaction Engineering, Third Edition. USA: John Wiley & Sons, 1999. Levenspiel, Octave. The Chemical Reactor Omnibook. Corvallis, OR: OSU Book Stores, 2002. Pecaj, Arta. Personal Interview. February 16, 2005. Tsujikawa, H. and Inoue, H. 1965. The Rate of the Alkaline Hydrolysis of Ethyl Acetate. Bulletin of the Chemical Society of Japan. 39: 1837-1839 http://www.woodlandsinstruments.com/conductivity_ values.htm

Questions ??