CNOA £J061199800441 Journal of the Chinese Institute of Engineers, Vol. 21, No. 4, pp. 441-447 (1998) 441 ELECTROLYSIS OF ACETONE IN A DIVIDED CELL Ming-Liao Tsai Department of Chemical Engineering National Chin-¥i Institute of Technology Taichung, Taiwan 411, R.0.C. ‘Tse-Chuan Chou* Department of Chemical Engineering National Cheng Kung University Tainan Taiwan 701, R.O.C. Key Words: aldol condensation, anolyte, catholyte ABSTRACT ‘The mechanism and kinetics of aldol condensation of acetone to produce diacetone alcohol (daa) by paired electrolysis are studied. The results indicate that the reaction orders in both anolyte and catholyte are first order with respect to acetone. The activation energies of aldol condensation of acetone in catholyte and anolyte are 45.3 and 90.0 kJ- mole™', respectively, In the temperature range from 298 to 304 K, the pH values in both anolyte and catholyte are 3 and 12, respectively. For 60 coulombs of electricity passed the rate of daa formation in the catholyte is faster than that in the anolyte I. INTRODUCTION To produce useful and special chemicals is an interesting and important technique. Aldol conden- sation is one type of organic synthesis technique. Aldol condensation is postulated to produce special chemicals using a chemical reaction method which, in general, generates a lot of pollutants as well as a catalyst which cannot not be regenerated. Catalysts or redox reagents can be regenerated by electrolysis [1-7]. Few or no pollutants are produced by elec- trolysis. Paired electrolysis for synthesis of special chemicals was reported in our previous paper [12] Traditionally, only one working electrode in an electrolysis system is used. However, two working electrodes are used simultaneously in a paired elec- trolysis system. Theoretically, yield as well as cur- rent efficiency by paired electrolysis is higher than that of a single working electrode. Power con- sumption is significantly decreased by using paired *Correspondence addressee electrolysis, Furthermore, in some cases, high selectivity of product is obtained by paired electroly- sis. Organic electrochemistry, using single or paired electrolysis, is a very popular method to synthesize organic compounds. Unfortunately, there are few or no papers concerned with aldol condensation by paired electrolysis. It is well known that aldol con- densation of acetone is catalyzed by both a proton, H°, and a OH” anion (8-13]. Based on the reaction mechanism of both anodic and cathodic aldol con- densation, the H” and OH" can be simultaneously gen- erated in situ by paired electrolysis in an aqueous solution. Then acetone is catalyzed by the generated H* and OH" species produced at the anode and cathode, respectively. The intermediates of carbocation and carboanion simultaneously appeared in the electrolyte. Diacetone alcohol was obtained when the intermediate reacted with the reactant again4a Journal of the Chinese Institute of Engineers, Vol. 21, No. 4 (1998) + g 1 Wo oe Fig. 1. Electrosynthesis set up. 1 Potentiostate/Galvonostate , 2 Pair Stirrer Thermostate, 3 Divided Cell, 4 Cooler $ Am- pere meter, 6 Voltmeter, ‘The factors affecting the aldol condensa- tion by paired electrolysis were described in a previous report [12]. However, the kinetics of paired electrolysis was not mentioned. In this study, the kinetics of aldol condensation of ace- tone to produce diacetone alcohol by paired elec- trolysis in a divided cell was systematically stu- died. II, EXPERIMENTAL The paired electrosynthesis of diacetone alcohol was performed in a divided cell using platinum plates as both anode and cathode. The platinum electrode (8 cm’) was pretreated by dipping in the | M base, after which the electrode was dipped in aqueous acid and then washed with distillated water. This procedure was repeated many times. The anolyte and catholyte were divided by a porous glass, as shown in Figs. 1 and 2. The electrolytes were prepared by mixing desired amounts of sodium chloride and acetone in a fixed volume of distillated water. The total volume of the solution was 120 ml. At the beginning of a run, the temperature of the cell was controlled at a desired value by a water bath. When the system reached a steady state, a given current was supplied from the power supply (Amel-550). During a run, both catholyte and anolyte were sampled periodically and analyzed by a gas chromatograph (Shimadzu GC- 9A) «| - an’__| Fig. 2. Divided cel, Paired ster thermostat, 2. Reactor 3 magnetic stirrer, 4. Sampling trap, 5. Reflux condense, 6. Electrode, 7. Thermometer, 8. Porous pyrex glass III. RESULTS AND DISCUSSION 1. Reaction mechanism and rate equation The acetone was the raw material for aldol con- densation to produce diacetone alcohol in both the catholyte and anolyte by paired electrolysis. Based on the paired electrolysis of water and the aldol con- densation of ketone, the mechanism of aldol conden- sation of acetone is proposed as follows: Cathode: 24,0+2¢°<¢>20H- +H a) Avoireoareino 2 Age °) B'sHa0-¢> BLO @ where A is acetone, A’ is acetone carboanion, Bis, diacetone alcohol carboanion and B is diacetone al- cohol. ks Anode: HaOqe>2H+1/20;+2e~ ©) Wag a"st0 © & Ava eee" o b BHO BH 8)M.L. Tsai & T.C, Chou: Electrolysis of Acetone in a Divided Coll 443 where A” is acetone carbocation, and B” is diacetone alcohol carbocation. Accordingly, the mechanism of aldol condensation of acetone in both cathodic and anodic reactions is shown in Eqs. (1) to (8). The for- mation rate of product, daa, in the catholyte is Ryaka(B?)-k.4(B)(OH). 0) The formation rate of A’ and B’ are Ry. and Ry, re spectively, Ryak{AYOH)-k(A’)-Ks(A WA) (B) (10) Ryaks(A(A)-Ks(B)-ke(B +k «(B(OH (11) Ata pseudo-steady state, Ry=0 «2 Ry=0 a3) Substituting Eq. (12) into Eq. (10), K{AOH) + k_(B") A) TE (4) ‘Combining of Eqs. (11), (13) and (14), OR 7 (6) hak MNOH IK (BOM IK24kA)) (5) 3k kk (AN) Substituting Eq. (15) into Eq, (9), the formation rate of daa, Rp, is kak ske(A)*(OH™) (B(OH YIk_>+k(A)] 7 tk Mlk atk A] Re (16) During the initial state of a run, the conversion of reactant A is very small; (B)=0 or (A)'>>(B). Since at the initial state, (B)=0, the term k.sk-«(B)(OH") (k.a+k3(A)] is very small. Furthermore, the forma- tion rate Ry>0, according to Eq. (16); therefore we can assume kakskq(A)(OH™)>>k-3k-4(B)(OH”) [k.o+k(A)], and Eq. (16) can be simplified, kaksk(A)*(OH) Kt kolkata Based on the reaction steps (2) and (3), if Ry is sig- nificant then k;>>k_, and at a at high concentration of acetone, kx(A)>>k-2, Ry=K(AOH") as) where k=kaka/(ks+ky). 14 Cathode 7 10} x3 3 4 4 ___,_ Anode 2 oh a ato ato Electricity , Coul Fig. 3. Plot of pH vs. time in a divided cell by paired electrolysis, Electrolyte:2M NaCI Temperature:25°C Acetone:? M Electrode:Pt Current density:25 mA-em™* After a fixed amount of electricity passed, (OH) is constant, then Re=k (A) as) where k” is KOH), Similarly, a rate equation can be obtained in an anolyte R (ay (20) where k’”=k(H"). 2, Effect of amount of electricity passed on pH. Figure 3 shows pH value vs. amount of electric- ity passed. The pH values in both catholyte and anolyte changed from 7 to 12 and 7 to 3, respectively, during the time that approximately 60 coulombs of electricity passed. Ata fixed applied potential, the electrochemical reactions are not rate determining steps as shown in Eqs. (1) and (5), So it does not af- fect the rate expressions such as Eqs. (19) and (20). Otherwise, the catalysts OH" and H* disappeared to react with acetone as shown in Eqs. (2) and (6), re- spectively, and reproduced as shown in Eqs. (4) and (8), respectively. So the pH value both in the anolyte and catholyte were constant during the passage of about 60 coulombs of electricity 3. Effect of current density on yield ‘The results show that the yield of daa is 780444 Journal of the Chinese Institute of Engineers, Vol. 21, No. 4 (1998) 1000) 4 node 3 A 900 BE 2 = + 8M ¢ 800 3” 7 ——___. 3 / i 3S 8 “4 ™M * 700 § 3 26 : 3 # 3 £ y . 4M * 600 3 a & = 2M 500] 1520 25 30 400, 20~30~«40~*~«S oo 2 Reaction Time, hr Current density , mA-cnr? Fig. 4. Effect of current density on the yield of paired electroly- sis. Cathode:Pt Anode:Pt_Electrolyte:2M NaCl Elec- ticity:120 cout Acetone:8M Temperature:25°C Fig. 6. Typical concentration profile of diacetone alcohol in anolyte. Cathode:Pt Anade:Pt. Electricity:120 coul Electeolyte:2M NaCl Current density:25 mA-cm™ ‘Temperature:25°C 35 Cathode Cathode 30 78M : Slope:0.99 ¥ 25 lope:0. = § 2 S 2 15 & Eo a Le bv 2 ys OOS 1.0 15 20S 800510 1520 25 30 eee ; Fig. 7. Effect of concentration of acetone on reaction rate in Reaction Time , hr catholyte. Cathode:Pt Anode:Pt_Electrvty:120 coul Fig. 5. Typical concentration profile of diacetone alcohol in catholyte Cathode:Pt_Anode:Pt Electricity:120 cout Electrolyte:2M NaCl Current density:25 mA-em? Temperature:25°C g-F" and is independent of the current density as shown in Fig. 4, The results also describe that the electrochemical reaction is not a rate determining step. 4. Effect of concentration of acetone on react rate Electrolyte:2M NaCl Current density:25 mA-cm™? Temperature:25°C The formation rates of daa in both catholyte and anolyte increased from 3.5 to 17 M-hr"' and 2 to 7.5 M-hr", respectively, by increasing the concentration of acetone from 2 to 8 M as shown in Figs. 5 and 6. The experimental results of the reaction order with respect to acetone in both anolyte and catholyte are 0.99 and 1.1, respectively, ie both of them are first order as shown in Figs. 7 and 8.ML. Tsai & T.C. Chou: Electrolysis of Acetone in a Divided Cell 445; 4,9} Anode 52 Anode 34 4. 7 5 Ea=90 kJ-mole! me Slope:1.1 ; a 7 B58 = 3 4 55 6.0 62 6.0) 64 65 os 10 15 20 25 LnCa Fig. 8. Effect of concentration of acetone on reaction rate in anolyte. Cathode:Pt_Anode:Pt Electricity:120 coul Electrolyte:2M NaCl Current density:25 mA-cm™? ‘Temperature:25°C Cathode Ea= 45.3 kJ-mole+ AS 46 47 3.28 330 332 334 336 338 VT, K-1#103 Fig. 9, The Arthenius plot of daa in catholyte. Cathode:Pt Anode:Pt Current density:25mA-cm™ Acetone:2M Electeolyte:2M NaCl 5, Effect of temperature on reaction rate Figures 9 and 10 show that the activation ener- gies of aldol condensation of acetone in both the catholyte and anolyte by paired electrolysis are 45.3 and 90.0 kJ-mole"', respectively. Accordingly, the sensitivity of the activation energy with temperature in the catholyte was less than that in the anolyte. The 328 330 332 334 336 338 VT , K-1#103 Fig. 10. The Archenius plot of daa in anolyte. Cathode:Pt Anode: Pt Current density:28 mA-cm? Acetone:2M Electrolyte:2M. Nac results indicated that the reaction rate by paired clec- trolysis in the catholyte was faster than that in the anolyte during the time the electricity passed above 60 coulombs. ‘The pH values both in the anolyte and catholyte were 3 and 12, respectively, and the reac- tion rate in the catholyte was faster than that in the anolyte at the temperature range from 298 to 304 K. In this case, the frequency factors which were ob- tained from intercepts of the lines as shown in Figs. 9 and 10 in the anolyte and catholyte are 1.06x10"* and 8.50x10" hr!-M"', respectively. ‘The Arrhenius Equations for the anolyte and catholyte are, ‘Anolyte:k=1.06x10"*exp[-90000/R7] ey Catholyte:k=8.50x10"exp[-45300/RT] (22) ‘Substituting Eq. (21) and (22) into Eq. (20) and (19), respectively, the rate equation of anolyte and catholyte are obtained, Anolyte:Ry=1.06x10"exp[-9000/RTI(H*)(A) (23) Catholyte:Rp=8.50X10"exp[-45300/RT(OH"(A) (24) 6. Energy consumption of paired electrolysis ‘The energy consumption could be decreased by446 Table 1, Energy consumption of paired electro! sis Energy consumption, kw-hr/mole daa Time, hr Cathode Anode Paired 1 0.072 0.220 0.054 2 0.057 0.119 0.039 3 0.048 0.093 0.032 4 0.043 0.065 0.026 5 0.041 0.057 0.024 applying an interrupt electrolysis. The energy con- sumption by using a single anode as the working elec- trode was higher than that of using a single cathode as the working electrode. However, the energy con- sumption of paired electrolysis was the smallest and was in the range from 0.054 to 0.024 kWH-mole~ daa in this system. Increasing the reaction time from 1 to 4 hrs causes a decrease in power consump- tion from 0.054 to 0.026 kWH-mole"' daa. Further extending the reaction time to 5 hrs, causes the power consumption to reache a minimum, 0.024 KWH-mole™! daa as shown in Table | IV. CONCLUSIONS Aldol condensation of acetone by paired elec- trolysis in a divided cell was obtained. The reaction orders of acetone in both catholyte and anolyte are first order. ‘The activation energies in both catholyte and anolyte were 45.3 and 90.0 kJ-mole", respec- tively. The experimental results correlated with the theoretical analysis ones well, ic Anolyte: Rg=106x10"exp[-90000/RT1(H")(A) Catholyte: Ry=8.50x107expl—45300/RT](OH")(A) At the temperature range from 298 to 304 K the pH values in both anolyte and catholyte were 3 and 12, respectively. For the passage of 60 coulombs elec- tricity, the reaction rate in the catholyte was faster than that in the anolyte. ACKNOWLEDGEMENT The support of National Science Council of the Republic of China (NSC83-0416-1600-016) and Na- tional Cheng Kung University is acknowledged. NOMENCLATURE A_ acetone Ay acetone carboanion B* diacetone alcohol carboanion B diacetone alcohol Journal of the Chinese Institute of Engineers, Vol. 21, No. 4 (1998) acetone carbocation diacetone alcohol carbocation forward reaction rate constant defined in Eq. (1) backward reaction rate constant defined in Eq, (1) forward reaction rate constant defined in Eq. (2) backward reaction rate constant defined in Eq. 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Manuscript Received: Sep. 24, 1997 Revision Received: Feb. 23, 1998 ‘and Accepted: Apr. 07, 1998 Pasta > MZ ERR BR ins TREE AR)II SER AAEL RARE RAASRAS ENCARTA RR RREAGW BEREAN ABE EEE SARE S RIE ° Wc 298 F 304K » EEN pH (AS 123 » AB AA 60 ‘ay + REARS PS PORES Ae AE HE Ae PNR + RL SE POT IL RES 5H)85 45.3 90.0 kJ-mole"* « GRE : ERR » MBAESEPS - SBE PY»