September, 1966] Reaction Rate of the Alling Hydrotys of Ethyl Acetate 1ea7 DULLETN OF THE CHRCAL socMETY OF JAPAN VOL, 3918371842 (1966) The Reaction Rate of the Alkaline Hydrolysis of Ethyl Acetate By Hiroo Tsunkawa and Hakuai INovr Department of Chemical Enginrng, The University of Tokyo, Hone, Tobye (Received November 11, 1965) ‘The reaction rate of the alkaline hydrolysis of ethyl acetate was studied by means of con- tinuous mearurement of the electric conductivity change. The second-order rate constant de- creased as the reaction proceeded. The decrease was evident when the initial concentrations fof the cter and the base were close together. The intial rate constant at 25°C: was measured 4: 0.1120 L/mal sc. and the activation energy wat 11,56 kcal/mol, values agreed well with thore of previous studies. From the standpoint of the electronic thoory of organic chemistry, ‘Day and Ingold proposed a sequential reaction mechanism passing through an addition complex. ‘The resulu of the approximate calculations to the preudo-fist-order reaction and the analog computation ofthe exact models coincided with the experimental renlts, The diference in the ‘ctivaton energies of the forward and revere reaction ratea was calculated fom the experi= ‘mental data. At lower temperatures ths reverse reaction race was small, and the overall reac- tion rate was approximated as 2 pure second-order reaction. Other probable reasons for the rate constant decrease were also discusted, ‘The reaction rate of the alkaline hydrolysis of ethyl acetate has been well exablihed to be a fecondvorder reaction, and the mechaniam has ‘been disused in_ detail? For the study of the performance of a flow-type stirred tank reactor, we carried out the hydrolysis reaction in it and analyzed the flow pattem in the reactor from the yield of the reaction. “How fever, during the experiments, we found that the hydrolyis reaction could not satisfactorily be exprened at a second-order reaction. It was fecewary to analyze.the rection rate more carful- Jy. Therefore, we measured and. analyzed. the te ofthe hydrolysis of ecb acetate continuously We will discus the mechanaim of the reaction kiaetiealy Expertmensal Apparncas—The reaction was catied out ina Datcheyge reactor, and the electric conductivity of the reacting volosion was meanued withthe tne. "The i ‘sia. apparatus is shown in Fig. 1.A2-1, polyebylene rater was uid ar the reaction vowel natend of » last > tn fe, became inthe ine ofa gla veel some alkaline Laat LI oan {ont dincived from the wall and so disturbed the exact. ‘Peasurement of the reaction rate ‘Daring the reaction hyaronide ions are consumed atm sod acetate fons ate produced. This change in on Wie ‘Hreenration rel ims condactivity change fe the ‘olution, and by the meanurement of this conductivity leet fre could sucertain he degree of sponifcation. wai fs “The electrode sed is shown in Fig. 2; it et horizon tally near the turbine x0 thet the reactant flows hoe Fig. 2. The electrode oughly in ie The cecal ceuls of the measuring System in shown in Fig. 3 AOSV. ac. current of 1000cje added atthe electrode + a S-ohm restr eas in series. The voltage Between the two sides of the 1M. L Bender, Chem. Rt, 60, 53 (1960), ‘itor sampled, converted into dey and recoded1698 ‘on a recording animeter. Generally, the inpat-outpat Character of a diode are mot linea, 40 the elation between the output curent and the OH~/CH,COO- ado must be caliesed.® "However, the. negative feeding back of the converted dies curent 10 he termediate pact af te amplifer (he 15 Eloohm resistor ed 10 mierofared condenser circuit of Bg. 8) forme 2 linear Felton betwen the current and the cane entation rato, ae ahown ia Fig. 4 By comparing the line in Fig. with the conductivity ofthe renetog ‘elution, ix which the val concentration af OH and {GH,COO™ was about 0.02 we can ealeulnte the degree of hyofys sith the he BS smn gm vn Fig. 3. ‘The eecric iret for the electoeanduc- i Fig. 4. The relaionthips berween the ammeter Tending and the reaction proceding Q Total concentration of Na =0.0200 moll © The ammeter was set 100 amp for 100% NOH Procedure —A sodium hydrovide solution was prepared by dinolvng sodium hycroxide (made by de ‘Wako Pure Chemicals Coy Lidy G. Re grade) i foe xchange water with relave renance of more thas 2100 ohmeom. "The concentration wat checked. by an automatic tater wing 0. w standard hydrochloric acid solution. Ethyl acetate (made by the Osaka Organic Chemicals Co, Led, G. Re grade) was wed Without any special procexingsftyt gave a mean equ rium converion of 975 which agrees with the theo reveal equilibrom convertion ‘To start the faction, 904 ml. of a 002. sadism Inyo solution was pourel into a beaker dipped in a hater bath and then vigrouly steve for more than S0'min, after which a definite volume of ethyl state ‘at adsed tothe solution under the suring. "ie tee. 3 D,,G. Flom and PJ. King, An Chm, 25, S541 (1953). ¥ = Hirgo Touyreawa and Hakuai Inoce [Wal 39, No. 9 perature of the mixture was kept constant during the Feaction witha 4 range of £01°C. Ethyl acetate diwolved into water within 10se¢ 10 the mixing te of te rer was negligible in comparaon with the reacting time. During the reaction the com: Soatviy of the olution was recorded. continaouly, and the degree of conversion wat caculted. A onal Portion of the soludom was sempled during the reac on and: was acidied to nop te reaction rapidly: by the backtitration of the aciy the remining hydroxide fon in the reacting ‘ym were determine’. The ‘concentition of hydrorde tnt at determined by thie tration greed well with at calculated fom the ‘conductivity measurement of the soluden. Rewules Some senull are shown in Fig. 5, where the concentration change is plotted as. (ep—s)/ Gay~#) against the reaction time. The circled joins io Fig. 5 stand for the experimental vals, While the straight line in the ‘gure shows the ‘theoretical relation derived from the second order rate equation. Time, se. Semblogathaie plot of experimental Expl. No. R27 xg 0.00897 Temp M07 ay O.021040 Aout, 0.857 mol ee e-the reaction i expreaed as that of a complete second-order reaction, all the experimental values ‘ust be on the line. However the points obtained from the experiments deviate downwards from the Unear relation. ‘The deviation of the rate from the second-order rate equation becomes more remarkable as the inital concentrations of ‘base and eater draw closer to each other. Previous works on this kinetice did not analyze the rate io detail; usually only the mean initial rate constant has been obiained. The deviation fom the second-order rate equation has never been analyzed in detail kinetically. Indeed, no auch deviation han even been actually observed in the initial rate of the bydralys,September, 1966) We meauured the inti rate constant by the ‘Addition of different amounts of the ester, and ‘observed the rate constant independent of the ‘concentration ofthe eter. These resulta coincided with howe of peevious works on the second-order rate equation, They are shown in Fig. 6, along with the inverse of the absolute temperature, UT. ‘The calculated activation energy of 11.56 Iealjmol. agrees well with thove obtained in previoun works; the rate constant at 25°C, 0.1125 Tinaee, also agrees with them?-© oe HTK Fig. 6. The Acrhenius plots of the inital rate © about 0.02 mob ex about 8,05 mol. A cht about 0:10meb. St shout 0.28 mal = Sekeat mot Analysis and Dincoasion “The mechanitnn of the base hydrolysis of exter thas been diseased hitherto, and it is well known that the mechanism may be expresed by the following reaction scheme: 3), Uae and H, Kawakami, Kepy-Keata Za 48, 331 (st "Man, Glen Aber, 8, 2890 4 (196). Tapeh aera a iat ins ON = Rs smide and W'S Levtmon, J. m. Glm sot) hy hi (89) ‘Reaction Rate of the Alkaline Hydrolysis of Ethyl Acetate 099 ‘This mechanism of the basic hydrolyse of eaters was proposed by Day and Ingold. and since analyzed: by Bender,” Swart, and many other nventigators.> However, these studies were ‘mainly ftom the viewpoint of organic chemistry; no detailed kinetic analysis of the hydrolysis of cthyl acetate has ever been made. Unally the reaction har been considered to. be a second- frder form, but, according to the above mvecha- biam, the necond-order rate equation is applicable fnly when the concentration of the addition ‘comple © is very small_and when the reverse reaction rate is negligible in comparison with the forward reaction rate ‘in general, the total reaction path may be cexpresed by the folowing mathematical equations: ey 7 heaen + bso o extn — (ha thsleo + heen @ ® “ where € micans the concentrations of chemical ‘compounds of fons, and where the sufies A, B, C, denote the compounds or ions shown above. ‘The Fe indicates the reaction rate constants; ky and k; are the rate constants for the forward and reverse reactions of ABC, fy and Ky are the fate constants of the forward and reverse reac: tions of C2D+E, and ky is that of the D+E—> FG reaction.” The reaction ratea were assumed to be proportional to the concentrations of all the reacting compounds, 8 denotes the time. “The deviation Irom the second-order rate form Which we observed seems to give the key to the analysis of the mechanism of the reaction. As the reaction proceeds, the concentration of the cater and hydroxide fons become very small; the ‘effect of the reverse reaction rate of the addition ‘complex on the total rate will therefore become remarkable ‘OF course, there are many possible causes of ‘the deviation of the rate from the second-order form. ‘The CH,COOGH, +-H,O;*CH,COOH | ‘HLH equilibrium muggest the reverse reaction ‘of the products, However, the deviation of the rate could ot be duc to this effect forthe follow ing reatons. According to the effet of thie reverse reaction, the overall reaction rate would be re- tarded by the addition of the reaction product. ‘We meacured the reaction rate in the presence of Daf Beh Qgy amt © tgs, Ten, Fert et (aah Am. hen, So, 73,1628 (1981). "Mc Bender, 3} PSone Bale cham Bales, 98,418 (1026)