iene Rudolf Holze WILEY-VCH Experimental Electrochemistry A Laboratory TextbookExperiment 3.7: Kinetics of Ester Saponifcation Experiment 3.7: Kinetics of Ester Saponification Task The rate of reaction, the activation energy, and the preexponential factor in the Arrhenius equation of a chemical reaction are determined by conductance mea- surements. Fundamentals ‘The experimental determination of the rate constant k of the alkaline ester sapo- nification of ethyl acetate and its dependence on temperature starts with the re- action equation sCOsCaHIg¢K' +O ECH,COs+K! +ELSOH 5.24) In this experiment we start with an equimolar mixture of ethyl acetate and po- tassium hydroxide, During the reaction hydroxyl ions are consumed and acetate ions are generated, whereas the concentration of potassitim ions stays constant Because the former ions have significantly different equivalent conductivities, progress of the reaction can be monitored by conductance measurements of the reaction mixture. From measurements of x'=K(t) the rate constant of the reac- tion & can be calculated. Evaluation of data is based on Eq. 3.42 (see below) and a plot of 1/{&y-K(t)) against 1/1. The slope of the graph yields k. Determination of k at different tem- peratures enables an Arthenius plot to be drawn, and this in tum provides the energy of activation and the preexponential factor of the Arhenius equation ‘The specific conductance «=x{!) at a time tis given with a value of xq at t=O by i=» ~ contribution of consumed ionic concentration + contribution of generated ionic concentration (3.25) The contribution of ions to the specific conductance is given by Aggy =) +A =K (2-0) (3.26) with z=1, cin mol-em * and dow ou (3.27) and Bac “tre (3.28) The concentration of hydroxyl ions consumed up to time 1 is (according to the reaction equation, equal to the concentration of generated acetate ions. It can be given by om oy-€ (3.29) With starting concentration cy and concentration ¢ in mol-I! at time 4. Eq, 3.26-3.29 can thus be rewritten, 5960] 3 Electrochemistry with Flowing Current W=Wo~AC: ont -0.0014A6- nc + 0.001 (3.30) or Ko Gow Arc) 0.001 Ac= G31) The factor 0.001 results from the conversion from the usual concentration value in mol-I* into the units mol-cm’? used for conduclance data, We assume that equivalent conductivities stay constant because the overall concentration of ions does not change markedly during the reaction thus we can simplify (Zon ~ anc) “0.001 = A (3.32) and we obtain with Eg. 3.30 Ac = > (3.33) a ‘The alkaline ester saponification is a second-order reaction according, to A+B C+D (3.34) With A-ester, B=hydroxyl ions; G=acetate and D=ethanol, these symbols are used as labels; and with stoichiometric factors equal to unity the reaction rate is given by deq = beng 3.35) v a AB ¢ Because Canta ton =6 (336) ig. 3.35 can be simplified to de , -Gek (337) or (3.38) 39) The fraction Ac consumed at time ¢ with a slarting concentration ¢ is given by