Hydrolysis of Ethyl Acetate Ethyl acetate (CH;COOC, Hs) hydrolyzes in alkaline solution according to the reaction EtAc + OH~ = EtOH + Ac” (26-1) Even at room temperature the rate of hydrolysis is appreciable. Since this aqueous solution contains ions, it conducts electricity. Initially, only Na* and OH" are present in the solution, but as the reaction progresses AC™ is produced. Since the conductivities of the hydroxyl and acetate ions are very different, the conductivity of the solution changes with time as the hydrolysis proceeds. The conductance of an ion depends on its ionic mobility, which in turn depends on the size of the ion. Since the conductance of the large acetate ion is less than that of the smaller, more mobile hydroxyl ion, the conductivity of the solution decreases as the hydrolysis proceeds. In. this experiment, the progress of the reaction is followed by measuring the conductance of the reaction mixture as a function of time. Since the reaction is found to be second order and goes essentially to completion (Walker, 1906), the rate law is —d(a- dt *) = Ka — x\(b- x) (26-2) b = initial molarity of sodium hydroxide x = moles of reactants/L reacting in time ¢ k = specific rate constant (L mol~! sec!) The integrated form of Equation 26-2 depends on whether the initial concentrations of the reactants are equal or not equal. If a does not equal b, then integration of Equation 26-2 (Moore and Pearson, 1981) leads to b(a~ x) _ _ In ab x) k(a- byt (26-3) If a equals b, then the integrated form of Equation 26-2 is ae (26-4 a(a-x) ’ In either case, it is possible to follow the course of the reaction by mea- suring the conductance as the reaction progresses with time.Conductance, Equivalent Conductance, and lonic Concentrations Conductance L (mhos) is just the reciprocal of resistance R (ohms): s 1 L=R (26-5) R The resistance of any conductor is directly proportional to its length a ; inversely proportional to jts cross-sectional area, £ F R=p] (26-6) where R is the resistance in ohms, 2 is the length in centimeters, and A is the cross-sectional area in square centimeters. The proportionality cone stant p is called the specific resistance. Equation 26-6 may be written in. terms of the conductance L, < A 4 L=Ls5 (26-7) where L, is the specific conductance with units of mho per centimeter. The usual laboratory conductance cell is constructed with two ay proximately parallel platinum electrodes, each with an area A of approx- imately 1 cm? separated by a distance @ of about 1 cm. Since Aand é are difficult to measure directly with such a cell, a cell constant is defined: £ Keen =] Equation 26-7 is then written L. L=— Keen The cell constant is determined by filling the cell with a substance 0 exactly known specific conductance and measuring the cell resistancé very precisely with a Wheatstone bridge, as described in Experiment 21 In this experiment, however, it is not necessary to know the cell constant it suffices to measure the resistance of the cell as a function of time. _ The conductance L of the reacting solution depends on the equiv alent conductances of the conducting species in the solutions and thei concentrations. The equivalent conductance (mho cm? equiv~') is de fined as . A= 10ers (26-10 where L, is the’specific conductance of the solution, cis the concentratio in equiv/L, and the constant is 1000 cm?/L. In this experiment, 1 equi6ll = | mole. Thus, the conductance of the solution in terms of the individual jonic conductances ), is given by 1 -p-it= cA _ Dieta + Zier 7 R Keen 1000 Ken 1000Kcen Consequently, the course of the reaction can be followed by mon- itoring the conductance of the solution as time passes. This is possible because the acetate ion produced by the reaction and the hydroxyl ion consumed have substantially different equivalent ionic conductances (at 25°C, Aac- = 40.9 and Aou- = 197.6 mho cm~? equiv™'). * Tt is convenient to treat separately the two cases, equal and unequal initial concentrations of reactants. (26-11) Reactant Concentrations Are Equal Since the conductance of the solution is proportional to the equivalent _ conductance of all the ions in the solution, we can write expressions for the conductance at times ¢ = 0, t, and t., the time for the reaction to go to completion. The expressions for the concentrations at various times are summarized in Table 26-1. According to Equation 26-11 and Table 26-1, the conductances are given by Lo = (Adnat + Qon-)/1000Keen (26-12) L, = (dwar + @on- — XAon- + XAac-)/ 1000kcen (26-13) Lg = (adnat + Oac-)/1000Keen (26-14) It follows by substitution that . x _b-h a-x L-L, (26-15) Thus, Equation 26-4 may be written in terms of experimentally measured conductances: In - ki Lol. = kat (26-16) TABLE 26-1 Concentrations at Various Times: Equal Reactant Concentrations ee Time* [EtAc] [OH] [EtOH] {Ac} t=0 a a 0 0 t a-x a-x x x te 0 0 a a a * It is assumed that the reaction goes essentially to completion after a long period of time f..Determining Ly. The value of Lo can be obtained by two mats First, extrapolation of a graph of the measured resistances back to 1 = gives a value for Ro from which Lo = 1/Ro. Second, direct measuremen; ofa solution of sodium hydroxide of the same concentration as the initial concentration in the run can be measured. Remember that the prepared stock standard solution of sodium hydroxide must be diluted with water to the same concentration as it would have initially in a run. Determining L,. With Equation 26-11 and Table 26-1 we can dee termine the value of L,, ‘ Le = (@dac~ + @dnat)/1000Keen (26-17) and similarly for Lo: Lo = (ahon~ + adxar)/1000keen (26-18). While the conductance at ¢ = 0 is just the conductance of a solution oa sodium hydroxide, the conductance when the reaction has gone to com. pletion is just the conductance of a solution of sodium acetate. To cal- culate L,, the conductance at completion, divide Equation 26-17 by Equation 26-18 and solve for L.: Nace + Anat L.={————*— 26-19) ec (s- wee Io (26-19) If the left side of Equation 26-16 is plotted against ¢, a straight line results, the slope of which equals ka. : ‘Reactant Concentrations Are Unequal When the reactant concentrations are unequal, one of the reactants is a limiting reagent and its concentration equals zero when the reaction is at completion. The changes in concentration for this condition are sum- marized in Table 26-2. The concentration of the spectator ion Na* re mains constant, while the concentrations of OH™ and Ac™ change witt TABLE 26-2 3 Concentrations at Various Times: Unequal Reactant Concentrations eet ee Time [EtAc] {OH7] [EtOH] [Ac] 1=0 a b 9 0 t a-x b-x x x 2 0 b-e c c 12 a-c 0 c c Sc * Let c equal the concentration of the limiting reagent, a. » Let c equal the concentration of the limiting reagent, bd613 the course of the reaction. With the data in Table 26-2 and Equation 26-11 one may show that Ly — Ly = XQou- ~ Nac-)/ 1000Keen (26-20) Io — L, = ¢(Xon- — Nac-)/ 1000 Keen (26-21) If Equations 26-20 and 26-21 are solved for x, the result is _ e(bo- Li) x= 26-22 (lo — Le) oe Determination of Ly and L,. The determination of Lo is exactly the same as discussed above for the case of equal reactant concentrations. The calculation of L, is similar. For ethyl acetate as the limiting reagent, we can determine L, with Equation 26-11 and Table 26-2: L, = [(b — €)don- + €Xpe> + dwar ]/1000Keen (26-23) The same expression is valid if sodium hydroxide is the limiting reagent, since the first term drops out when b= c. Att = 0 Equation 26-23 is still valid since the solution is simply a sodium hydroxide solution. If Equation 26-18 is combined with Equation 26-23, L, can be calculated for the case of unequal reactant concentrations: (b — c)ou- + CMe + Puee| BQ\ou- + Anat) Now, with values of x calculated from Equation 26-22, it is possible to plot In [b(a — x)]/[a(b — x)] against ¢. According to Equation 25-3, a straight line results, the slope of which equals k(a — b), so that the specific rate constant may be evaluated. L.= 14] (26-24) Apparatus The experiment requires miscellaneous glass and volumetric ware, a con- ductance cell, a conductance bridge, a buret, 25 and 35°C thermostats, and a timer. : SAFETY CONSIDERATIONS Many conductance cells make electrical contact by a bare lead inserted into a well in the cell filled with mercury. Mercury is very toxic. Take care to avoid spilling it. Handle the cell over a large enameled photographic tray. The electrodes of the conductance cell should always be covered with water and not allowed to dry out. If they dry out, they may need a fresh coat of platinum black.ny * EXPERIMENTAL PROCEDURE In a 250-ml volumetric flask, prepare a 0.04 M solution of ethyl acetate. Weigh the required amount of ethyl acetate into a tared ~ weighing bottle containing water. Adding the ethyl acetate (0.001 a g) to the water prevents loss of the ester from evaporation. Keep \ the weighing bottle tightly closed before washing the solution of the — ester into the volumetric flask and diluting to the mark. Calculate — the exact molarity. This solution should be prepared on the same — day it is used, since appreciable hydrolysis can take place in a few © days even in a neutral solution. Calculate the number of milliliters of standard 0.1 M NaOH required to make 250.0 ml NaOH with exactly the same molarity as the ethyl acetate solution. With a buret, deliver the required NaOH © solution into a 250-ml volumetric flask and dilute to the mark. Prior to making a run, immerse the solutions of the ester and the base, and the conductance cell, in the 25°C thermostat and | allow them to come to thermal equilibrium. A flask for mixing should also be immersed. A special flask (Daniels et al., 1970) containing the ester and base in two compartments is especially convenient (Fig. 26-1). Pipet a 25-ml aliquot of base into the inner cylinder and 50 ml of ester solution into the region outside the cylinder. Replace in the ther- mostat until it reaches thermal equilibrium. Clamp the empty con- ductance cell in the thermostat. ee® Figure 26-1 Mixing flask. (Source: Daniels et al., 1970.)615 Alternatively, clamp in place in the thermostat a glass-stoppered test tube containing a 25-ml aliquot of the ethyl acetate solution and a stoppered 250-ml Erlenmeyer flask containing a 50-ml aliquot of the sodium hydroxide solution. After the solutions have attained thermal equilibrium, mix them quickly in the flask and transfer a portion to a thermostatted conductance cell. After mixing the solutions, start the timer and begin measuring resistance every minute for the first 10 minutes, then every 2 min- utes, and finally every 5 or 10 minutes until a total run time of about 45 minutes is achieved. Although Ro can be determined by extrapolating a plot of R versus ¢ back to zero time, it can also be measured with the con- ductance bridge directly. Mix an aliquot of the NaOH solution with an aliquot of water equal in size to the ester aliquot used. The re- sistance of this solution equals Ro. This is a good exercise to do if you are unfamiliar with the conductance bridge and need a practice solution. Having measured Rp directly, you can preset your bridge settings to facilitate initiating a run. Make three more runs, reversing the ratios of ester and base in one, and with equal concentrations of ester and base in the other two. Of the four runs, make two at 25°C and two at 35°C. Remember to calculate the initial concentrations of the reac- tions afier mixing! Results and Calculations Equal Reactant Concentrations. For each run, identify Ro, R., T, and a. Tabulate and graph R and t. Determine Ro graphically and by direct measurement. Use Equation 26-16 to treat the data when a = b. Tabulate and graph the left side of Equation 26-16 against time ¢ in seconds. Calculate k. Report the error in k determined from a least- squares analysis of the data. Unequal Reactant Concentrations. For each run, identify Ro, R., T, a, b, and c. Tabulate and graph R and t. Determine Ro graphically and by direct measurement. Compare and comment on the direct and graphical measurements. When a and b are unequal, tabulate and plot the left side of Equation 26-3 against time t in seconds. List Ro, R., a, b, c, and T. From a least-squares analysis of the data, determine the specific rate constant k and its standard deviation. Activation Energy. Prepare a tabular summary of T, k, In k, and 1/T. From an Arrhenius plot of In k versus 1/T, calculate the activation energy E, and the preexponential factor A: Ey = - Ink prt ina (26-25) (Text continues on page 620.)