using three or four concentrations of hydrochloric acid, ranging, after mixing With acetal, from 0.001 to 0.0003M. . ‘The strength of other acids, such as monochloroaeetic, trichloroacetic, sulfuric, and boric, may be determined in the manner described for acetic acid. The concentration of hydrochloric acid may be so adjusted that the reaction rate can be measured conveniently at several temperatures (e.g. 0°, 20°, 30°), and from these data the energy of activation may be calculated. Other hydrolysis reactions may be studied in the dilatometer, using ethyl orthoformate, ethyl orthoacctate, ketal,? dimethyl] acetal, and ethylene acetal.” References 1, Amis, ‘Kinetics of Chemical Change in Solution,” The Macmillan Company, New York (1949). 2, Bronsted and Grove, J. ‘Am, Chem. Soc., 52, 1894 (1930). 3. Bronsted and Wynne-Jones, Trans, Faraday Soc., 25, 59 (1929). 4, Kilpatrick and Chase, J. Am. Chem, Soc., 58, 1732 (1931). 81. Inversion of Sucrose This experiment illustrates the use of the polarimeter, the calcu- lation of reaction-rate constants, and the influence of substitution of atoms on the ionization of an organic acid. Theory. The theory is discussed in Exp. 27. The inversion of cane sugar can be followed without disturbing the system. © The angle of rotation of polarized light passing through the solution is measured with a polarimeter. The reaction is CyH2On + H.0 + Ht CoH 206 + CoHi200 + Ht sucrose glucose fructose The sucrose is dextrorotatory, and the resulting mixture of glucose and fructose is slightly levorotatory because the levorotatory fructose js slightly more active optically than the dextrorotatory glucose. As the sucrose is used up and the invert sugar is formed, the angle of rotation to the right becomes less and less, and finally the light is rotated to the left. ‘The rotation is determined at the beginning and at the end of the reaction, and the algebraic difference between these two readings is a measure of the original concentration of the sucrose. Tt is assumed that the reaction goes to completion, and practically no sucrose remains at “infinite” time. At any time, a number propor- tional to the concentration ¢ of sucrose js obtained from the difference between the final reading and the reading at the time t. The reaction proceeds too slowly to be measured in pure water, but it is catalyzed by hydrogen ions. The water is in such large excessExp. 31) CHEMICAL KINETICS 151 that the reaction follows the equation for a first-order reaction, although it is a bimolecular reaction. Apparatus. Polarimeter (described on page 34); mereury-vapor lamp with filters (page 505) or sodium-vapor lamp; thermostat and circulating pump; two water-jacketed polarimeter tubes; pure sugar; 100 ml of 4N hydrochloric acid; 100 ml of 4N monochloroacetic acid. Procedure. Twenty grams of pure cane sugar (rock candy) is dissolved in water (filtered, if necessary, to give a clear solution) and diluted to 100 ml. , Two jacketed polarimeter tubes are connected in series with the circulating water from a thermostat at 25°. A zero reading is taken with a mercury-vapor lamp and Corning glass filters arranged to transmit only the green light (page 505). A sodium-vapor lamp is equally satisfactory. A small piece of fused sodium chloride, placed ona Méker burner, may be used in case special lamps are not available. After letting the sugar solution and a solution of exactly 4N hydro- chloric acid solution stand in the thermostat for a few minutes, 25 ml of each are mixed together thoroughly. One of the polarimeter tubes is rinsed out with successive small portions of the solution, and then the tube is filled with the solution and stoppered. The second tube is filled, in a similar manner, with a mixture of the sugar solution and exactly 4N monochloroacetic acid solution (exactly 25 ml of each). The tubes are filled as soon as possible after mixing, so that an early reading of the angle of rotation may be obtained. The time of the first reading is recorded, and polarimeter readings of the hydrochloric acid solutions and the corresponding times are taken as rapidly as convenient (10 min) over a period of Lhrorso. As the reaction slows down, the observations may be taken less frequently. The observations should extend over a period of 3 hr or more. The reaction goes much more slowly with the monochloroacetic acid, and the readings are taken less frequently. They are taken at convenient intervals of time when the polarimeter is not being used for readings on the solution of hydrochloric acid. The final readings are taken after the solutions have stood in a tightly stoppered flask long enough for the reaction to be completed, at least 2 days for the hydrochloric acid and a week for the mono- chloroacetic acid. It is important to preserve a sufficient quantity of each of the original solutions to rinse and fill the polarimeter tube for these readings. Calculations. The time is plotted along the X-axis, on coordinate paper, and the corresponding values of a — a. along the Y-axis.152 LABORATORY EXPERIMENTS Exp. 31 ‘As stated before, the concentration ¢ of sucrose may be expressed in terms of the angles of rotation and is proportional to a — a where a is the angle of rotation at time ¢ and aw is the final angle (negative in this particular case). The logarithms of (« — @) are plotted against time. Plotting the logarithms of (w — a.) gives the same slope as plotting the logarithms of (a — a) multiplied by a constant. The best straight line is drawn through the points, one for the hydrochloric acid and one for the monochloroacetic. The specific reaction rates are calculated from the slopes of the lines. The ratio of the constants for the two different acids is a measure of the ratio of activity of the hydrogen ions of the acids at 2N, provided that in both cases the acids were exactly 4N. This ratio may be compared with the hydrogen-ion-activity ratio as calculated from the disgociation constant and the concentration. ‘A calculation is made to show what the concentration of suérose was in each case exactly 10 hr after starting the reaction. The precisior of this calculation is estimated. The value of & is checked by solving two simultaneous. equation: based on measurements of a near the beginning and near the end o the recorded observations. In this way both unknown constants, ] and e, may be evaluated without getting an experimental value fo Om. More accurate values of & and a. may be obtained by averagin; several sets of data. On the assumption that the hydrochloric acid is completely dis sociated, and that the rate of inversion is directly proportional to th activity of hydrogen ions, the degree of ionization of monochloroaceti acid in 2N solution and the ionization constant are calculated. Th rate of this reaction depends upon the concentration of the sucrose but this quantity appears to remain constant when the reaction i carried out as described. Practical Applications. ‘These are discussed under Exp. 27. Suggestions for Further Work. Some suggestions for further work are discusse under Exp. 27, Trichloroacetic acid and sulfuric acid, and other acids, each 4N, may be used 8 catalysts. Trichloroacetic acid is about as strongly dissociated as hydrochlori acid. (Caution. It is corrosive.) The relative acid strengths of monochlorc acetic acid and trichloroacetic acid are to be explained on the basis of molecule structure. The activation energies may be calculated by running a second set of dete: minations, using water pumped from a thermostat at 30° or at 20°. A mixture of methyl acetate and sucrose may be followed both with titratio measurements and rotation measurements, to determine if the hydrogen ior can catalyze both reactions simultaneously with undiminished efficiency,Exp. 32] CHEMICAL KINETICS 153 References 1, Moran and Lewis, J. Chem. Soc., 121, 1613 (1922). 2. Pennycuick, J. Am. Chem. Soc., 48, 6 (1926). 3. Scatchard, J, Am. Chem. Soc., 48, 2259 (1926). 32. Clock Reactions Clock reactions are reactions that go on unobserved for a time and then suddenly give a color change or precipitate. Such reactions make good lecture demonstrations,! and one is used here to illustrate the formulas of chemical kinetics, which deal with the influence of , concentration on reaction rate. Theory. When solutions of KI, KIOs, and KAsOz are mixed in an acetic acid-sodium acetate buffer solution at a pH of 4 to 5, the successive reactions which occur may be represented by the following equations: 10; + 5I- + 6H+33L,43H,0 9 Sino 0) 2( Ta AsOy it H,0> +2 + ~AsOy + 2H out ") pe @) fo 10, rT a. Between pH 4 oad 5 She first reaction i is relatively alow, whereas the second one is instantaneous. The first reaction is therefore the rate determining step. There is no free iodine in the solution until the sodium arsenite has been used up. Therefore if starch solution is added to the solution, a, blue color is developed suddenly when reaction (2) ceases and free iodine is liberated. Since the color appears sharply only after some time, such a reaction is known as a clock reaction. The iodate ion does not react to any significant extent with arsenite ion at this pH. As a consequence, the influence of concentration, pH, and temperature on the rate of the first reaction may be determined by adding a known quantity of KAsO: solution to a solution of KI, and then adding a solution of KIO; in such quantity as to give an excess .of KIO; over the KAsOs. The original concentration of K10; will be known, and the time required for a small amount of iodine (equivalent to the amount of KAsO: present) to be formed is . determined. Since the iodide ion is regenerated by reaction (2), its concentration remains essentially constant (being increased only slightly by that I- coming from the reduction of I0}), so that the rate of reaction may be expressed by the first-order equation — TE 04 = pctos) (3)