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Ionization Constants of T2O and D2O at 25° from Cell emf's. Interpretation of the Hydrogen Isotope Effects in emf's
1.E. J. Roberts, J. Am. Chem. Soc. 52, 3877 (1930).
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3.A. V. Covington, R. A. Robinson, and R. G. Bates, J. Phys. Chem. 70, 3820 (1966).
4.M. Goldblatt, J. Phys. Chem. 68, 147 (1964).
5.M. Goldblatt and W. M. Jones, Anal. Chem. 36, 431 (1964).
6.A. S. Brown, J. Am. Chem. Soc. 56, 646 (1934).
7.R. G. Bates, Determination of pH (John Wiley & Sons, Inc., New York, 1964), p. 241.
8.The temperature difference between the solution in a cell and the bath, due to the radioactivity, was measured with differential thermocouples as a function of bubbling rate. A typical cell and electrodes were used, but the 1 g of 98% contained no solute. With no circulation the temperature of the water was 0.4° above that of the bath. At the standard one bubble per sec the temperature difference was 0.15°. Emf’s of cells were corrected for heating effects to 25° by using the temperature coefficients, for the acid cell and for the alkaline cell. Corrections were less than 0.1 mV.
9.I. Kirshenbaum, Physical Properties and Analysis of Heavy Water (McGraw‐Hill Book Co., New York, 1951), p. 20.
10.W. M. Jones, J. Chem. Phys. 48, 207 (1968).
11.R. Gary, R. G. Bates, and R. A. Robinson, J. Phys. Chem. 68, 1186 (1964).
12.E. Noonan and V. K. La Mer, J. Phys. Chem. 43, 247 (1939).
13.H. S. Harned and R. N. Ehlers, J. Am. Chem. Soc. 54, 1350 (1932).
14.H. S. Harned and B. B. Owen, Physical Chemistry of Electrolytic Solutions (Reinhold Publ. Corp., New York, 1958), 3rd ed., p. 716.
15.Debye‐Hückel theory gives at at at (Ref. 7: Eq. (18), p. 80, and Table IV, p. 406, with adjustments for dielectric constants and densities).
15.We assumed Dielectric constants for and were obtained from C. G. Malmberg [J. Res. Natl. Bur. Std. 60, 609 (1958)] and densities from Ref. 4 and Ref. 9 The ion size parameter was 4.3 Å (Ref. 11, Footnote 9).
16.Activity coefficients of DCl in have been reported by Lietzke and Stoughton [J. Phys. Chem. 68, 3043 (1964)]. Although their observed emf’s at 25° are for the most part in reasonable agreement with those of Gary, Bates, and Robinson11 and of Noonan and La Mer12 (and with this work at ), their values of seem low.
16.This is apparently connected with their low value of the standard potential which leads to on the scale. Thus at from Lietzke and Stoughton; 0.999 from Gary, Bates, and Robinson11 and Bates and Bower [J. Res. Natl. Bur. Std. 53, 283 (1954)] and 1.0010 from Debye‐Hückel theory.
17.V. Gold and B. M. Lowe, Proc. Chem. Soc. 1963, 140.
18.W. F. Libby, J. Chem. Phys. 11, 101 (1943);
18.W. F. Libby, 15, 339 (1947)., J. Chem. Phys.
19.S. Korman and V. K. La Mer, J. Am. Chem. Soc. 58, 1396 (1936).
20.(a) C. J. Hochanadel, J. Phys. Chem. 56, 587 (1952);
20.(b) A. O. Allen, C. J. Hochanadel, J. A. Ghormley, and T. W. Davis, J. Phys. Chem. 56, 575 (1952); , J. Chem. Phys.
20.(c) A. O. Allen, The Radiation Chemistry of Water and Aqueous Solutions (D. Van Nostrand Co., Inc., Princeton, N.J., 1961).
21.(a) J. Bigeleisen, Proceedings of the International Symposium on Isotope Separation (Interscience Publishers, Inc., New York, 1958);
21.(b) J. Chem. Phys. 34, 1485 (1961).
21.Methods of improving convergence are given by J. Bigeleisen and T. Ishida, J. Chem. Phys. 48, 1311 (1968)., J. Chem. Phys.
22.R. E. Kerwin, Ph.D. thesis, University of Pittsburgh, Pittsburgh, Pa., 1964.
22.See also J. Greyson, J. Phys. Chem. 71, 259, 2210 (1967).
23.H. S. Harned and G. E. Mannweiler, J. Am. Chem. Soc. 57, 1873 (1935).
24.W. R. Busing and D. F. Hornig [J. Phys. Chem. 65, 284 (1961)] observed the Raman band in KOH solution. The frequency changes slightly with concentration, from at 14m to 3614 in dilute solution.
25.L. H. Jones, J. Chem. Phys. 22, 217 (1954); for was calculated from the fundamentals in LiOH(s) and LiOD(s).
26.C. G. Swain and R. F. W. Bader, Tetrahedron 10, 182 (1960), applied the librational part of Eq. (9a) in discussing the free energy of transfer of salts from to See Appendix of the present paper.
27.G. E. Walrafen, J. Chem. Phys. 47, 114 (1967).
28.(a) Evidence is summarized by G. Yagil and M. Anbar, J. Am. Chem. Soc. 85, 2376 (1963). From data on the indicator acidity function these authors suggest association of three water molecules to
28.(b) see, however, K. Heinzinger and R. E. Weston, J. Phys. Chem. 68, 2179 (1964). These authors state that water molecules which behave as if strongly bonded to from the standpoint of some measurements may still be bonded weakly enough that their contribution to isotopic fractionation with the solvent is negligible.
29.J. H. Hibben, J. Chem. Phys. 5, 166 (1937).
30.S. Golub and B. Steiner, J. Chem. Phys. 49, 5191 (1968), have recently identified the hydroxyl monohydrate negative ion in the gas phase. The structure might be or a ring in which the oxygen of hydroxyl is bonded to both water hydrogens.
31.H. C. Urey and D. Rittenberg, J. Chem. Phys. 1, 139 (1933).
32.K. Heinzinger and R. E. Weston, J. Phys. Chem. 68, 744 (1964).
33.V. Gold, Proc. Chem. Soc. 1963, 141.
34.A. J. Kresge and A. L. Allred, J. Am. Chem. Soc. 85, 1541 (1963).
35.J. Schachtschneider and R. G. Snyder, Spectrochim. Acta 19, 117 (1963).
36.G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Co., Inc., Princeton, N.J., 1945), p. 188, Eqs. (II, 248).
37.For force constants see M. Salomon, Can. J. Chem. 44, 689 (1966).
38.G. E. Walrafen, J. Chem. Phys. 36, 1035 (1962).
39.A procedure alternative to the one adopted would be to ignore in Eq. (8), on the assumption that the differential effects of dissolved NaCl on surrounding and molecules, which are represented by the free energy of transfer, would be canceled by similar effects of isotopic sodium hydroxide. When this procedure was applied to the basic‐cell data, a much less satisfactory fit was obtained than is shown in Table V.
40.J. Greyson, J. Phys. Chem. 66, 2218 (1962);
40.J. Greyson, 71, 259, 2210 (1967)., J. Phys. Chem.
41.Y.‐C. Wu and H. L. Friedman, J. Phys. Chem. 70, 166 (1966).
42.H. A. Lauwers and G. P. van der Kelen, Bull. Soc. Chim. Belges 72, 477 (1963).
43.P. Kebarle, M. Arshadi, and J. Scarborough, J. Chem. Phys. 49, 817 (1968).
44.P. Kebarle, Advan. Chem. Ser. 72, 24 (1968).
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