Hydrogen Bonding in Tetramethylammonium Ion Salts
Keferences and Notes M. Che. C. Naccache, and B. Imelik. J. Cafe/..24, 328 (1972). T. Purcell and R. A. Weeks, J. Chem. Phys.. 54, 2800 (1971). G. L. W e d . Phofogr Sci. Eng.. 13, 93 (1969). J. Cunningham. J. J. KeHy. and A. L. Penny, J. mys. Chem.. 75. 617 (1971); H. J. Price. Photog. Sci. Eng.. 14, 391 (1970): P. J. Boddy. J. E/ecfrochem. Soc.. 115, 199 (1968); R. A. L. Vanden Berghe. F. Cardon. and W. P. Go". Surface Sci., 39, 368 (1973). (5) P. D. Fleischauer. ti. K. A. Kan, and J. R. Shepherd. J. A m . Chem. Soc.. 94, 283 (1972). (6) f%ysical development. where the source of metal ions for precipitation is the develope solution. is distinguished in photographic literature from the m e common "chemical or direct development," where the source of the oxidant is the lattice of the exposed grain in the photographic emulsion, (7) T H. James in "The Theory of the Photographic Process." 3rd ed. C. E. K. Mees and T. H J a m s , Ed.. Macmihn. New York. N.Y.. 1966, Chapter 15. (8)ti. Jonker, A . Mok?naar. and C. J. Dippel, "gr.Sci. Eng., 13, 38 (1969). (9) D. C. Shuman awl T. H. J a m s , Phofogr. Sci. Eng., 15,42 (1971). (10) P. 0 . Fleischauer and A. B. Chase, J. Phys. Chem. Solids. 35, 1211 (1973). ( 1 1) L. F. Goldstein. unpublished results. (12) These soakiw procedures were necessary in order to remove Ag(l) ad-
(1) (2) (3) (4)
2585 sorbed on the suface of TO2.The influence of adsorption on reaction rates is discussed hter in this paper, and more details will be presented in a subsequent paper.13 (13) P. D. Fleischauer and J. R. shepherd, Presented at the 9th Western Re&mal Meeting of the American chemical society. San Diego. Calif., 1-3 Nov 1973: submitted for publication in J. phys. Chem. (14) J. R. Shepherd and H. Hedgpeth. Rev. Sci. Insfrum.,44, 338 (1973). (15) H. Jonker. C. J. G. F. Janssen. C. J. Dippel, Th. P. G. W. Thijssens. and L. Postrna. Photog. Sci. Eng.. 13,45 (1969). (16) E. J. Delotenzo. L. K. Case. E. M. Stickles, and W. A. Stamoulis, P b toq. Sci. Eng., 13. 95 (1969). (17) R. Mate@ and E. Mdsar. /="fog.Kwresp.. 100, 39 (1964). (18) E. Chaffee. Ph.D. Dissertation. Brown University, 1971; A. A. Green. J. 0. Edwards, and P. Jones. h r g . Chem.. 5. 1858 (1966). (19) A novel method involving the use of surfactants for stabilizing the type of sdutions stud& here has been reported." However. this method is unsatisfactory for use with T i 0 2 thin-fihn substrates because the same mechanism that staMUzes the solotion. Le.. interaction of the surfactant with nuclei that tend to form spontaneously in solution. wOUM prevent reaction at the surface catalytic nuclei since these nuclei are not masked from the surfactant by a gelatin binder. (20) L. G. W n and A. E. MarteU. "Stability Constants of h4etaLlon Cornplexes." The Chemical Socity. London. 1964. (21) P. D. Fleichauef, unpublished results. (22) R. B. Ponthus. R. G. WiQis. and R. J. Newmilk, Phofog Sci. ET.. 16, 406 (1972).
Hydrogen Bonding. IV. Correlation of Infrared Spectral Properties with C-H Hydrogen Bonding and Crystal Habit in Tetramethylammonium Ion Salts'
X
Kenneth M. Harmon,' Irene Gennick,2a*b and Susan L. Madeira2' Deparfmenf of Chemistry. Oakland University. Rochester Michigan 48063 (ReceivedJanuary 2 1. 1974, Revised Manuscript Received June 14. 1974)
Pubkafbn costs assisfedby fhe Pefrdwm Research Fund
Examination of the solid state infrared spectrum of the tetramethylammonium cation in twelve salts shows that three areas of the readily accessible s'odium chloride region are sensitive to crystal environment, and de"nstrates the existence of cation C-H to anion hydrogen bonding in a number of salts such as the flnoride, chloride, bromide, iodide, perchlorate, and borohydride. The C-H stretching region gives characteristic hydrogen bonding shifts in the above salts; this effect is particularly intense in the fluoride. The ('-H deformation modes in the 140
