Reactions of hydrogen atoms and aliphatic radicals with monovalent cadmium and nickel ions as a source of hydrogen yield in some radiation chemical systems

Mira Freiberg; Dan Meyerstein

doi:10.1039/F19777300622

Reactions of hydrogen atoms and aliphatic radicals with monovalent cadmium and nickel ions as a source of hydrogen yield in some radiation chemical systems

Mira Freiberg, Dan Meyerstein

Department of Chemistry

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16 Scopus citations

Abstract

The effect of CdSO₄ and NiSO₄ on the radiolytic hydrogen yield and its isotopic composition in the systems H₂O + CH₃OH, H₂O + CD₃OH, D₂O + CH₃OD, H₂O + (CH₃)₂CHOH, H₂O + (CH₃)₂ CDOH and D₂O + (CH₃)₂CHOD are reported. The results suggest that hydrogen atoms and aliphatic radicals oxidize Cd_aq⁺ and Ni_aq⁺. Furthermore it is suggested that the reaction Cd-C(CH₃)₂OH⁺ → CdH⁺ + (CH₃)C^OH=CH₂ occurs in aqueous solutions. The implications of these observations on earlier results are discussed.

Original language	English
Pages (from-to)	622-631
Number of pages	10
Journal	Physical Chemistry Chemical Physics
Volume	73
DOIs	https://doi.org/10.1039/F19777300622
State	Published - 1 Dec 1977

ASJC Scopus subject areas

General Chemistry

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10.1039/F19777300622

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@article{18b4f66e0a0e4f67a8d52d0fc2e22ea5,

title = "Reactions of hydrogen atoms and aliphatic radicals with monovalent cadmium and nickel ions as a source of hydrogen yield in some radiation chemical systems",

abstract = "The effect of CdSO4 and NiSO4 on the radiolytic hydrogen yield and its isotopic composition in the systems H2O + CH3OH, H2O + CD3OH, D2O + CH3OD, H2O + (CH3)2CHOH, H2O + (CH3)2 CDOH and D2O + (CH3)2CHOD are reported. The results suggest that hydrogen atoms and aliphatic radicals oxidize Cdaq+ and Niaq+. Furthermore it is suggested that the reaction Cd-C(CH3)2OH+ → CdH+ + (CH3)COH=CH2 occurs in aqueous solutions. The implications of these observations on earlier results are discussed.",

author = "Mira Freiberg and Dan Meyerstein",

note = "Funding Information: Haikand Mr. A. Amar for technical assistance. This work was partially supported by agrant from the United States-Israel Binational Science Foundation (B. S . F.), JerusalemIsrael.(a) T. Rigg, G. Stein and J. Weiss, Proc. Roy. SOC. A, 1952, 211, 375; (b) G. Czapski, J.Jostner and G. Stein, J. Phys. Chem., 1961, 65,960; (c) H. A. Schwarz, J. Phys. Chem., 1963,67, 2827; ( d ) G. G. Jayson, J. P. Keene, D. A. Stirling and A. J. Swallow, Trans. FaradaySOC. 1969, 65,2453.(a) H. Cohen and D. Meyerstein, J.C.S. Dalton, 1974, 2559 ; (6) D. Behar and A. Samuni,Chem. Phys. Letters, 1973, 22, 105 ; (c) M. Freiberg and D. Meyerstein, J.C.S. Chem. Comm.,submitted for publication and J. R. Kochi, Accounts Chem. Res., 1974, 7, 351.(a) M. Kelm, J. Lilie, A. Henglein and E. Janata, J. Phys. Chem., 1974, 78, 882 ; (b) M. Kelm,J. Lilie and A. Henglein, J.C.S. Faraday I, 1975, 71, 1132; (c) A. M. Tait, M. Z . Hoffmanand E. Hayon, J. Amer. Chem. Soc., 1976, 98, 86 ; ( d ) H. Cohen and D. Meyerstein, Inorg.Chem., 1974, 13, 2434 and references therein; (e) D. Ellis, M. Green, D. G. Sykes, G. V.Bwton and R. M. Sellers, J.C.S. Dalton, 1973, 1724; (f) D. Behar, A. Samuni and R. W.Fessenden, J. Phys. Chem., 1973,77,2055 ; (9) T. S. Roche and J. F. Endicott, Inorg. Chem.,1974, 13, 1575; (h) J. M. Pratt and P. J. Graig, Advances in Organometallic Chemistry I1(1970), p. 331 ; (i) K. Elroi and D. Meyerstein, to be published.M. Anbar and D. Meyerstein, J. Phys. Chem. 1964, 68,1713.M. Matheson and L. M. Dorfman, Pulse Radiolysis (M.I.T. Press, Boston, 1969).(a) M. Anbar, M. Bambenek and A. B. Ross, NSRDS-NBS, 43,1973 ; (b)L. M. Dorfman andG. E. Adams, NSRDS-NBS. 46, 1973.M. Anbar and D. Meyerstein, J. Phys. Chem., 1964, 68, 3184.J. Rabani, J. Amer. Chem. SOC., 1962,84,868 ; L. M. Dorfman, I. A. Taub and R. E. Buhler,J. Chem. Phys., 1962, 36, 3051 ; A. Appleby, G. Scholes and M. Simic, J. Amer. SOC., 1963,85, 3891 ; G. Scholes and M. Simic, J. Phys. Chem., 1964, 68,1731, 1738.{\textquoteright} A. Barkatt and J. Rabani, J. Phys. Chem., 1975, 79,2592.l o H. A. Schwarz, J. Phys. Chem., 1969, 73, 1928.l 1 D. Meyerstein, Accounts Chem. Res., submitted for publication.l 2 A. Kuppermann, Radiation Chemistry (North Holland, Amsterdam, 1967), p. 212 ; M. Anbar,Fundamental Processes in Radiation Chemistry, ed. P. Ausloos (John Wiley and Sons, 1968) ;M. Faraggi, Int. J. Radiation Phys. Chem., 1973, 5, 197; E. Peled, Ph.D. Thesis (HebrewUniversity, Jerusalem, 1972).l3 M. Anbar and P. Neta, Int. J. of Appl. Radiation Isotopes, 1967, 18, 493.l4 D. Meyerstein, Ph.D. Thesis, (Hebrew University, 1965).(PAPER 6/1608",

year = "1977",

month = dec,

day = "1",

doi = "10.1039/F19777300622",

language = "English",

volume = "73",

pages = "622--631",

journal = "Physical Chemistry Chemical Physics",

issn = "0300-9599",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Reactions of hydrogen atoms and aliphatic radicals with monovalent cadmium and nickel ions as a source of hydrogen yield in some radiation chemical systems

AU - Freiberg, Mira

AU - Meyerstein, Dan

N1 - Funding Information: Haikand Mr. A. Amar for technical assistance. This work was partially supported by agrant from the United States-Israel Binational Science Foundation (B. S . F.), JerusalemIsrael.(a) T. Rigg, G. Stein and J. Weiss, Proc. Roy. SOC. A, 1952, 211, 375; (b) G. Czapski, J.Jostner and G. Stein, J. Phys. Chem., 1961, 65,960; (c) H. A. Schwarz, J. Phys. Chem., 1963,67, 2827; ( d ) G. G. Jayson, J. P. Keene, D. A. Stirling and A. J. Swallow, Trans. FaradaySOC. 1969, 65,2453.(a) H. Cohen and D. Meyerstein, J.C.S. Dalton, 1974, 2559 ; (6) D. Behar and A. Samuni,Chem. Phys. Letters, 1973, 22, 105 ; (c) M. Freiberg and D. Meyerstein, J.C.S. Chem. Comm.,submitted for publication and J. R. Kochi, Accounts Chem. Res., 1974, 7, 351.(a) M. Kelm, J. Lilie, A. Henglein and E. Janata, J. Phys. Chem., 1974, 78, 882 ; (b) M. Kelm,J. Lilie and A. Henglein, J.C.S. Faraday I, 1975, 71, 1132; (c) A. M. Tait, M. Z . Hoffmanand E. Hayon, J. Amer. Chem. Soc., 1976, 98, 86 ; ( d ) H. Cohen and D. Meyerstein, Inorg.Chem., 1974, 13, 2434 and references therein; (e) D. Ellis, M. Green, D. G. Sykes, G. V.Bwton and R. M. Sellers, J.C.S. Dalton, 1973, 1724; (f) D. Behar, A. Samuni and R. W.Fessenden, J. Phys. Chem., 1973,77,2055 ; (9) T. S. Roche and J. F. Endicott, Inorg. Chem.,1974, 13, 1575; (h) J. M. Pratt and P. J. Graig, Advances in Organometallic Chemistry I1(1970), p. 331 ; (i) K. Elroi and D. Meyerstein, to be published.M. Anbar and D. Meyerstein, J. Phys. Chem. 1964, 68,1713.M. Matheson and L. M. Dorfman, Pulse Radiolysis (M.I.T. Press, Boston, 1969).(a) M. Anbar, M. Bambenek and A. B. Ross, NSRDS-NBS, 43,1973 ; (b)L. M. Dorfman andG. E. Adams, NSRDS-NBS. 46, 1973.M. Anbar and D. Meyerstein, J. Phys. Chem., 1964, 68, 3184.J. Rabani, J. Amer. Chem. SOC., 1962,84,868 ; L. M. Dorfman, I. A. Taub and R. E. Buhler,J. Chem. Phys., 1962, 36, 3051 ; A. Appleby, G. Scholes and M. Simic, J. Amer. SOC., 1963,85, 3891 ; G. Scholes and M. Simic, J. Phys. Chem., 1964, 68,1731, 1738.’ A. Barkatt and J. Rabani, J. Phys. Chem., 1975, 79,2592.l o H. A. Schwarz, J. Phys. Chem., 1969, 73, 1928.l 1 D. Meyerstein, Accounts Chem. Res., submitted for publication.l 2 A. Kuppermann, Radiation Chemistry (North Holland, Amsterdam, 1967), p. 212 ; M. Anbar,Fundamental Processes in Radiation Chemistry, ed. P. Ausloos (John Wiley and Sons, 1968) ;M. Faraggi, Int. J. Radiation Phys. Chem., 1973, 5, 197; E. Peled, Ph.D. Thesis (HebrewUniversity, Jerusalem, 1972).l3 M. Anbar and P. Neta, Int. J. of Appl. Radiation Isotopes, 1967, 18, 493.l4 D. Meyerstein, Ph.D. Thesis, (Hebrew University, 1965).(PAPER 6/1608

PY - 1977/12/1

Y1 - 1977/12/1

N2 - The effect of CdSO4 and NiSO4 on the radiolytic hydrogen yield and its isotopic composition in the systems H2O + CH3OH, H2O + CD3OH, D2O + CH3OD, H2O + (CH3)2CHOH, H2O + (CH3)2 CDOH and D2O + (CH3)2CHOD are reported. The results suggest that hydrogen atoms and aliphatic radicals oxidize Cdaq+ and Niaq+. Furthermore it is suggested that the reaction Cd-C(CH3)2OH+ → CdH+ + (CH3)COH=CH2 occurs in aqueous solutions. The implications of these observations on earlier results are discussed.

AB - The effect of CdSO4 and NiSO4 on the radiolytic hydrogen yield and its isotopic composition in the systems H2O + CH3OH, H2O + CD3OH, D2O + CH3OD, H2O + (CH3)2CHOH, H2O + (CH3)2 CDOH and D2O + (CH3)2CHOD are reported. The results suggest that hydrogen atoms and aliphatic radicals oxidize Cdaq+ and Niaq+. Furthermore it is suggested that the reaction Cd-C(CH3)2OH+ → CdH+ + (CH3)COH=CH2 occurs in aqueous solutions. The implications of these observations on earlier results are discussed.

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U2 - 10.1039/F19777300622

DO - 10.1039/F19777300622

M3 - Article

AN - SCOPUS:37049102706

SN - 0300-9599

VL - 73

SP - 622

EP - 631

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

ER -

Reactions of hydrogen atoms and aliphatic radicals with monovalent cadmium and nickel ions as a source of hydrogen yield in some radiation chemical systems

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