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Volumn 131, Issue 12, 2009, Pages

Large variations in the propensity of aqueous oxychlorine anions for the solution/vapor interface

Author keywords

[No Author keywords available]

Indexed keywords

ANOMALOUS BEHAVIOR; AQUEOUS SOLUTIONS; CHARGE ASYMMETRIES; CORE-LEVEL PHOTOELECTRON SPECTROSCOPY; ELECTRON BINDING ENERGY; MOLECULAR DYNAMICS SIMULATIONS; POLARIZABILITIES;

EID: 70349630070     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.3236805     Document Type: Article
Times cited : (26)

References (28)
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    • Kang, N.1    Anderson, T.A.2    Andrew Jackson, W.3
  • 5
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    • Molecular structure of salt solutions: A new view of the interface with implications for heterogeneous atmospheric chemistry
    • DOI 10.1021/jp012750g
    • P. Jungwirth and D. J. Tobias, J. Phys. Chem. B 1089-5647 105, 10468 (2001). 10.1021/jp012750g (Pubitemid 35338534)
    • (2001) Journal of Physical Chemistry B , vol.105 , Issue.43 , pp. 10468-10472
    • Jungwirth, P.1    Tobias, D.J.2
  • 7
    • 0037123079 scopus 로고    scopus 로고
    • Molecular mechanism of ion binding to the liquid/vapor interface of water
    • DOI 10.1021/jp011853w
    • L. X. Dang and T. M. Chang, J. Phys. Chem. B 1089-5647 106, 235 (2002). 10.1021/jp011853w (Pubitemid 35281711)
    • (2002) Journal of Physical Chemistry B , vol.106 , Issue.2 , pp. 235-238
    • Dang, L.X.1    Chang, T.-M.2
  • 10
    • 77950626769 scopus 로고    scopus 로고
    • Photoelectron spectroscopy of liquid water and aqueous solution: Electron effective attenuation lengths and emission-angle anisotropy
    • 0368-2048 (in press).
    • N. Ottosson, M. Faubel, S. E. Bradforth, P. Jungwirth, and B. Winter, " Photoelectron spectroscopy of liquid water and aqueous solution: Electron effective attenuation lengths and emission-angle anisotropy.," J. Electron Spectrosc. Relat. Phenom. 0368-2048 (in press).
    • J. Electron Spectrosc. Relat. Phenom.
    • Ottosson, N.1    Faubel, M.2    Bradforth, S.E.3    Jungwirth, P.4    Winter, B.5
  • 19
  • 22
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    • see.
    • P. Pianetta, see: http://xdb.lbl.gov/section3/sec-3-2.html.
    • Pianetta, P.1
  • 23
    • 70349633007 scopus 로고    scopus 로고
    • Note
    • At a high enough KE, we would expect to obtain 1:1 signal ratios of ClO n- and Cl- (n=2-4), corresponding to the macroscopic stoichiometric proportions, given our assumption that the Cl 2p photoionization cross section is the same for all ionic species. While this assumption might not be fully accurate, e.g., due to small variations in the intensity of satellites which redistribute signal from the main PE line (Ref.) different cross sections for the ions are highly unlikely to explain the ClO n- / Cl- ratio of 1.2 at 900 eV KE. Rather, one must keep in mind that the photoemission signals are integrals of the total density distributions from the surface into the bulk, exponentially attenuated by the electron mean free path. In a recent photoemission study of aqueous NaI we have shown that the surface enhancement of iodide relative to sodium was observable only for electron KEs smaller than 600 eV; higher KEs primarily probe the bulk solution (Ref.). Probably, for the systems investigated here the preferential surface segregation is significantly stronger than for NaI solutions, and hence surface contributions to the total signal remain detectable at the highest KE achieved here. It would require considerably higher KEs for the surface contributions to become negligible.
  • 24
    • 70349614797 scopus 로고    scopus 로고
    • Note
    • While the rest of the ClO- / Cl- data set is consistent with a lower surface segregation of hypochlorite relative to chloride, the sharp jump in Fig. from 0.47 to 0.70 when going from 100 to 50 eV hardly seems to be consistent with the bulk stoichiometry of ClO- to Cl- -if the bulk ratio is 1:2 the PE ratio should not exceed 0.5. Neither can any single IMFP function explain this large variation with KE for hypochlorite, and at the same time account for the much smaller changes ClO n- / Cl- in the same KE range for the larger oxychlorine anions. One possibility would be to assume a dramatic dependence of the IMFP values on the ionic species, but this assumption could hardly be physically justified. Rather, at 50 eV KE we are apparently too close to the ionization threshold for making the approximation that the effective Cl 2p cross section is ion independent. In the condensed phase, low KE electrons can give rise to complex scattering phenomena and even in the gas phase, severe dependence of the effective core-electron cross sections has been observed on the local molecular structure at the ionized site. Above 100 eV KE these effects should however be very small; L. Saethre (private communication).
  • 27
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    • Specific ion effects at the air/water interface
    • DOI 10.1021/cr0403741
    • P. Jungwirth and D. J. Tobias, Chem. Rev. (Washington, D.C.) 0009-2665 106, 1259 (2006). 10.1021/cr0403741 (Pubitemid 43676510)
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    • Jungwirth, P.1    Tobias, D.J.2
  • 28
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    • Interfacial behavior of perchlorate versus chloride ions in aqueous solutions
    • 1932-7447 (submitted).
    • M. D. Baer, I. -F. W. Kuo, H. Bluhm, and S. Ghosal, " Interfacial behavior of perchlorate versus chloride ions in aqueous solutions.," J. Phys. Chem. C 1932-7447 (submitted).
    • J. Phys. Chem. C
    • Baer, M.D.1    Kuo, I.-F.W.2    Bluhm, H.3    Ghosal, S.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.