Understanding the linear correlation between diffusion coefficient and molecular weight. A model to estimate diffusion coefficients in acetonitrile solutions

被引:79
作者
Valencia, Drochss P. [1 ]
Gonzalez, Felipe J. [1 ]
机构
[1] IPN, Dept Quim, Ctr Invest & Estudios Avanzados, Mexico City 07360, DF, Mexico
关键词
Diffusion coefficients; Molecular weight; Linear model; Stokes-Einstein; Organic molecules; Organometallic molecules; ELECTRODE-REACTION; VOLTAMMETRY; MIXTURES; NMR;
D O I
10.1016/j.elecom.2010.11.032
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
In this work, diffusion coefficients (D) for a family of quinones, nitroaromatics, ferrocenes and aromatic hydrocarbon compounds, in acetonitrile, were obtained by single potential step chronoamperometry. A plot of the diffusion coefficient against the molecular weight of each compound shows a linear correlation, which is unexpected from the point of view of the Stokes-Einstein equation. The rearrangement of this equation as a function of the molecular weight (M-w), reveals in fact, a non-linear functional dependence D=f(M-w(-1/3)). however, the linear experimental behaviour was consistent with a model derived from linearization of this function. The resulting model involves variables easily obtained, and can be applied to predict diffusion coefficients of compounds in acetonitrile that cannot be easily measured, either by physicochemical or electrochemical methods. In this first approach, the model seems to be general and open the possibility to generalize the correlation considering other solvents and different kind of molecules. (C) 2010 Elsevier B.V. All rights reserved.
引用
收藏
页码:129 / 132
页数:4
相关论文
共 17 条
  • [1] ABSOLUTE DETERMINATION OF ELECTRON CONSUMPTION IN TRANSIENT OR STEADY-STATE ELECTROCHEMICAL TECHNIQUES
    AMATORE, C
    AZZABI, M
    CALAS, P
    JUTAND, A
    LEFROU, C
    ROLLIN, Y
    [J]. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1990, 288 (1-2) : 45 - 63
  • [2] USE OF MICROELECTRODES FOR THE RAPID-DETERMINATION OF THE NUMBER OF ELECTRONS INVOLVED IN AN ELECTRODE-REACTION
    BARANSKI, AS
    FAWCETT, WR
    GILBERT, CM
    [J]. ANALYTICAL CHEMISTRY, 1985, 57 (01) : 166 - 170
  • [3] Bard AllenJ., 2001, Fundamentals and applications, V2nd
  • [4] DERIVATIZATION OF SURFACES AND SELF-INHIBITION IN IRREVERSIBLE ELECTROCHEMICAL REACTIONS - CYCLIC VOLTAMMETRY AND PREPARATIVE-SCALE ELECTROLYSIS
    BHUGUN, I
    SAVEANT, JM
    [J]. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1995, 395 (1-2): : 127 - 131
  • [5] DETERMINATION OF MOLECULAR-WEIGHT DISTRIBUTIONS FOR POLYMERS BY DIFFUSION-ORDERED NMR
    CHEN, A
    WU, DH
    JOHNSON, CS
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (30) : 7965 - 7970
  • [6] Theoretical and electrochemical study of the quinone-benzoic acid adduct linked by hydrogen bonds
    Garza, J
    Vargas, R
    Gómez, M
    González, I
    González, FJ
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (50) : 11161 - 11168
  • [7] The association of neutral systems linked by hydrogen bond interactions:: a quantitative electrochemical approach
    Gómez, M
    González, I
    González, FJ
    Vargas, R
    Garza, J
    [J]. ELECTROCHEMISTRY COMMUNICATIONS, 2003, 5 (01) : 12 - 15
  • [8] CORRELATIONS FOR PREDICTION OF MOLECULAR DIFFUSIVITIES IN LIQUIDS
    HAYDUK, W
    MINHAS, BS
    [J]. CANADIAN JOURNAL OF CHEMICAL ENGINEERING, 1982, 60 (02) : 295 - 299
  • [9] Variable-temperature microelectrode voltammetry: Application to diffusion coefficients and electrode reaction mechanisms
    Jacob, SR
    Hong, Q
    Coles, BA
    Compton, RG
    [J]. JOURNAL OF PHYSICAL CHEMISTRY B, 1999, 103 (15) : 2963 - 2969
  • [10] Levine I.N., 2009, PHYS CHEM