Conductometric study on higher ion aggregation of lithium and sodium nitrophenolates in aprotic solvents

被引:16
|
作者
Hojo, M
Hasegawa, H
Hiura, N
机构
[1] Department of Chemistry, Faculty of Science, Kochi University
来源
JOURNAL OF PHYSICAL CHEMISTRY | 1996年 / 100卷 / 02期
关键词
D O I
10.1021/jp951556p
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ion associations of lithium and sodium nitrophenolates (2-, 4-, 2,4-, 2,5-, and 2,4,6-derivatives) were examined by means of conductometry at 25 degrees C in several aprotic solvents (MeCN, DMF, acetone, and PhCN). The molar conductivities (Lambda) of lithium 2,4-dinitrophenolate in acetonitrile were explained by the formation of ''symmetrical'' triple ions (M(2)X(+) and MX(2)(-)) as well as ion pairs (MX); however, those of the sodium salt were explained by the formation of ion pairs alone. The salts of 2,5-dinitrophenol in acetonitrile gave larger formation constants than those of 2,4-dinitrophenol. The molar conductivities of lithium 2-nitrophenolate in acetonitrile were explained by the strong formation of quadrupoles (M(2)X(2)) in addition to triple ions and ion pairs, although the (direct) Shedlovsky analysis gave a ''pseudo'' value of K-a = 0 (no association between simple ions). Any species from lithium 2-nitrophenolate could not be ignored even at lower concentrations because the ratio of the concentration of a species (e.g., [X(-)]/C-s) to the salt concentration (C-s) was greater than ca. 1% for C-s = (0.16-2.0) x 10(-3) mol dm(-3). Lithium 4-nitrophenolate gave formation constants smaller than those of the 2-nitrophenolate because of no nitro-group at the ortho-position. Ion aggregations occurred to the higher extent for salts of ortho-substituted nitrophenols with weaker (Bronsted) acidities of phenols (2,4,6- < 2,4- < 2,5- < 2-). In the stronger solvating solvent, DMF, the high ion aggregation above ion pair formation was observed only for lithium 2-nitrophenolate but not for other salts. The logarithms of the formation constants for lithium 2,4-dinitrophenolate decreased linearly with increasing value of the (geometric) average between the donor and acceptor numbers [(DN x AN)(1/2)] of the solvents. The results of the present study provided the quantitative interpretation for the promotion of proton transfer from nitrophenols to amine or pyridine bases by the addition of LiClO4 or NaClO4 in acetonitrile.
引用
收藏
页码:891 / 896
页数:6
相关论文
共 50 条
  • [21] Ion Association in Aprotic Solvents for Lithium Ion Batteries Requires Discrete-Continuum Approach: Lithium Bis(oxalato)borate in Ethylene Carbonate Based Mixtures
    Korsun, Oleksandr M.
    Kalugin, Oleg N.
    Fritsky, Igor O.
    Prezhdo, Oleg V.
    JOURNAL OF PHYSICAL CHEMISTRY C, 2016, 120 (30): : 16545 - 16552
  • [23] Spectroscopic study of solvation processes and ionic association in lithium salt solutions with ionic and aprotic solvents
    M. M. Gafurov
    S. A. Kirillov
    K. Sh. Rabadanov
    M. B. Ataev
    D. O. Tret’yakov
    Journal of Structural Chemistry, 2014, 55 : 67 - 71
  • [24] STUDY OF HYDRODIMERIZATION OF ACRYLONITRILE .5. HYDRODIMERIZATION OF ACRYLONITRILE WITH SODIUM AMALGAM IN POLAR APROTIC SOLVENTS
    KAWAMATA, M
    KOG KAGAKU ZASSHI, 1971, 74 (12): : 2479 - &
  • [25] VIBRATIONAL STUDY OF IONIC ASSOCIATION IN APROTIC-SOLVENTS .13. THERMAL DESOLVATION OF THE LITHIUM ISOCYANATE ION-PAIR IN HEXAMETHYLPHOSPHORIC TRIAMIDE
    RANNOU, J
    LEGOFF, D
    CHABANEL, M
    JOURNAL OF CHEMICAL RESEARCH-S, 1989, (10): : 324 - 325
  • [26] Aggregation and micellization of sodium dodecyl sulfate in the presence of Ce(III) at different temperatures: A conductometric study
    Valente, Artur J. M.
    Burrows, Hugh D.
    Cruz, Sandra M. A.
    Pereira, Rui F. P.
    Ribeiro, Ana C. F.
    Lobo, Victor M. M.
    JOURNAL OF COLLOID AND INTERFACE SCIENCE, 2008, 323 (01) : 141 - 145
  • [27] Conductometric study of lithium halides and thiocyanate in the mixed solvents of tetrahydrofuran and 2-ethyl-1-hexanol
    Hojo, M
    Ueda, T
    Chen, ZD
    Nishimura, M
    JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1999, 468 (01): : 110 - 116
  • [28] A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes
    Fears, Tyler M.
    Sacci, Robert L.
    Winiarz, Jeffrey G.
    Kaiser, Helmut
    Taub, Haskell
    Veith, Gabriel M.
    JOURNAL OF POWER SOURCES, 2015, 299 : 434 - 442
  • [29] Theoretical study of the mechanism and regioselectivity of the alkylation reaction of the phenoxide ion in polar protic and aprotic solvents
    Nogueira, Isac C.
    Pliego, Josefredo R., Jr.
    COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2018, 1138 : 117 - 122
  • [30] Mixed Lithium and Sodium Ion Aprotic DMSO Electrolytes for Oxygen Reduction on Au and Pt Studied by DEMS and RRDE
    Hegemann, M.
    Bawol, P. P.
    Koellisch-Mirbach, A.
    Baltruschat, H.
    ELECTROCATALYSIS, 2021, 12 (05) : 564 - 578