Relative extractabilities of cations and anions in the extraction of ion associates and estimation of extraction constants from chemical structure

• MOTOMIZU Shoji

  Department of Chemistry, Faculty of Science, Okayama University

Bibliographic Information

Other Title

• イオン会合抽出における陽，陰イオンの相対的抽出性と抽出定数の推定
• イオン カイゴウ チュウシュツ ニ オケル ヨウ,インイオン ノ ソウタイテキ

Abstract

Extraction constant, K_ex, for the chloroform extraction of ion associates from aqueous solution was divided into two parameters, C and A, assigned to the cation and the anion, respectively: logK_ex=C+A. In estimating the values of C or A for various ions, a hypothetical cation, -_??_-⁺ (long-chain alkyltrimethylammonium type), with no alkyl groups nor hydrogen atoms was chosen as a reference ion for which C=0. C value for long-chain alkyltrimethylammonium cations can be calculated from C=0.59n, where n is the number of carbons and 0.59 is the value of π_CH<SUB>2</SUB>, contribution constant of methylene group to extraction constant. C values for other alkylammonium ions were determined experimentally and compared with those calculated on the assumption of additivity of contribution constants of functional groups. C values for other cationic groups were as follows: -1.20 for -_??_-⁺ (symmetrical tetraalkylammonium type), -0.56 for >-NH₃⁺ 0.40 for NH₂⁺, 1.29 for →NH⁺, 4.72 for -NH⁺, 7.53 for -⁺N-N=N-N(C₂H₅)₂, and 10.74 for C(C₆H₄-)₃⁺, respectively. By using these C values, A values for inorganic and organic anions were determined. A values for inorganic anions were as follows: -11.06 for F^-, -9.07 for OH^-, -8.11 for NO₂^-, -8.08 for Cl^-, -7.05 for NO₃^-, -6.89 for Br^-, -5.80 for BF₄^-, -5.32 for I^-, -5.17 for SCN^-, -5.03 for ClO₄^-, and -4.45 for ReO₄^-, respectively. A values for anionic groups were as follows: -9.08 for -SO₃^-, -10.73 for -COO^-, and -7.38 for -OSO₃^-, respectively. By using the values of C and A, the extraction constants (logK_ex) for ion associate (C⁺·A^-) were estimated and compared with those obtained experimentally. The differences between them were smaller than ±0.3 log unit.

Journal

• BUNSEKI KAGAKU

  BUNSEKI KAGAKU 33 (1), 31-36, 1984

  The Japan Society for Analytical Chemistry

Keywords

• relative extractability of cations and anions
• estimation of extraction constants of ion associates
• extraction with chloroform

Details

• CRID: 1390001204052160896
• NII Article ID: 110002908767
• NII Book ID: AN00222633
• DOI: 10.2116/bunsekikagaku.33.31
• COI: 1:CAS:528:DyaL2cXhs1aks70%3D
• NDL BIB ID: 2972586
• ISSN: 05251931
• ISSN: http://id.crossref.org/issn/05251931
• Web Site: https://ousar.lib.okayama-u.ac.jp/19938
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I2972586
• Web Site: http://www.jstage.jst.go.jp/article/bunsekikagaku1952/33/1/33_1_31/_pdf
• Web Site: http://dl.ndl.go.jp/info:ndljp/pid/10890412
• Text Lang: ja
• Data Source:
  • JaLC
  • IRDB
  • NDL
  • Crossref
  • NDL-Digital
  • CiNii Articles
• Abstract License Flag: Disallowed