INTERPRETATION OF THE ACID-BASE-EQUILIBRIUM OF HUMIC-ACID BY A CONTINUOUS PK DISTRIBUTION AND ELECTROSTATIC MODEL

被引:57
作者
FUKUSHIMA, M [1 ]
TANAKA, S [1 ]
HASEBE, K [1 ]
TAGA, M [1 ]
NAKAMURA, H [1 ]
机构
[1] HOKKAIDO UNIV,GRAD SCH ENVIRONM EARTH SCI,DIV MAT SCI,SAPPORO,HOKKAIDO 060,JAPAN
关键词
ACID-BASE EQUILIBRIA; HUMIC ACID;
D O I
10.1016/0003-2670(94)00471-W
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
Acid-base equilibria of a humic al:id were characterized by considering ionic group heterogeneity and electrostatic effects. The continuous pK distribution model, in which acidic functional groups having two centers of distribution were assumed in the humic molecule, was adapted to the experimental titration data by non-linear least square regression analysis. Excellent curve-fitting was obtained, and two centers of pK distribution (mu(1) and mu(2)) and the total amounts of functional groups (C-A1 and C-A2) were evaluated. It was suggested that there are strong and weak acidic groups in the humic molecule and that they continuously deprotonate;according to their pK distribution. The mu values were evaluated in media of various ionic strength (I = 0.004-1); mu(1) (strong: groups): 3.4-5.1, mu(2) (weak groups): 6.0-7.9, and the ratio of C-A1 to C-A2 was ca. 5:2. The electrostatic model including the Debye-Huckel theory was adapted to evaluate the intrinsic dissociation constants, pK(i,int). From the relationship between the mu values and I-1/2, the intrinsic pK(i) values of two centers of distributions, mu(int), could be evaluated; mu(1,int),int: 3.03, mu(2,int): 5.12. The intrinsic pK distribution and the species distribution curves were calculated under electrostatic-free conditions. Investigation of Fourier transform infrared spectra and the species distribution curves suggested that the two different types of carboxylic groups would contribute to the pK distribution of each functional group.
引用
收藏
页码:365 / 373
页数:9
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