Study of the equilibrium of formation of arsenic(III) lacunar heteropolytungstates by Raman spectroscopy

被引：10

作者：

Detusheva, LG ^{[1
]}

Kuznetsova, LL ^{[1
]}

Dovlitova, LS ^{[1
]}

Likholobov, VA ^{[1
]}

机构：

[1] Russian Acad Sci, Siberian Branch, GK Boreskov Inst Catalysis, Novosibirsk 630090, Russia

来源：

RUSSIAN CHEMICAL BULLETIN | 2003年 / 52卷 / 02期

关键词：

heteropolytungstates; heteropolyanions; arsenic(III); ion equilibria; equilibrium constant; Raman spectroscopy; IR spectra;

D O I：

10.1023/A:1023454715292

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The formation of lacunar heteropolyanions (HPA): [AsW9O33](9-), [AS(2)W(19)O(67)(H2O)](14-), and [AS(2)W(20)O(68)(H2O)](10-) in aqueous solutions was investigated by Raman spectroscopy at [Na2HAsO3](0) = 0.1, [Na2WO4](0) = 0.9 mol L-1 and pH 9.4-1.6. The [AsW9O33](9-) HPA is characterized by the most intense band nu(s) (W=O) at 948 cm(-1) retaining its position in the pH range from 8.9 to 7.5. Under these conditions, the equilibrium constant of [ASW(9)O(33)](9-) formation from H2AsO3- and WO42- ions was estimated (logK = 87.0 +/- 1.0). The asymmetrical band at 952 cm(-1) corresponding to H-x[As2W19O67(H2O)]((14-x)-) shifts to 960 cm(-1) as the pH decreases from 6.5 to 5.5, which is due to the change in HPA protonation. The [As2W20O68(H2O)](10-) HPA is formed at pH 3.1-1.6; it is characterized by a band at 972 cm(-1).

引用

页码：370 / 374

页数：5

共 28 条

[1]

DETUSHEVA LG, 1990, KOORDINATS KHIM+, V16, P796

[2]

DETUSHEVA LG, 1991, KOORDINATS KHIM+, V17, P1078

[3]

DETUSHEVA LG, 1999, KOORDINATS KHIM, V25, P611

[4]

GUTSUL TD, 1992, KOORDINATS KHIM+, V18, P944

[5] HOMOGENEOUS CATALYSIS BY TRANSITION-METAL OXYGEN ANION CLUSTERS [J].

HILL, CL ;

PROSSERMCCARTHA, CM .

COORDINATION CHEMISTRY REVIEWS, 1995, 143 :407-455

[6] Formation and conversion of molybdophosphate and -arsenate complexes in aqueous solution [J].

Himeno, S ;

Hashimoto, M ;

Ueda, T .

INORGANICA CHIMICA ACTA, 1999, 284 (02) :237-245

[7] A novel polytungstate [As4W20O72(H2O)2]12- formed by connecting two α-B-AsW9O33 units by two unprecedented bridges O2AsOWO4(H2O). [J].

Jeannin, Y .

COMPTES RENDUS DE L ACADEMIE DES SCIENCES SERIE II FASCICULE C-CHIMIE, 1999, 2 (03) :161-165

[8] X-RAY STUDY OF (NH4)7[H2ASW18O60].16H2O - 1ST EXAMPLE OF A HETEROPOLYANION CONTAINING PROTONS AND ARSENIC(III) [J].

JEANNIN, Y ;

MARTINFRERE, J .

INORGANIC CHEMISTRY, 1979, 18 (11) :3010-3014

[9] W-183 NMR AND X-RAY STUDY OF A HETEROPOLYANION [AS2W21O69(H2O)]6- EXHIBITING A RARE SQUARE-PYRAMIDAL ENVIRONMENT FOR SOME TUNGSTEN(VI) [J].

JEANNIN, Y ;

MARTINFRERE, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (07) :1664-1667

[10] SYNTHESIS AND STRUCTURE OF POTASSIUM OCTATUNGSTODIARSENATE(III) [J].

LEYRIE, M ;

TEZE, A ;

HERVE, G .

INORGANIC CHEMISTRY, 1985, 24 (08) :1275-1277

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