Cryoscopy of Amine-Polytungstates

다중텅그스텐산 아민염의 분자량 측정

  • 변종홍 (한국과학기술연구소) ;
  • 연손수 (한국과학기술연구원 무기화학연구실)
  • Published : 1974.04.30

Abstract

Trioctylamine-and tricaprylylmethylammonium chloride-tungstate salts have been prepared by solvent extraction from the sodium tungstate solution of various acidities(pH = 2, 4, 6). The molecular weights of the amine-tungstate salts thus obtained could be cryoscopically measured in benzene by means of a home-built Wheatstone bridge utilizing thermistor with sensitivity of 1/$4000^{\circ}C$. The cryoscopic data along with the results of chemical analysis and infrared spectra of the salts indicate that the amine-tungstates prepared at pH = 2 and 4 are all metatungstate whereas the salt obtained at pH = 6 is an unknown form quite different from the expected paratungstate.R = 0.14. By hydrogen bonding a guanidyl nitrogen of a sulfaguanidine molecule is linked to the sulfonyl oxygens of the other molecules indirectly through two different water molecules. The role of water molecule is both a .nor and an acceptor in hydrogen-bonding formation and these hydrogen bonds are tetrahedrally o?ented. The hydrogen-bonding networks form infinite molecular layers parallel to (001) plane.

비수용성 긴고리 지방족 아민인$(n-C_8H_{17})_3N$$(n-C_8H_{17})_3NCH_3Cl$을 사용하여 산도가 틀린 텅그스텐산수용액(pH=2, 4, 6)으로 부터 용매추출법에 의하여 유기용매에 녹는 다중텅그스텐산아민염을 제조하는데 성공하였다. 제조된 텅그스텐산 아민염의 분자량을 벤젠용매에서 더미스트를 이용한 감도 1/$4000^{\circ}C$의 훼트스톤 브리지를 사용하여 측정할 수 있었다. 분자량 측정결과와 화학분석 및 적외선 스펙트럼으로 부터 pH=2, 4에서 생긴 아민염은 메타텅그스텐산염, pH=6에서 생긴 아민염은 파라텅그스텐산염이 아니고 미지의 새로운 다중텅고스텐산염임을 알 수 있었다.

Keywords

References

  1. Z. Naturforschung v.20b O. Glemser;W. Holznagel;W. Holtje;E. Schwarzmann
  2. Prog. Inorg. Chem. v.4 D. L. Kepert
  3. Proc. Rny. Soc. (London) v.A144 J. F. Keggin
  4. J. Korean Chem. Soc. v.16 Hoosung Lee;Young Sun Uh;Youn Soo Sohn
  5. J. Korean Chem. Soc. v.17 Young Sun Uh;Hoosung Lee;Youn Soo Sohn
  6. Experimental Physical Chemistry F. Daniels;J. W. Williams;P. Bender;R. A. Alberty;C. D. Cornwell
  7. Modern Aspects of Inorganic Chemistry H. J. Emeleus;J. S. Anderson
  8. Z. anorg. Chem. v.143 J. A. M. Van Liempt
  9. Z. anorg. Chem. v.177 F. Hoermann
  10. J. Gen. Chem. U.S.S.R. v.8 V. I. Spitsyn;I. M. Kuleshov;I. I. Tikhomirov
  11. Zhur Fiz. Khim. v.24 V. I. Spitsyn;I. M. Kuleshov