Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Studies of Magnesium-Eriochrome Black T Complex in Acetonitrile

Acetonitrile에서의 Mg-EBT$^-$ 착물에 관한 연구

  • Doo Won Park (Department of Chemistry, College of Liberal Arts & Sciences, Kyungpook National University) ;
  • Won Hyung Choi (Busan Custom's Laboratory) ;
  • Heung Lark Lee (Department of Chemistry, College of Liberal Arts & Sciences, Kyungpook National University)
  • Published : 1973.08.30
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Abstract

Complex formation of magnesium-Eriochrome Black T at constant ionic strength and hydrogen ion concentration have been studied spectrophotometrically in acetonitrile solution. The measured pH values were calibrated with standard buffer solutions by using a glass electrode Ag/0.1M $AgNO_3$ reference electrode couple. The results are as follows;$E_{glass}=716+59.1\;logA_{H+}[mv]$+(in mv. vs. Ag reference electrode for picric acid $-10^{-3}M$ tetramethylammonium picrate buffer), and $E_{glass}=1,193+59.1\;logA_{H+}[mv]$(in mv. vs. Ag reference electrode for 1,3-diphenylguanidine $-3{\times}10^{-3}M $ 1,3-diphenylguanidine perchlorate buffer). The acid dissociation exponent of ligand, $ pK_{H,EBT-}$was found to be 9.1. The conditional formation constants of $MgEBT^{-}$complex by log-ratio method were 3.97 (when m = 2) and 5.02 (when m = 1) as $log K_n$, respectively, for the reaction of $H_mEBT^{(3-m)-} + Mg^{2+} {\leftrightarrow}MgEBT^{-} + mH^{+}$. The present study showed that$MgEBT^{-}$ has the composition of 1:1 which agrees with the result of Schwarzenbach et al. in aqueous solution.

Mg(II)과 Eriochrome Black T가 Acetonitrile용액속에서 반응하여 만든 착물을 일정한 이온의 세기와 일정한 수소이온농도에서 분광광도법으로 연구했다. 유리전극과 Ag/0.1 M $AgNO_3$기준전극쌍을 써서 Acetonitrile 용액속에서 측정한 pH 값은 표준완충용액으로 검정했으며 그 결과는 다음과 같다. Picric acid$-10^{-3}M$ tetramethylammonium picrate 완충용액에 있어서는 은기준전극에 대한 유리 전극의 $25^{\circ}C$에서의 전위는 $E_{glass}=716+59.1logA_{H+}[mv]$이고, 1,3-Diphenylguanidine$-3{\times}10^{-3}M $1,3-diphenylguanidine perchlorate 완충용액에서는 $E_{glass}=1,193+59.1 logA_{H+}[mv]$이다. 리간드 Eriochrome Black T의 산해리지수$ pK_{H,EBT-}$는 9.1이었으며, 반응 $H_mEBT^{(3-m)-} + Mg^{2+} {\leftrightarrow}MgEBT^{-} + mH^{+}$ 으로 생성된 착물 $MgEBT^{-}$의 조건안정도상수를 log-ratio method으로 구하니 m이 2일때는 $logK_{MgEBT^-} + 3.97$이고, m이 1일 때는 $logK_{MgEBT^-} + 5.02$이었다. 착물의 조성은 수용액에서 Schwarzenbach씨 등이 구한 결과와 같이 비수용매 Acetonitrile속에서도 한 종류의 착물 $MgEBT^{-}$만이 생성됨을 알 수 있었다.

Keywords

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