산소-17 핵자기공명분광법을 이용한 디옥소우라늄(VI) 이온의 질산 이온과의 착물형성에 관한 연구

정우식

Journal of the Korean Industrial and Engineering Chemistry, Vol.3, No.2, 312-317, June, 1992

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산소-17 핵자기공명분광법을 이용한 디옥소우라늄(VI) 이온의 질산 이온과의 착물형성에 관한 연구

Study of Complex Formation of Dioxouranium(Ⅵ) Ion with Nitrate Ion by ¹⁷O NMR Spectroscopy

정우식

초록

디옥소우라늄(Ⅵ) (우라닐) 이온과 질산 이온과의 상호작용을 산소-17 핵자기공명분광법으로 연구하였다. UO₂NO₃⁺의 우라닐 산소 원자(이후 우라닐 산소)의 산소-17 공명신호는 우라닐 이온의 그것보다 낮은 자기장에서 나타났다. UO₂NO₃⁺의 안정도상수를 5, 15, 25, 35℃에서 질산 이온 농도에 따른 산소-17 화학적 이동의 변화로부터 구했으며, 그 값은 이온강도에 따라 달랐다. 안정도상수의 온도 의존성으로부터 계산한 열역학적 파라미터는 다음과 같다 : .ΔH=-(27.2±1.7)kJ mol^-1와 ΔS=-(110±7)JK^-1mol^-1. 우라닐 이온과 여러가지 음이온의 배위자와의 1 : 1 착물형성 반응에 대한 엔탈퍼와 엔트로피 사이에는 직선관계가 있었다.

The interaction of dioxouranium(Ⅵ)(uranyl) ion with nitrate ion has been studied by ¹⁷O NMR spectroscopy. The ¹⁷O resonance of uranyl oxygen atoms(uranyl oxygens hereafter) of UO₂NO₃⁺ was at lower field than that of uranyl ion. The stability constants of UO₂NO₃⁺ were obtained from the variation of ¹⁷O chemical shifts with nitrate-ion concentration at 5, 15, 25, 35℃ and depend on the ionic strength. Thermodynamic parameters calculated from temperature dependence of the stability constants were as follows : ΔH=-(27.2±1.7)kJ mol^-1 and ΔS=-(110±7)JK^-1mol^-1. There was a linear relationship between the enthalpy and entropy for 1:1 complex formation of the uranyl ion with a variety of anionic ligands.

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[1] Klemperer WG, Angew. Chem.-Int. Edit., 17, 246 (1978)

[2] Harris RK, Mann BE, "NMR and the Periodic Table," p. 383, Academic Press (1978)

[3] Kintzinger JP, Marsmann H, "Oxygen-17 and Silicon-29," p. 1, Springer-Verlag (1981)

[4] Jung WS, Tomiyasu H, Fukutomi H, Bull. Chem. Soc. Jpn., 58, 938 (1984)

[5] Jung WS, Tomiyasu H, Fukutomi H, Bull. Chem. Soc. Jpn., 60, 489 (1987)

[6] Betts RH, Michels RK, J. Chem. Soc., S, 286 (1949)

[7] Brooker MH, Huang CH, Sylwestrowicz J, J. Inorg. Nucl. Chem., 42, 1431 (1980)

[8] Ohashi H, Morozumi T, Nippon Genshiryoku Gakkaishi, 9, 65 (1967)

[9] Azenha MEDG, Burrows HD, Formosinho SJ, Leitao MLP, Miguel MGM, J. Chem. Soc.-Dalton Trans., 2893 (1988)

[10] Day RA, Powers RM, J. Am. Chem. Soc., 76, 3895 (1951)

[11] Ekstrom A, Loeh H, Randall CH, Szego L, Taylor JC, Inorg. Nucl. Chem. Lett., 14, 301 (1961)

[12] Jung WS, Ikeda Y, Tomiyasu H, Fukutomi H, Bull. Chem. Soc. Jpn., 57, 2317 (1984)

[13] Ikeda Y, Soya S, Fukutomi H, Tomiyasu H, J. Inorg. Nucl. Chem., 41, 1333 (1979)

[14] Harris RK, "Nuclear Magnetic Resonance Spectroscopy," p. 118, Pitman (1983)

[15] Marcantonatos MD, Deschaux M, Celardin F, Chem. Phys. Lett., 69, 144 (1980)

[16] Choppin GR, Radiochim. Acta, 32, 43 (1983)