여러가지 금속 이온과 Formylcarboxylate 리간드들과의 착물형성반응에 관한 열역학적 연구 = Complex formation of various metal ions with formylcarboxylate ligands

다국어 초록 (Multilingual Abstract)

Enthalpy changes and stability constants of the complexes between various metal cations and formylcarboxylate have been measured using potentiometric and titration calorimetric methods, in an ionic medium of o.1 M(NaClO₄) at 25℃. The metal cations studied in this work are bivalent ions of the first transition metal series and trivalent lanthanide series. The formylcarboxylates, used in this work as the ligands are 2-formylbenzoate, 4-formylbenzoate and glyoxylate. For the bivalent transition metal complexes, the order of Mn^2+< Co^2+< Ni^2+< Cu^2+> Zn^2+ has been found to hold for the stability of all complexes irrespective of the nature of the coordinated ligand. All copper formylcarboxylate complexes are formed with abnormally large endothermic enthalpy change, due to the tetragonal distortion of the octahedral symmetry, as a result of Jahn-Teller effect. For the trivalent lanthanide complexes, glyoxylate forms more stable complexes with the heavier lanthanide cations while 2-formylbenzoate and 4-formylbenzoate are similar to each other regardless of the atomic number of the elements. That order of the basicities of the ligands is glyoxylate< 4-formylbenzoate< 2-formylbenzoate does not consistence with the sequence of the stability of their complexes which is 4-formylbenzoate< glyoxylate< 2-formylbenzoate for a given transition metal and lanthanide elements. From the relation between the bascity and characteristic structure of the ligands it can be proposed that 2-formylbenzoate ligand may react strained seven-membered ring. The glyoxylate complex formation, appears to offer a more favorable orientation then the case of other two ligands, but reaction here may be inhibited by conversion of this acid by hydration to its gem-diol form. The 4-formylbenzoate ligand forms more stable complex with the metal ion through a conjugate π system then expected from its basicity, resulting of such a intealigand charge polarization in the complexation.

목차 (Table of Contents)

• 목차
• I. 서론 = 1
• II. 이론 = 10
• 1. 약산의 해리상수 = 12
• 2. 금속착물 형성반응의 안정도 상수 = 14
• 3. 수소 첨가반응의 엔탈피 변화(ΔH_HL)와 엔트로피 변화(ΔS_HL) = 15
• 4. 금속착물 형성반응의 엔탈피 변화(ΔH_ML)와 엔트로피 변화(ΔS_ML) = 16
• III. 실험 = 18
• 1. 시약 및 실험용액의 조제 = 18
• 2. 전위차 적정 = 19
• 2-1. 장치 = 19
• 2-2. 적정실험 = 19
• 3. 열량 적정 = 21
• 3-1. 적정 열량계의 설계 및 제작 = 21
• 3-2. 적정 열량계의 보정 = 26
• 3-3. 열량 계산 = 28
• 3-4. 적정 실험 = 38
• IV. 결과 및 고찰 = 39
• 1. 리간드산의 해리상수와 열역학적 함수 = 39
• 2. 금속착물의 안정도 상수와 열역학적 함수 = 45
• 2-1. 3d 전이금속착물 = 54
• 2-2. 4f 란탄족 금속착물 = 69
• V. 결론 = 89
• VI. References = 92
• VII. APPENDIX(I-II) = 96
• ABSTRACT = 198