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Abstract  

The complexes of [Sm(o-MOBA)3bipy]2·H2O and [Sm(m-MOBA)3bipy]2·H2O (o(m)-MOBA = o(m)-methoxybenzoic acid, bipy-2,2′-bipyridine) have been synthesized and characterized by elemental analysis, IR, UV, XRD and molar conductance, respectively. The thermal decomposition processes of the two complexes were studied by means of TG–DTG and IR techniques. The thermal decomposition kinetics of them were investigated from analysis of the TG and DTG curves by jointly using advanced double equal-double steps method and Starink method. The kinetic parameters (activation energy E and pre-exponential factor A) and thermodynamic parameters (ΔH, ΔG and ΔS) of the second-step decomposition process for the two complexes were obtained, respectively.

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Abstract  

A ternary binuclear complex of dysprosium chloride hexahydrate with m-nitrobenzoic acid and 1,10-phenanthroline, [Dy(m-NBA)3phen]2·4H2O (m-NBA: m-nitrobenzoate; phen: 1,10-phenanthroline) was synthesized. The dissolution enthalpies of [2phen·H2O(s)], [6m-HNBA(s)], [2DyCl3·6H2O(s)], and [Dy(m-NBA)3phen]2·4H2O(s) in the calorimetric solvent (VDMSO:VMeOH = 3:2) were determined by the solution–reaction isoperibol calorimeter at 298.15 K to be

\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[2phen·H2O(s), 298.15 K] = 21.7367 ± 0.3150 kJ·mol−1,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[6m-HNBA(s), 298.15 K] = 15.3635 ± 0.2235 kJ·mol−1,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[2DyCl3·6H2O(s), 298.15 K] = −203.5331 ± 0.2200 kJ·mol−1, and
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{s}} H_{\text{m}}^{\theta }$$ \end{document}
[[Dy(m-NBA)3phen]2·4H2O(s), 298.15 K] = 53.5965 ± 0.2367 kJ·mol−1, respectively. The enthalpy change of the reaction was determined to be
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{r}} H_{\text{m}}^{\theta } = 3 6 9. 4 9 \pm 0. 5 6 \;{\text{kJ}}\cdot {\text{mol}}^{ - 1} .$$ \end{document}
According to the above results and the relevant data in the literature, through Hess’ law, the standard molar enthalpy of formation of [Dy(m-NBA)3phen]2·4H2O(s) was estimated to be
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Updelta_{\text{f}} H_{\text{m}}^{\theta }$$ \end{document}
[[Dy(m-NBA)3phen]2·4H2O(s), 298.15 K] = −5525 ± 6 kJ·mol−1.

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Abstract  

The two complexes of [Ln(CA)3bipy]2 (Ln = Tb and Dy; CA = cinnamate; bipy = 2,2′-bipyridine) were prepared and characterized by elemental analysis, infrared spectra, ultraviolet spectra, thermogravimetry and differential thermogravimetry techniques. The thermal decomposition behaviors of the two complexes under a static air atmosphere can be discussed by thermogravimetry and differential thermogravimetry and infrared spectra techniques. The non-isothermal kinetics was investigated by using a double equal-double steps method, the nonlinear integral isoconversional method and the Starink method. The mechanism functions of the first decomposition step of the two complexes were determined. The thermodynamic parameters (ΔH , ΔG and ΔS ) and kinetic parameters (activation energy E and the pre-exponential factor A) of the two complexes were also calculated.

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Abstract  

The complex of [Nd(BA)3bipy]2 (BA = benzoic acid; bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction, and TG/DTG techniques. The crystal is monoclinic with space group P2(1)/n. The two–eight coordinated Nd3+ ions are linked together by four bridged BA ligands and each Nd3+ ion is further bonded to one chelated bidentate BA ligand and one 2,2′-bipyridine molecule. The thermal decomposition process of the title complex was discussed by TG/DTG and IR techniques. The non-isothermal kinetics was investigated by using double equal-double step method. The kinetic equation for the first stage can be expressed as dα/dt = A exp(−E/RT)(1 − α). The thermodynamic parameters (ΔH , ΔG , and ΔS ) and kinetic parameters (activation energy E and pre-exponential factor A) were also calculated.

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