光度法测定铋(Ⅲ)与N-苯基硫脲配合反应的热力学参数

前人对于N-苯基硫脲(PTU)作为配位体与金属离子形成配合物的稳定性的研究工作颇少.近年来有用电位法测定Cu(Ⅰ),Ag(Ⅰ),Cd(Ⅱ),Zn(Ⅱ)与PTU所成配合物平衡常数的报道;但研究上述配合反应的热力学参数的报道仍较少见.PTU与Bi(Ⅲ)在高氯酸根存在下可形成橙黄色的配合物,其晶体Bi(PTU)_5(ClO_4)_3已经分离而     

p-CH3C6H4SR型硫醚与钯(II)配合物热分解反应动力学

热重分析(TG)和微商热重法(DTG)广泛应用于各个研究领域,用非等温热重法测定固体化合物的热分解动力学参数已有报导.许多作者提出各种不同的数据处理方法.本文用的ρ-CH_3C_6H_4SR 型硫醚对钯的萃取具有选择性好、分配比高、气味较小、易溶于脂肪烃类溶剂、易于合成、是很有发展前途的一类萃取剂.我们合成五种ρ-CH_3C_6H_4SR(R:n-C_4H_9,n-C_6H_(13),n-C_8H_(17),n-C_(10)H_(21),n-C_(12)H_(25))型硫醚与钯(Ⅱ)的配合物,用TG-DTG 法研究它们的热分解过程,用微商法(Freeman-Carroll 方程)及积分法(Coats-Redfern 方程)获得了这些配合物的热分解动力学参数.     

DSC法研究液晶物质2-(4-烷氧苯基)6-取代苯并噻唑的相变热性质

The phase transitions of a new group of mesogens, 2-(4-alkoxyphenyl)-6-substituted benzothiazoles were thermodynamically studied by DSC, and their transition temperatures and enthalpy changes were measured, from which the transition entropy changes were calculated. The results obtained were discussed. In addition, the phe-nomenon of super-cooling of the compounds were quantitatively observed.     

光度法测定铋(III)与N-苯基硫脲配合反应的热力学参数

The stability constants of complexes of N-phenylthiourea with bismuth (III) in 1M perchloric acid have been studied spectrophotemetrically by the method of corresponding solutions. The enthalpy change ΔH5^0 is obtained from the temperature coefficient data. The Gibbs free energy changes ΔG5^0 and the entropy changes ΔS5^0 are calculated from known formulas respectively. The experimental results are discussed. The successive accumulative stability constants and thermodynamic parameters ΔH5^0, ΔG5^0, ΔS5^0 are listed in Table 6 of the Chinese Text.     

Thermal Behavior and Decomposition Kinetics of the Complexes of CuX2 （X=NO3, Br, CI and CIO4） with 3,3＇-Dimethyl-1 -（1 H-1,2,4-triazol-1-yl）-2-butanone

The thermal behaviors of the complexes of Cu(DMTZB)4X2 (DMTZB=3,3‘-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, X=NO3 or ClO4) and Cu(DMTZB)2 X2 (X=Br or Cl) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC, EDS and elemental analysis techniques. The resuits showed that their decomposition proceeded in three different ways mainly depending on the anions in the molecules. The heat effect associated with the decomposition step of DMTZB molecules was also different. The decomposition mechanisms and the kinetic parameters of DMTZB were determined and calculated by jointly using four methods, which showed that its pyrolysis was controlled by D3 mechanism but with different activation energies and pre-exponential factors for different complexes.     

Non-Isothermal Kinetics of the Decomposition Reaction of Cluster [Ag3WS3Br]（PPh3）3 and [Cu3WS3Br]（PPh3）3

The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolution was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase composed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.     

热分析动力学的新进展

综述了热分析法研究非均相体系反应动力学方面的进展，评述了热分析动力学(TAK)现用方法的成功和局限，介绍了新的分析方法和新技术。     

用过氧化氢氧化溴邻苯三酚红的催化动力学光度法测定钢中的微量铬

提出了借助于微酸性溶液中用过氧化氢催化氧化溴邻苯三酚红测定微量铬（Ⅵ）的方法,研究了指示反应的最佳条件和各种离子的干扰影响。用Ａｒｒｈｅｎｉｕｓ方程计算了催化与非催化反应表观活化能。校准曲线的线性范围为０．１－０．６μｇＣｒ（Ⅵ）／２５ｍＬ。检出限为９．１×１０＾－１０ｇ／ｍＬ。方法成功地应用于钢中微量铬的测定 。     

对甲苯基烷基亚砜与钯(Ⅱ)配合物的合成及热分析研究

对甲苯基烷基亚砜(RSOPhCH_3)对钯的萃取研究及其与钯(Ⅱ)的固体配合物的合成迄今尚未见报道。本文首次制备了五种不同取代烷基的系列配体的钯(Ⅱ)配合物(R=n-C_4H_9,C_6H_(13),C_8H_(17),C_(10)H_(21)和C_(12)H_(25)),采用元素分析、红外光谱等方法鉴定其组成。由于研究该系列配合物的性质,如热稳定性等能有助于对它们萃取机理的进一步探索,因此,本文应用热重分析法(TG-DTG)研究了配合物的热分解过程,分别应用Freeman-Carroll,Coats-Redfern和Kissinger方程获得了它们的热分解活化能,并讨论了配合物的热分解行为与配合物配体中取代烷基之间的关系。     

四种苯甲酰丙酮合铜和1，1，1-三氟-3-(2-噻吩基)丙酮合铜的偶氮二吡啶长链配合物的热分析研究

用热重法(TG)研究了4种苯甲酰丙酮合铜和1，1，1-三氟-3-(2-噻吩基)丙酮合铜的偶氮二吡啶一维长链聚合配位化合物在动态氮气气氛下的热行为，结合元素分析和能谱技术，确定了各步分解的组分，并讨论了其晶体结构与热性质的关系。应用新的非线性等转化率法，并结合其他方法考察了各步分解反应的属性，进行了动力学分析，并试对传统动力学方法的适用性进行了讨论。