A study of the thermal decarboxylation of three perfluoropolyether salts

The thermal decarboxylation of three dicarboxylic perfluoropolyether potassium salts of relatively short chain length has been investigated and the products and kinetics of the main reactions have been defined. From the rate constants and Arrhenius parameters data, the second decarboxylation appears to be quantitatively rather close to the first.     

催化光度法测定痕量甲醛

基于磷酸介质中甲醛催化溴酸钾氧化溴甲酚紫的褪色反应 ,建立了测定痕量甲醛的方法。方法的检出限为 1.0× 10 - 5g·L- 1,线性范围为 0 .0 2 0～ 0 .4 8μg·ml- 1,方法简便 ,用于空气中测定痕量甲醛 ,结果满意。     

氟化钾团簇的相变、成核和重结晶的分子动力学模拟

我们利用Born-Mayer-Huggins相互作用势函数对(KF)_N(N=108，256，500和864)团簇进行了分子动力学(MD)模拟。为了避免周期性边界条件对相变、成核和重结晶的干扰作用，对体系采用了自由边界。基于MD模拟结果，对团簇的熔化温度、熔化焓、扩散系数、成核速率、固液界面自由能、临界核大小等进行了计算和讨论。在对(KF)₈₆₄双晶团簇的热退火模拟中，观察到了固态的重结晶和晶粒的生长。经典的成核理论成功地解释了(KF)₈₆₄双晶团簇的重结晶MD模拟结果。     

Combined study of thermochemical properties of nitroform and its salts

A combined method for determination of the standard enthalpies of formation of nitroform and its salts was proposed. The enthalpies of dissolution of nitroform and its ammonium, hydrazinium, guanidinium, and potassium salts in water were measured. The enthalpy of combustion of hydrazinium salt of nitroform was determined by a combustion calorimetry, and its standard enthalpy of formation was calculated. The enthalpy of formation of trinitromethyl anion in indefinitely diluted aqueous solution −24.94±0.79 kJ mol⁻¹, was calculated on the basic of the data obtained for enthalpies of formation and dissolution of ammonium and hydrazinium salts of nitroform. Standard enthalpies of formation of nitroform and its salts were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2451–2454, December, 1998.     

Ion-exchange selectivity of a network calixarene-containing polymer obtained by the template synthesis on Na<Superscript>+</Superscript>, K<Superscript>+</Superscript>, and Ba<Superscript>2+</Superscript> matrices

The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na⁺, K⁺, and Ba²⁺ as matrices was studied. The selectivity coefficients of ion exchanges Ba²⁺-H⁺, Na⁺-H⁺, K⁺-H⁺, Na⁺-K⁺, and Na⁺-NH₄ ⁺ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol⁻¹. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005.     

钾(Ⅰ)(苯并－15－冠－5)新型配合物的合成及性质

在非水溶剂中合成并－１５－冠－５与碘化钾,硫氰化钾及苦味酸钾形成的三种新型固体配合物,并进行了有关物理,化学性质表征,结果表明,钾（Ⅰ）离子不仅易苯并－１５－冠－５天成常见的１：２夹心式配合物,而且还能生成稳定的１：１型固体配合物。     

Synthesis and crystal structure of ternary molybdate compound K<Subscript>5</Subscript>Pb<Subscript>0.5</Subscript>Hf<Subscript>1.5</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>6</Subscript>

Single crystals of triple molybdate of composition 5:1:3 K₅Pb_0.5Hf_1.5(MoO₄)₆ have been grown and their crystal structure has been solved from X-ray diffraction data (an automated diffractometer X8 APEX, MoK _α -radiation, 2173 F(hkl), R = 0.0321). Trigonal unit cell parameters are: a = b = 10.739(2) Å, c = 37.933(9) Å; V = 3789(1) ų, Z = 6, ρ_calc = 4.014 g/cm³, space group \(R\bar 3\). Three-dimensional mixed framework of the structure is formed by two types of MoO₄ tetrahedra and Pb and Hf octahedra linking via common O-vertices. Potassium atoms of three types occupy large vacancies in the framework.     

Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide

Multiblock copolymers of ethylene oxide, with four and five different blocks, were synthesized by the sequential anionic polymerization of styrene, isoprene, 2-vinyl pyridine, t-butyl methacrylate, and ethylene oxide with benzyl potassium as an initiator. The monomer sequence was based on the relative nucleophilicity of the active centers. Characterization of the multiblock copolymers by size exclusion chromatography (with refractive-index and UV detectors), membrane osmometry, and NMR spectroscopy confirmed that benzyl potassium is an efficient initiator for the synthesis of well-defined multiblock multicomponent copolymers of ethylene oxide. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2166–2170, 2002     

Protonation and sodium ion-pairing of the sulfite ion in concentrated aqueous electrolyte solutions

A protocol has been developed for the reliable titration of aqueous sulfite solutions which minimizes photodecomposition effects. This procedure has been used to measure the protonation constants of the sulfite ion in aqueous solution by glass electrode potentiometry at 25.0‡C and ionic strengths (I) from 0.1 to 5.0M in NaCI media and atI = 1.0M in KC1 and Me₄NCl media. These measurements provided evidence of weak but significant ionpairing between SO2/3 -and Na⁺ with a formation constant of logK _Na = 0.431 in 1.0M Me₄NCl. This was in very good agreement with the value logK _Na = 0.410 measured directly by Na⁺ ion-selective electrode potentiometry. Evidence is also presented for an extremely weak association of K⁺ and SO ₂ ³ -with logK _k = 0.22 in 1.0M Me₄NCl.     

Molar conductance of aqueous solutions of sodium, potassium, and nickel trifluoromethanesulfonate at 25‡C

The electrical conductivities of aqueous solutions of NaCF₃SO₃, KCF₃SO₃, and Ni(CF₃SO₃)₂ have been measured at 25‡C in the concentration range 1 to 25X 10^-3 mol-dm^-3 The data approach the Onsager limiting law at low concentrations, leading to a limiting molar ion conductivity for the CF₃SO ₃ ⁻ ion of 44.5±0.2 S-cm²-mol^-1, based on standard values for the cations. Using a simple size parameter for unsymmetrical polyatomic ions, based on the ion geometry, it is shown that the well known empirical relation between the molar conductivities of symmetrical ions and their radii can be extended to include certain polyatomic anions including CF₃SO ₃ ⁻ . The results suggest that the CF₃SO ₃ ⁻ ion is either a weak structure breaker in aqueous solution or neutral in this respect.