含有冠醚基团的有机硅化合物 Ⅲ.烯氧甲基15-冠-5和18-冠-6的硅氢化

本文报道了烯丙氧甲基及十一烯氧甲基15-冠-5与18-冠-6的合成、硅氢化、固载化,以及所得到的气相法二氧化硅固载的冠醚和含冠醚侧基的有机硅树脂对苦味酸钠、钾的络合容量和正溴壬烷碘代反应的相转移催化活性。     

微粉型四钼酸铵热容的测定

Single phase of ammonium tetramolybdate in the micro power form was prepared from polyphase ammonium paramolybdate. Its heat capacity from 14.25℃ to 120.12 ℃ was measured by drop method and the result is
Cp=0.3936+7.4047×10-4T+6.3543×10-3T-2(J•K-1•g-1)     

Reversible Melting of Semi-Crystalline Polymers 2. Annealing Near to the Melting Point

Annealing experiments have been carried out at a few degrees below the melting point of different polyethylenes (LDPE, LLDPE, HDPE), of polypropylene (PP) and of Nylon-6. The heat capacities decrease during the annealing, within a 2-4 min time scale, to a lower value which corresponds to the extrapolated heat capacity values obtained for the cooling cycle when the polymer is cooled from the melt. Heat capacities in the heating cycle following the cooling cycle of PP, Nylon-6 and HDPE have the same value as during the cooling section. This is not the case for LDPE and LLDPE. Exothermic total heat flow in the cooling section following the annealing indicates that the crystallisation takes place during the cooling rather than during the annealing period. The total melting enthalpy measured before and after the annealing cycle is the same. The reversing heat flow shows an excellent fit to the change of the crystallinity measured by small angle scattering of synchrotron radiation during a heating cycle at temperatures below the melting peak. A coupled thermodynamic interaction of the crystalline and the amorphous phases is concluded from this study. This kind of interaction is possible at the lateral end of polymeric chains incorporated into the crystalline phase. This is an indication of the portion of tie molecules in the system, i.e. the portion of fringed micelle type of crystalline morphology with respect to that of folded chain lamellae. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and thermodynamic properties of a metal-organic framework: [LaCu6(μ-OH)3(Gly)6im6](ClO4)6

A metal-organic complex, which has the potential property of absorbing gases, [LaCu₆(μ-OH)₃(Gly)₆im₆](ClO₄)₆ was synthesized through the self-assembly of La³⁺, Cu²⁺, glycine (Gly) and imidazole (Im) in aqueous solution and characterized by IR, element analysis and powder XRD. The molar heat capacity, C_p,m, was measured from T = 80 to 390 K with an automated adiabatic calorimeter. The thermodynamic functions [H_T − H_298.15] and [S_T − S_298.15] were derived from the heat capacity data with temperature interval of 5 K. The thermal stability of the complex was investigated by differential scanning calorimetry (DSC).     

Electrochemical characterization of negative electrodes consisting of surface-modified Zr0.9Ti0.1(Ni1.1Co0.1Mn0.5V0.2Cr0.1)x Laves-phase alloys

Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy with a composition of Zr_0.9Ti_0.1Ni_1.1Co_0.1Mn_0.5V_0.2Cr_0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and diffusion path length of hydrogen.     

Heat conduction effects during the calorimetric determination of absorbed dose to water in radiotherapy beams

A transportable water calorimeter for the determination of the quantity of absorbed dose to water in radiotherapy beams has been developed at the PTB and is presented in detail in this investigation. Heat conduction effects occurring in the calorimeter are studied for different lateral sizes of high-energy photon beams, for different depth dose distributions of electron beams and for a scanned-beam irradiation with a heavy ion beam. The corresponding correction factors are calculated and arguments are given under which conditions these can adequately be applied.     

Theoretical study on the molecule C30H20: five carbon–carbon single bonds linking a dodecahedrane cage and a pentaprismane cage

Using geometry optimization and DFT method at the B3LYP/6-31G* level of theory for C₃₀H₂₀, an equilibrium geometry is identified that has the form of polyhedral hydrocarbon with five carbon–carbon single bonds linking a dodecahedrane cage and a pentaprismane cage. Thus, this molecule is a tri-cage molecule with two pentaprismane cages and one dodecahedrane cage. Vibrational frequencies and the infrared spectrum are computed at the same level of theory. The heat of formation for C₃₀H₂₀ has been estimated in this paper. The heat of formation of C₃₀H₂₀ as well as the vibrational analysis indicates that this molecule enjoys sufficient stability to allow for its experimental preparation.     

Analysis of the contribution of skeletal vibrations to the heat capacity of linear macromolecules in the solid state

Automatic computer programs are developed to calculate one- two-, and three-dimensional Debye functions. Prior tables of these functions are critically reviewed. Also, strategies are derived to calculate Debye temperatures from heat capacities. Both, simple three-dimensional Debye analyses and Tarasov analyses were carried out on 35 linear macromolecules. The experimental heat capacities for these analyses were collected in the ATHAS data bank. It is shown that the skeletal heat capacity of linear macromolecules is often best represented by only two vibrations per chain atom. For most of the all-carbon chain macromolecules the intramolecular skeletal heat capacity can be given by C_vs=D₁[520 (28/MW)^1/2] whereMW is the molecular mass andD ₁ represents the one-dimensional Debye function. Polyoxides show a higher intramolecular theta temperature, but a lower intermolecular theta temperature. Double bonds and phenylene groups in the chain increase the intramolecular theta temperature.Dedicated to Prof. Dr. F. H. Müller.On leave from the Lumumba Peoples' Friendship University, Moscow, USSR.     

Thermodynamics of phenylated polyphenylene between 0 and 340 K

In an adiabatic vacuum calorimeter, the temperature dependence of the heat capacity C _p of phenylated polyphenylene and initial comonomer 1,4-bis(2,4,5-triphenylcyclopentadienone-3-yl)benzene was studied between 6 and 340 K with an uncertainty of about 0.2%. In a calorimeter with a static bomb and an isothermal shield their energies of combustion DUcomb were measured. From the experimental data, the thermodynamic functions C _p ⁰ (T), H ⁰(T)-H ⁰(0), S ⁰(T)-S⁰(0), G ⁰(T)-H ⁰(0) were calculated from 0 to 340 K, and standard enthalpies of combustion ΔH _comb ⁰ and thermodynamic parameters of formation-enthalpies ΔH _f ⁰, entropies ΔH _f ⁰, Gibbs functions ΔG _f ⁰ - of the substances studied were estimated at T=298.15 K at standard pressure. The results were used to calculate the thermodynamic characteristics (ΔH _f ⁰ ,ΔS _f ⁰, ΔG _f ⁰) of phenylated polyphenylene synthesis in the range from 0 to 340 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

An equilibrium and calorimetric investigation of the hydrolysis of L-tryptophan to (indole + pyruvate + ammonia)

Apparent equilibrium constants and calorimetric enthalpies of reaction have been measured for the reaction L-tryptophan(aq) + H₂O(l) = indole(aq) + pyruvate(aq) + ammonia(aq) which is catalyzed by L-tryptophanase. High-pressure liquid-chromatography and microcalorimetery were used to perform these measurements. The equilibrium measurements were performed as a function of pH, temperature, and ionic strength. The results have been interpreted with a chemical equilibrium model to obtain thermodynamic quantities for the reference reaction: L-tryptophan(aq) + H₂O(l) = indole(aq) + pyruvate^–(aq) + NH ₄ ⁺ (aq). At T=25°C and I_m=O the results for this reaction are: K^o=(1.05±0.13)×10^–4, G°=(22.71±0.33) kJ-mol^–1, H°=(62.0±2.3) kJ-mol^–1, and S°=(132±8) J-K^–1-mol^–1. These results have been used together with thermodynamic results from the literature to calculate standard Gibbs energies of formation, standard enthalpies of formation, standard molar entropies, standard molar heat capacities, and standard transformed formation properties for the substances participating in this reaction.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.