THERMOCHEMISTRY AND MECHANISM ON THE PROCESS OF PREP ARING POWDER OF Bi_2O_3 USING MELT-ATOMIZING-COMBUSTION METHOD

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Thermochemistry on coordination behavior of samaric chloride hydrate with diethylammonium diethyldithiocarbamate

The complex of samaric chloride lower hydrate with diethylammoniumdiethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N_2atmosphere. The title complex was identified as Et_2NH_2[Sm(S_2CNEt_2)_4] by chemical and elementalanalyses, the bonding characteristics of which was characterized by IR. The enthalpies of solutionof samaric chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change ofliquid-phase reaction of formation for Et_2NH_2[Sm(S_2CNEt_2)_4] at different temperatures weredetermined by mi-crocalorimetry. On the basis of experimental and calculated results, threethermodynamic parameters (the activation enthalpy, the activation entropy, and the activation freeenergy), the rate constant, and three kinetic parameters (the apparent activation energy, thepre-exponential constant, and the reaction order) of liquid phase reaction of formation wereobtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by athermochemical cycle.

Thermochemistry on Coordination Behavior of Neodymium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of neodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N_2 atmosphere. The title complex was identified as Et_2NH_2[Nd(S_2CNEt_2)_4] by chemical and elemental analyses and the bonding characteristics of which was characterized by IR. The enthalpies of solution of neodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et_2NH_2[Nd (S_2CNEt_2)_4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid-phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.

Thermochemistry on Coordination Behavior of Praseodymium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of praseodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) has been synthesized conveniently in absolute alcohol and dry N_2 atmosphere. The title complex was identified as Et_2NH_2[Pr- (S_2CNEt_2)_4] by chemical and elemental analyses, the bonding characteristics of which were characterized by IR spectrum. The enthalpy of solution for praseodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K, and the enthalpy changes of liquid-phase reaction of formation for Et_2NH_2[Pr-(S_2CNEt_2)_4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid phase reaction of formation were obtained. The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.

Investigation on influence of alloying on phase transitions of duplex stainless steel based on thermochemical calculation

This paper investigated on influence of different alloying elements added into duplex stainless steel (DSS) on phase transitions using thermochemical methods in comparison with experiment.The results showed that the most possible species in the ferrite phase,austenite phase,σphase,Hcp phase,χphase,and carbide were Cr:Va-type,Fe:Va-type,Ni:Cr:Mo-type,Cr_(2)N-type,Fe_(24)Mo_(10)Cr_(24)-type,and Cr:Mo:C-type,respectively.Furthermore,the Ni,N,Cr,and Mo alloying had significant influences on the transition of each DSS phase.The Ni and N additions obviously raised the temperature at ferrite-1/austenite-1 balance while the Cr and Mo decreased the dual-phase balance temperature.In addition,the Ni addition can promote the precipitating ofσphase at relatively high temperature while the precipitating of Hcp phase at relatively low temperature.The Hcp phase andχphase can be obviously increased by the N addition.The introduction of Cr and Mo notably enhances the precipitation ofσphase.However,the promotion ofχphase precipitation is facilitated by the presence of Mo,while the Cr element acts as an inhibitor forχphase precipitation.Furthermore,the ferrite/austenite ratio tested by experiment was higher than that calculated by thermochemical methods,thus pre-designed solution temperature should be lower about 30-100℃than that calculated by thermochemical methods.

NUMERICAL SIMULATION OF THERMAL NON-EQUILIBRIUM RADIATION ON UNSTRUCTURED GRIDS

A numerical method is developed based on an unstructured mesh to compute an ionized hypersonic flowfield with radiation in the thermo-chemical nonequilibrium. The flowfield is described by multi-species NavierStocks equations. The chemical model includes 11 species （O2, N2, O, N, NO, NO^＋ , N^＋ , O^＋, N2^＋ , O2^＋, e^- ） and 20 reactions. For simulating the thermal non-equilibrium effect, the two-temperature model is considered. The finite volume method （FVM） used for the spatial and directional discretization of radiative transfer equation（RTE） is described for unstructured grids. The numerical code can handle different kinds of species and radiative bands in a gas thermodynamicly described by two temperatures. In particular, the Delta, Epsilon, Beta prime, and Gamma prime bands of NO are choosen and the distribution of the radiation intensity is obtained.

Oral absorption of hyaluronic acid and phospholipids complexes in rats

AIM： To prepare a complex of hyaluronic acid （HA） and phospholipids （PL）, and study the improvement effect of PL on the oral absorption of HA. METHODS： The complex of HA-PL （named Haplex） was prepared by film dispersion and sonication method, its physico-chemical properties were identified by infrared spectra and differential scanning calorimetry （DSC）. The oral absorption of Haplex was studied. Thirty-two healthy rats were divided into 4 groups randomly： （1） a normal saline （NS） control group; （2） an HA group; （3） a mixture group and （4） a Haplex group. After intragastric administration, the concentration of HA in serum was determined. RESULTS： The physico-chemical properties of Haplex were different from HA or PL or their mixture. After Haplex was administered to rats orally, the serum concentration of HA was increased when compared with the mixture or HA control groups from 4 h to 10 h （P 〈 0.05）. The AAUCo-12, of Haplex was also greater than that of the other three groups （P 〈 0.05）. CONCLUSION： The method of film dispersion and sonication can prepare HA and PL complex, and PL can enhance the oral absorption of exogenous HA.

Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb(Et_2dtc)_3(phen)

A ternary solid complex Yb（Et2dtc）3（phen） was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate （NaEt2dtc）, and 1, 10-phenanthroline （o-phen·H2O） in absolute ethanol. The bonding characteristics of the complex were characterized by IR. The result shows Yb3^＋ bands with two sulfur atoms in the Na（Et2dtc）3 and two nitrogen atoms in the o-phen. The enthalpy change of liquid-phase reaction of formation of the complex △rHm^θ（Ⅰ）, was determined as being （-24.838±0.114） kJ·mol^-1 at 298.15 K, by an RD-496 Ⅲ type heat conduction microcalormeter. The enthalpy change of the solid-phase reaction of formation of the complex △rHm^θ（s）, was calculated as being （108.015±0.479） kJ·mol^-1 on the basis of an appropriate thermochemistry cycle. The thermodynamics of liquid-phase reaction of formation of the complex was investigated by changing the temperature during the liquid-phase reaction. Fundamental parameters, the activation enthalpy, △H≠^θ, the activation entropy, △S≠^θ, the activation free energy,△G≠^θ, the apparent reaction rate constant k, the apparent activation energy E, the pre-exponential constant A, and the reaction order n, were obtained by a combination of the reaction thermodynamic and kinetic equations with the data from the thermokinetic expenments. At the same time, the molar heat capacity of the complex cm. p, Was determined to be （86.34± 1.74） J·mol^-1·K^-1 by the same microcalormeter. The constant-volume combus- tion energy of the complex, △cU, was determined to be （ - 17954.08 ± 8.11） kJ·mol^-1 by an RBC-Ⅱ type rotating-bomb calo- rimeter at 298.15 K. Its standard enthalpy of combustion, △cHm^θ, and standard enthalpy of formation, △fHm^θ, were calculated to be （- 17973.29±8.11） kJ·mol^-1 and （-770.36±9.02） kJ·mol^-1, respectively.

Thermochemical Study on Ternary Solid Complex of La(Gly)_2(Ala)_3Cl_3·2H_2O(s)

The complex of lanthanum chloride with Glycine and Alanine,La（Gly）2（Ala）3Cl3·2H2O,was synthesized and characterized by IR,elementary analysis,thermogravimetric analysis,and chemical analysis.The dissolution enthalpies of LaCl3 ·7H2O（s）,2Gly（s）＋ 3Ala（s）and La（Gly）2（Ala）3Cl3 ·2H2O（s）were determined in 2 mol·L-1 HCl by a solution-reaction isoperibol calorimeter.By designing a thermochemical cycle in terms of Hess＇ Law and through calculation,the reaction enthalpy of lanthanum chloride seven-hydrate with Glycine and Alanine was obtained：ΔrHθm（298.15 K）=（29.652±0.504）kJ·mol-1,and the standard enthalpy of formation of La（Gly）2（Ala）3Cl3·2H2O（s）ΔfHθm [La（Gly）2（Ala）3Cl3·2H2O,s,298.15 K]=-4467.6±8.3 kJ·mol-1.

Thermochemical Properties of the Complexes RE(HSal)_3·2H_2O (RE=La,Ce,Pr,Nd,Sm)

Five solid rare earth salicylate complexes were synthesized by low hydrated lathanide chloride and salicylic acid. The complexes in this experiment were identified as the general formula RE（HSal）3·2H2O（RE = La, Ce, Pr, Nd, Sm） by elemental analysis and EDTA volumetric analysis. IR spectra of the complexes show that carboxyl of salicylic acid coordinates to RE^3＋ ions. Electrochemical behaviors of the complexes on the glass-carbon electrode were researched with cyclic voltammetry （CV）. It is indicated that the electrochemical process of the complexes is a one-electron redox process and the electrochemical reversibility of complexes is less than that of the lanthanide chlorides. The constant-volume combustion energies of complexes,△c U, were determined with a precise rotating-bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, △cH^θm, and standard molar enthalpies of formation, △fH^θm, were calculated.

Thermochemical Study of Coordination of Holmium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of holmium chloride hydrate with diethylammonium diethyldithiocarbamate(D-DDC) was synthesized via mixing their solutions in absolute alcohol under a dry N 2 atmosphere. The elemental and chemical analyses show that the complex has the general formula Et 2NH 2[Ho(S 2CNEt 2) 4]. It was also characterized by IR spectroscopy. The enthalpies of the dissolution of holmium chloride hydrate and D-DDC in absolute alcohol at 298.15 K, and the enthalpy changes of liquid-phase reactions of the formation of Et 2NH 2[Ho(S 2CNEt 2) 4] at different temperatures were determined by microcalorimetry. On the basis of experimental and calculated results, three thermodynamic parameters(the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters(the apparent activation energy, the pre-exponential constant and the reaction order) of the liquid-phase reaction of the complex formation were obtained. The enthalpy change of the solid-phase complex formation reaction at 298.15 K was calculated by means of a thermochemical cycle.

Attack of Tunisian Phosphate Ore by a Mixture of Sulfuric and Phosphoric Acid: Thermochemical Study by Means of Differential Reaction Calorimetry

A calorimetric, Differential Reaction Calorimetry (DRC), study of the thermochemical of the attack of a phosphate ore from Gafsa region (Tunisia) by a mixture of sulfuric and phosphoric acid is undertaken at different solid-liquid ratio and different temperature. The plot of the quantity of heat measured by integrating the raw signal as a function of the dissolved mass in the same volume solution at 25℃ presents three straight segments attributed at the formation of the hemihydrate (CaSO4·1/2H2O:HH), the dihydrate (CaSO4·2H2O:DH) or a mixture of these two products checked by X-ray diffraction, infrared spectroscopy and thermal analysis (Differential Scanning Calorimeter: DSC). The attack by the acid mixture was performed at higher temperature and showed in addition the formation of another form of calcium sulfate:anhydrous (CaSO4:AH). Moreover, the variation of mass enthalpy versus temperature presents a break at the T = 45℃. According to our results, it seems that the effect of the temperature on the sulfo-phosphoric attack reaction on the natural phosphate (NP) generates a change of mechanism at around 45℃.

Analysis of Time-Dependent Density Functional Theory of Transition Wavelengths of Thioaldehydes and Thioketones

Thioaldehydes and thioketones are candidates of new photoluminescence materials. The time-dependent density functional theory is applied to calculate the absorption and emission wavelengths of ten thiocarbonyl compounds using both B3LYP and PBEO functionals. The theoretical results are in agreement with the measurable ones. Furthermore, it is found that the maximum absorption and emission wavelengths are linearly correlated to the C-S bond lengths.

Thermochemical Study on Coordination Complex of Neodymium Trichloroacetic Acid with 8-Hydroxyquinoline

Two coordinate reactions, NdCl 3·6H 2O(s) +3CCl 3COOH(s)( or TCA) =Nd(TCA) 3·3H 2O(s) +3HCl(g) +3H 2O(l) and Nd(TCA) 3·3H 2O(s) +2C 9H 7NO(s)= Nd(TCA)(C 9H 6NO) 2 (s) +2CCl 3COOH(s) +3H 2O(l), were studied by the classical solution calorimetry at 298.15K. The molar dissolution enthalpies of the reactants and the products in certain solvent (the first reaction in 1 mol·L -1 HCl, the second in a mixed solution consisting of absolute ethyl alcohol, dimethyl sulfoxide and 4 mol·L -1 HCl ) were measured by using an isoperibol calorimeter at 298.15K . From the results and other auxiliary quantities, the standard molar formation enthalpies of [Nd(TCA) 3·3H 2O,s,298.15K] and [Nd(TCA) (C 9H 6NO) 2 ,s, 298.15K] are determined as Δ fH m °[Nd(TCA) 3·3H 2O,s,298.15K]= -3053.3 kJ·mol -1 and Δ fH m° [Nd(TCA) (C 9H 6NO) 2 ,s, 298.15K] = -1355.6 kJ·mol -1 .

Standard energies of combustion and standard enthalpies of formation for the complexes RE (Et_2dtc)_3(phen) (RE = Ho,Er,Tm,Yb,Lu)

The treatment of RECl3.xH2O （RE = Ho, Er, Tm, Yb, Lu; x = 3-4） with sodium diethyldithiocarbamate （NaEtEdtc-3H2O） and 1,10-phenanthroline hydrate （o-phen.H2O） in absolute ethanol yielded five ternary solid complexes RE（EtEdtC）a（phen）. IR spectra of the complexes showed that RE^3＋ coordinated to two sulfur atoms in NaEt2dtc and two nitrogen atoms in o-phen. The constant-volume energies of combustion of the complexes have been determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion and standard enthalpies of formation were calculated.

A Thermochemical Study of the Reaction of Lanthanum Nitrate with Alanine

The standard molar reaction enthalpy of the solid-solid coordination reaction La(NO3)3. 6H2O (s) +4Ala(s) (Ala is Alanine)=La(NO3)3·(Ala)4·H2O(s) + 5H2O(1) was studied by using classical solution calorimetry. The molar dissolution enthalpies of the reactants and the product of the solid-solid coordination reaction in 2 mol/L HCl were measured by using an isoperibol calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpy of [La (NO3)3·(Ala)4·H2O, s, 298. 15 K] has been determined to be △fHm[La(NO3)3·(Ala)4·H2O, s, 298. 15 K]=-3 864. 248 kJ/mol.

Phase Chemistry of the Complexes of RE Amino Acids

Forty three phase diagrams of ternary system concerning rare earth salts, α amino acids and water, which were constructed by phase equilibrium methods, were expounded. The influences of the factors such as cations, anions, the structure of amino acids, temperature on the phase diagrams were discussed. Under the guidance of phase equilibrium results, over 150 new solid complexes were prepared. IR, reflecting, UV, FS, and Raman spectra for these complexes were investigated and the regularity of 'tripartite effect', 'tetrad effect', 'Nephelanxetic effect', 'Oddo Harkins' was observed. Thermal decomposition processes of the complexes were confirmed. Based on the comparison with the known crystal structures of rare earth amino acid complexes, an estimation method for predicting the crystal structure data of series complexes was founded. The constant volume combustion energies of the complexes were determined by RBC 1 type rotating bomb calorimeter. The standard enthalpies of combustion and standard enthalpies of formation were calculated for these complexes.

Thermochemical Study of Lanthanum Complex Crystal with β-Alanine

Lanthanum complex crystal with β alanine (1∶3) was synthesized. Through the DTA,TG,chemistry analysis and comparison with literature, it shows that its form is {[La 2(β ala) 6· (H 2O) 4](ClO 4) 6·H 2O} n , and its purity is 98.86%. The dissolution enthalpy of the reactants and products in 2 mol·L -1 HCl solution (298.15K) was measured by using the isoperibol reaction calorimetry. Δ rH m was calculated by a designed thermochemical cycle of the coordination reaction. From the results and other auxiliary quantities, the standard molar enthalpy of formation of [La 2(β ala) 6·(H 2O) 4](ClO 4) 6·H 2O is obtained to be Δ fH m°{[La 2(β ala) 6·(H 2O) 4](ClO 4) 6·H 2O} = - 7062.911 kJ·mol -1 .

Microcalorimetric Study of the Effect of Porphyrin－Cholesterol Esters on Cancer Cells HL－60

By using an LKB-2277 Bioactivity Monitor, the effect ofporphyrin-cholesterol esters on cancer cells RL-60 were examined at 25℃.There is a dirrerence in the shape of the thermogenesls curve samong different kinds or Porphyrln-cholesterol esters,and the death rate or HL-60 cells is also different. The results show that porphyrin-chsterol esters can powerfully inhibit their metabolism, the inhibitory sequence is Ⅱ >I >Ⅲ,but the inhibitory way of each ester is different.

Thermochemical properties of Ternary Complex Yb[(C_5H_8NS_2)_3(C_(12)H_8N_2)]

A novel ternary solid complex, Yb （C5H8NS2）3 （C12H8N2）, was obtained from treating hydrous ytterbium chloride, ammonium pyrrolidin- edithiocarbamate （ APDC ） and 1, 10-phenanthroline （o-phen· H2O） in absolute ethanol, and characterized by elemental analysis. The enthalpies of solution of hydrous ytterbium chloride, APDC, o-phen·H2O, the mixture of APDC with o-phen· H2O in absolute ethanol at 298. 15 K, and the enthalpy changes of liquid- phase reaction of formation for Yb （ C5H8NS2 ）3 （ C12H8N2） at different temperatures were measured by using a RD496-Ⅲ microcalorimeter. Fundamental paconduction microcalorimeter, determining the specific heat a calculation model for capacity of solid subrameters, the activation enthalpy （ΔH≠^θ）, the activation entropy （ΔS≠^θ）, the activation free energy （ΔG≠^θ）, the apparent reaction rate constant （k）, the apparent activation energy （ E ）, the pre-exponential constant （A） and the reaction order （n）, were obtained by the combination of the thermochemical data of the reaction and kinetic equations with the data of thermokinetic experiments. The enthalpy change of complex formation from the reaction of the regents in solid phase, ΔrH≠^θ（s）, was calculated on the basis of an appropriate thermochemical cycle and other auxiliary thermodynamic data. Based on a RD496-Ⅲ heat stance was developed, and the title complex, c m, were accordingly determined.