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.     

The solubilization of alcohols in micellar solutions

The specific conductivities of dodecyldimethylbenzylammonium bromide (C12BBr) have been determined in aqueous butanol and aqueous benzyl alcohol solutions in the temperature range of 5-40°C. From these data the temperature dependent critical micelle concentration (cmc) was determined. The molar fraction of alcohol in the micelle was estimated using the theory suggested by Motomura et al. for surfactant binary mixtures. The thermal properties such as standard Gibbs free energy, enthalpy and entropy of solubilization of alcohols in the micelles were estimated for the phase separation model. The change in heat capacity upon solubilization of alcohol in the micelle has been estimated form the above properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

On the applicability of the “abt” concept

Kaiser's “abt” concept rests on the experimental establishment of a linear relation between band width at half height, b_0.5, and capacity ratio, k, according to His column specification quantity, h_real, is dependent on the square of the slope a, obtained from a linear regression analysis based on this relation. It is shown in the present paper that an improvement of the experimental conditions leading to a lower extra-column contribution to band broadening, b, introduces a tendency towards a negative curvature in the plot at low k values. The mean slope increases, and an uncritical linear regression would yield an h_real-value which is higher than before and which would be in the opposite direction to the requirements of a reliable column specification. Generally the linear regression analysis has to be moved to higher k regions in cases of curvature, especially as it is also shown that h_real is an estimation of the traditional HETP value, H∞, that would be obtained when k approaches infinity. This theoretically expected relation is a strong motivation for the use of h_real as a column specification, since the b_0.5-value associated with H∞ is expected to be practically independent of b.     

Apparent molar heat capacities of aqueous solutions of acetic,propanoic and succinic acids,sodium acetate and sodium propanoate from 300 to 525 K and a pressure of 28 MPa

The apparent molar heat capacities of dilute aqueous solutions of acetic, propanoic and succinic acid and sodium salts of the two monofunctional acids were measured at 300 Kp,2 ^o . After subtracting the heat capacity of a point mass, the remaining heat capacity was successfully decomposed into functional group contributions at all temperatures. Together with the results of our previous paper on alcohols and diols the heat capacity contributions of the CH₂, CH₃, OH, COOH, (COOH)₂, and COONa groups are now available and these allow reasonably accurate predictions of the heat capacities of all compounds composed of these groups in this temperature range.     

Thermodynamics of dimethylene urethane and poly(dimethylene urethane) in the range from T → 0 to 490 K at standard pressure

By high-precision dynamic calorimetry the temperature dependences of heat capacity of dimethylene urethane (DMU) between 320 and 370 K and partially crystalline poly(dimethylene urethane) (PDMU) in the range 326-490 K at standard pressure have been determined within ±1.5%. The thermodynamic characteristics of fusion of the substances, namely the temperature interval of melting, temperature, enthalpy and entropy of fusion, as well as the characteristics of devitrification and glassy state for poly(dimethylene urethane) have been estimated. The first and the second cryoscopic constants have been calculated for dimethylene urethane. The experimental data obtained in the present work and literature findings on the heat capacity of the substances were used to calculate their thermodynamic functions: the heat capacity C°_p (T), enthalpy H°(T)−H°(0), entropy S°(T) and Gibbs function G°(T)−H°(0) over the range from T→0 to (370-480) K. Based on the data, the thermodynamic characteristics of polymerization process with five-membered ring opening Δ_polH°, Δ_polS° and Δ_polG° of dimethylene urethane with the formation of linear partially crystalline poly(dimethylene urethane) have been evaluated.     

低于300℃时两种氧化铈材料对稀燃阶段NOx存储性能的影响

研究了低于300 ℃时两种氧化铈对稀燃阶段NO_x存储性能的影响,催化剂由2%（w）Pt/Al₂O₃（PA）与CeO₂-X（X=S,I）机械混合制备. X射线衍射（XRD）,BET表面积和扫描电子显微镜（SEM）用于表征材料的物理结构. X射线光电子能谱（XPS）和H₂程序升温还原（H₂-TPR）用于表面Ce³⁺和活性氧定量. 原位漫反射傅里叶变换红外光谱（in-situ DRIFTS）用于分析表面NO_x吸附物种. 相比于CeO₂-I,CeO₂-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce³⁺浓度. 因而,Pt/Al₂O₃+CeO₂-S 表现出优异的NO_x存储能力. 此外,PA+CeO₂-X（X=S,I）上存在Pt 与CeO₂之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NO_x存储. PA+CeO₂-S上的这种相互作用要强于PA+CeO₂-I. 研究表明,表面Ce³⁺浓度和活性氧含量对NO_x存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈（ACS,ACI）之间的相互作用降低,并且两种氧化铈NO_x存储性能显著下降. 另外,与PA+ACS（ACI）相比,PA+PACS（PACI）样品NO_x存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成.     

Synthesis and Investigation of Soluble Polymer-supported Dendrimers

Poly（ethylene glycol） （PEG）-supported dendrimers have been synthesized using 2.4,6-trichloro-1,3,5-triazine （TCT） as dendrons and tris（hydroxymethyl）aminomethane as tinkers with high loading capacity, excellent solubility and thermal stability by divergent method. The new synthesized PEG-supported G2.0 dendrimer has 10 times as large functional group loading capacity as commercial PEG3400 with overall yield 44.0%.     

Thermodynamic properties of hydrated sodium l-threonate Na(C4H7O5)·H2O(s)

Low-temperature heat capacities of the compound Na(C₄H₇O₅)·H₂O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are Δ_transH_m = (5.75 ± 0.01) kJ mol⁻¹ and Δ_transS_m = (18.47 ± 0.02) J K⁻¹ mol⁻¹. The enthalpy and entropy of the dehydration are Δ_dH_m = (15.35 ± 0.03) kJ mol⁻¹ and Δ_dS_m = (41.35 ± 0.08) J K⁻¹ mol⁻¹. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations.     

Thermodynamic quantities for the interaction of SO 4 2− with H+ and Na+ in aqueous solution from 150 to 320°C

The aqueous reactions,

Enthalpies of Phase Transitions and Heat Capacity of TbCl3 and Compounds Formed in TbCl3–MCl Systems (M=K, Rb, Cs)

The molar enthalpies of the solid–solid and solid–liquid phase transitions were determined by differential scanning calorimetry for pure TbCl₃ and KTb₂Cl₇, RbTb₂Cl₇, CsTb₂Cl₇, K₃TbCl₆, Rb₃TbCl₆ and Cs₃TbCl₆ compounds. Both types of compounds, i.e. M₃TbCl₆ and MTb₂Cl₇ (M=K, Rb, Cs) melt congruently and show additionally a solid–solid phase transition with a corresponding enthalpy Δ_trs H ⁰ of 6.1, 7.6 and 7.0 kJ mol^–1 for potassium, rubidium and caesium M₃TbCl₆ compounds andΔ_trs H ⁰ of 17.1 (rubidium) and of 12.1 and 10.9 kJ mol^–1 (caesium) for MTb₂Cl₇ compounds, respectively. The enthalpies of fusion were measured for all the above compounds with the exception of Rb₃TbCl₆ and Cs₃TbCl₆. The heat capacities of the solid and liquid compounds have been determined by differential scanning calorimetry (DSC) in the temperature range 300–1100 K. The experimental heat capacity strongly increases in the vicinity of a phase transition, but varies smoothly in the temperature ranges excluding these transformations. C _p data were fitted by an equation, which provided a satisfactory representation up to the temperatures of C _p discontinuity. The measured heat capacities were checked for consistency by calculating the enthalpy of formation of the liquid phase, which had been previously measured. The results obtained agreed satisfactorily with these experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.