在确定的热力学状态下测量气体导热系数与黏度

气体的导热系数和黏度是重要的热物性参数,其数值大小取决于所处的热力学状态。在目前的导热系数和黏度主要测量方法中,待测工质在测量时需经历非定常的过程或处于具有物性梯度的非平衡态之下,使得待测工质的物性在时间或者空间上不处于一个确定的热力学状态。本文利用圆柱定程干涉法,通过分析气体导热系数和黏度导致的声波能量耗散,结合气体输运理论中对稀疏气体的描述,探索了在确定的热力学状态下同时测量气体导热系数和黏度的方法,并以氩(Ar)为例进行了实验验证。测量结果与已有文献一致性较好,初步证实了方法的可行性。     

四硅氧烷Gemini咪唑表面活性剂的合成及表面性能

以三甲基氯硅烷、 γ-氯丙基三氯硅烷、 1,4-二氯丁烷和咪唑等为原料合成了一种新型的四硅氧烷Gemini咪唑表面活性剂([Si₄-4-Si₄im]Cl₂), 通过质谱(MS)和核磁共振氢谱(¹H NMR)证明所得产物为目标产物. 通过Wilhelmy板法测得其在25 ℃下的临界胶束浓度(cmc)为0.54 mmol/L, 水溶液的表面张力(γ_cmc)降至18.6 mN/m. 通过电导率法研究了其胶束形成热力学参数(Δ\begin{array}{c}{G}_m^{0—}\end{array},Δ\begin{array}{c}{H}_m^{0—}\end{array}和Δ\begin{array}{c}{S}_m^{0—}\end{array}), 表明在15~35 ℃下其胶束化过程是自发进行的, 且为熵驱动过程.     

Remarks on the notion of “pressure”

In addition to understanding the various meanings attached to the word “pressure” one also has to comprehend the meanings of the phrases in which the term “pressure” appears. For instance one comes across the following combinations: “static-fluid pressure”, “thermodynamic pressure”, “mechanical pressure”, “contact pressure”, “stagnation pressure”, “vapor pressure”, “electro-osmotic pressure”, etc., One also often comes across the comment that “pressure is the Lagrange multiplier that enforces the constraint of incompressibility” and that “pressure is the mean normal stress”. In general the word “pressure” with different significations, is used with gay abandon without paying proper attention to its usage¹. The distinction in the meanings of the above terms assumes paramount significance when discussing properties of materials, which could possibly depend on “pressure”. In this short note we discuss the distinction between various significations of the word “pressure”, and their implications with regard to response relations for bodies.     

Investigation on Exciton Relaxation Kinetics of ZnCuInS/ZnSe/ZnS Quantum Dots by Time-Resolved Spectroscopy Techniques

Based on the location of bromine substituents and conjugation matrix, a new substituent po-sition index ⁰X not only was defined, but also molecular shape indexes K_m and electronega-tivity distance vectors M_m of diphenylamine and 209 kinds of polybrominated diphenylamine (PBDPA) molecules were calculated. Then the quantitative structure-property relationships (QSPR) among the thermodynamic properties of 210 organic pollutants and ⁰X、K₃、M₂₉、M₃₆ were founded by Leaps-and-Bounds regression. Using the four structural parameters as input neurons of the artificial neural network, three satisfactory QSPR models with network structures of 4:21:1, 4:24:1, and 4:24:1 respectively, were achieved by the back-propagation algorithm. The total correlation coefficients R were 0.9999, 0.9997, and 0.9995 respectively and the standard errors S were 1.036, 1.469, and 1.510 respectively. The relative mean deviation between the predicted value and the experimental value of S^?,Δ_fH^? and Δ_fG^? were 0.11%, 0.34% and 0.24% respectively, which indicated that the QSPR models had good stability and superior predictive ability. The results showed that there were good nonlinear correlations between the thermodynamic properties of PBDPAs and the four structural pa-rameters. Thus, it was concluded that the ANN models established by the new substituent position index were fully applicable to predict properties of PBDPAs.     

A Facile Strategy for Construction of Sensor for Detection of Ondansetron and Investigation of its Redox Behavior and Thermodynamic Parameters

A sodium dodecylsulfate‐doped polypyrrole (SDS‐PPy) film was elaborated on glassy carbon electrode (GCE) by an electrodeposition method in phosphate buffer solution (pH 2.0) containing pyrrole (Py) and sodium dodecyl sulfate (SDS). SDS‐PPy/GCE was used for the construction of sensor, which showed excellent electrochemical response for the detection of ondansetron (OND) compared to conventional PPy. The application of the square wave (SW), with the adsorptive accumulation, indicates a maximum response at 1.33 V in H₂SO₄ (0.5 M). The influence of experimental parameters on determination of OND is discussed. The adsorptive stripping technique showed to be more sensitive, giving responses twice as big as those of non‐accumulated OND. The substantial improvement of response permits the development of an electroanalytical technique with a linear concentration in the range (1.0–80 μM), low detection (0.09 μM), and quantification limits (0.3 μM), and acceptable relative standard deviations of repeatability (0.59 %), and reproducibility (1.51 %). Consequently, this electrode is promising candidate for an accurate electroanalytical determination of OND in pharmaceutical samples with high sensitivity and selectivity, good accuracy and precision. The electrooxidation of OND at SDS‐PPy/GCE at various temperatures were studied by cyclic voltammetry to evaluate both the kinetic (k_s and E_a) and thermodynamic (ΔG*, ΔH* and ΔS*) parameters.     

Effect of the alkyl chain of quaternary ammonium cationic surfactants on corrosion inhibition in hydrochloric acid solution

In this study, the effect of the alkyl chain of quaternary ammonium cationic surfactants on corrosion inhibition in hydrochloric acid (HCl) solution was investigated by using dodecyl trimethyl ammonium chloride (DTAC), tetradecyl trimethyl ammonium chloride (TTAC), cetyl trimethyl ammonium chloride (CTAC), and octadecyl trimethyl ammonium chloride (OTAC) as corrosion inhibitors to uncover their structure–efficiency relationships. The effect of the alkyl chain of quaternary ammonium cationic surfactants on corrosion inhibition in HCl solution was studied under different conditions, such as corrosion inhibitor concentration, temperature, and acidity, and this was done using the weightlessness method. The results obtained show that these inhibitors have high corrosion inhibition effect on A₃ steel, and the corrosion inhibition efficiency is dependent on the length of the alkyl chain. At the same concentration, the longer the alkyl chain, the weaker the corrosion inhibition effect. When the temperature was 50 °C and the concentration of corrosion inhibitor was 70 mg/L, the corrosion inhibition efficiency order of the four cationic surfactants was DTAC > TTAC > CTAC > OTAC. Besides, the experimental results obtained show that the adsorption of the inhibitor on the A₃ steel surface conforms to the Langmuir type isotherm, and then the corresponding adsorption thermodynamic parameters were obtained according to these parameters. It was observed that ΔH, ΔS, and E_a increased with increase in the length of the alkyl chain. The adsorption of the inhibitor on the steel surface is an exothermic, spontaneous, entropy process.     

Thermodynamic modeling of Fe–Ni pentlandite

Gibbs energy modeling of iron–nickel pentlandite has been performed using experimental data of ternary phase equilibria. A three-sublattice approach in the framework of the Compound Energy Formalism is developed to refine a two-sublattice model of pentlandite recently applied within a complete assessment of the Fe–Ni–S system. Experimental data about the iron site fraction on the octahedral sublattice at 523.15 K for the composition Fe₅Ni₄S₈ as well as the enthalpy of formation at 298.15 K for the composition Fe_4.5Ni_4.5S₈ are predicted satisfactorily by the novel model. New possibilities to interpret experimental phase equilibrium data on complex phase relations with pentlandite are discussed together on the basis of the recent extension of a second high-temperature heazlewoodite phase to a ternary solution phase.     

On the mechanism of the zircon-reidite pressure induced transformation

We report first principles results of a detailed investigation directed to elucidate mechanistic aspects of the zircon-reidite phase transition in ZrSiO₄. The calculated thermodynamic boundary is located around 5 GPa, and the corresponding thermal barrier, estimated from temperatures at which the transition is observed at zero and high pressure, is 133 kJ/mol. Under a martensitic perspective, we examine two different transition pathways at the thermodynamic transition pressure. First, the direct, displacive-like, tetragonal I4₁/a energetic profile is computed using the c/a ratio as the transformation parameter, and yields a very high activation barrier (236 kJ/mol). Second, a quasi-monoclinic unit cell allows us to characterize a transition path from zircon (β=90^°) to reidite (β=114.51^°) with an activation barrier of around 80 kJ/mol at β=104^°. This energy is somewhat lower than our previous estimation and supports the reconstructive nature of the transformation at the thermodynamic transition pressure.     

Synthesis and Thermodynamic Properties of M2L[M=Li,Na; L=3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine]

Two novel energetic alkalic metal salts of 3,6-bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz), Li₂(BTATz)·6H₂O(compound 1) and Na₂(BTATz)·2H₂O(compound 2), have been synthesized by the reaction of BTATz with lithium hydroxide or sodium hydroxide in dimethylsulfoxide(DMSO) solution, respectively, and their structures were characterized by means of elemental analysis and Fourier transform infrared spectrometry(FTIR). Moreover, the single-crystal structure of compound 1 was determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P1/c. Furthermore, their thermal decomposition behaviors were investigated by means of differential scanning calorimetry(DSC) and thermogravimetry-differential thermal gravimetry(TG-DTG). The results show that the exothermic decomposition peak temperatures for compounds 1 and 2 were 642.65 and 644.46 K, respectively, and the kinetic equations of the main exothermic decomposition were also derived from non-isothermal method. Additionally, the thermal safety of the two compounds was evaluated by calculating self-accelerating decomposition temperature(T_SADT) and critical temperature of thermal explosion(T_b). The results(the T_SADT and T_b values are 605.43 and 635.69 K for compound 1; 607.38 and 638.96 K for compound 2) reveal that the two compounds exhibit better thermal safety than BTATz.     

尿嘧啶和5-溴尿嘧啶的低温热容

采用综合物性测量系统(PPMS)的热容测量模块在1.9-300 K温度区间内对两种药物中间体(尿嘧啶和5-溴尿嘧啶)的低温热容进行了测量与研究. 结果表明, 在测量温区内两种化合物的低温热容随温度的上升而逐步增加, 无任何热异常现象产生; 在相同温度下, 5-溴尿嘧啶的热容数值始终高于尿嘧啶. 利用低温热容理论模型对热容数据进行了拟合, 并计算得到了0-300 K温区的摩尔熵变、焓变等热力学函数. 此外, 通过热容拟合数据计算得到的尿嘧啶和5-溴尿嘧啶在298.15 K的标准摩尔规定熵分别为(132.48±1.32)和(165.39±1.65) J·K^-1·mol^-1.