Di-hydroxybenzenes: Catechol, resorcinol, and hydroquinone: Enthalpies of phase transitions revisited

Molar enthalpies of sublimation of 1,2-di-hydroxybenzene, 1,3-di-hydroxybenzene, and 1,4-di-hydroxybenzene were obtained from the temperature dependence of the vapor pressure measured by the transpiration method. The molar enthalpies of fusion of 1,2- and 1,4-isomers were measured by differential scanning calorimetry (DSC). A large number of the primary experimental results on the temperature dependences of vapor pressure and phase transitions have been collected from the literature and have been treated in a uniform manner in order to derive sublimation, vaporization and fusion enthalpies of di-hydroxybenzenes at the reference temperature 298.15 K. The data sets on phase transitions were checked for internal consistency. This collection together with the new experimental results reported here has helped to resolve contradictions in the available thermochemical data and to recommend consistent and reliable sublimation, vaporization and fusion enthalpies for all three isomers under study.     

The H2+ molecular ion: Low-lying states

Matching for a wavefunction the WKB expansion at large distances and Taylor expansion at small distances leads to a compact, few-parametric uniform approximation found in Turbiner and Olivares-Pilon (2011). The ten low-lying eigenstates of H₂⁺ of the quantum numbers (n,m,Λ,±)$(n,m,\Lambda ,\pm )$  with n=m=0$n=m=0$ at Λ=0,1,2$\Lambda =0,1,2$, with n=1$n=1$, m=0$m=0$ and n=0$n=0$, m=1$m=1$ at Λ=0$\Lambda =0$ of both parities are explored for all interproton distances R$R$. For all these states this approximation provides the relative accuracy ?10⁻⁵$?10^{-5}$ (not less than 5 s.d.) locally, for any real coordinate x$x$ in eigenfunctions, when for total energy E(R)$E\left(R\right)$ it gives 10-11 s.d. for R∈[0,50]$R\in [0,50]$  a.u. Corrections to the approximation are evaluated in the specially-designed, convergent perturbation theory. Separation constants are found with not less than 8 s.d. The oscillator strength for the electric dipole transitions E1$E1$ is calculated with not less than 6 s.d. A dramatic dip in the E1$E1$ oscillator strength f_{1sσg−3pσu}$f_{1s{\sigma }_g-3p{\sigma }_u}$ at R∼R_eq$R\sim R_{eq}$ is observed. The magnetic dipole and electric quadrupole transitions are calculated for the first time with not less than 6 s.d. in oscillator strength. For two lowest states (0,0,0,±)$(0,0,0,\pm )$ (or, equivalently, 1sσ_g$1s{\sigma }_g$ and 2pσ_u$2p{\sigma }_u$ states) the potential curves are checked and confirmed in the Lagrange mesh method within 12 s.d. Based on them the Energy Gap between 1sσ_g$1s{\sigma }_g$ and 2pσ_u$2p{\sigma }_u$ potential curves is approximated with modified Pade Re^−R[Pade(8/7)](R)$R{e}^{-R}\left[Pade(8/7)\right]\left(R\right)$ with not less than 4-5 figures at R∈[0,40]$R\in [0,40]$ a.u. Sum of potential curves E_1sσg+E_2pσu$E_{1s{\sigma }_g}+E_{2p{\sigma }_u}$ is approximated by Pade 1/R[Pade(5/8)](R)$1/R\left[Pade(5/8)\right]\left(R\right)$ in R∈[0,40]$R\in [0,40]$ a.u. with not less than 3-4 figures.     

Remarks on a posteriori error estimation for finite element solutions

We utilize the classical hypercircle method and the lowest-order Raviart–Thomas H(div)$H(\mathrm{div})$ element to obtain a posteriori error estimates of the _P1$P_1$ finite element solutions for 2D Poisson's equation. A few other estimation methods are also discussed for comparison. We give some theoretical and numerical results to see the effectiveness of the methods.     

Microwave assisted volatilization of silicon as fluoride for the trace impurity determination in silicon nitride by dynamic reaction cell inductively coupled plasma-mass spectrometry

A low pressure microwave assisted vapor phase dissolution procedure for silicon nitride and volatilization of in situ generated SiF₄ has been developed using H₂SO₄, HF and HNO₃ for the determination of trace impurities present in silicon nitride. Sample was taken in minimum amount (0.5 mL for 100 mg) of H₂SO₄ and treated with vapors generated from HF and HNO₃ mixture in presence of microwaves in a closed container. An 80 psi pressure with ramp and hold times of 30 min and 60 min respectively, operated twice, resulted in 99.9% volatilization of Si. Matrix free solutions were analyzed for impurities using DRC-ICP-MS. The recoveries of Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Y, Cd, Ba and Pb were between 80 and 100% after volatilization of Si. The blanks were in lower ng g⁻¹ with method detection limits in lower ng g⁻¹ to sub ng g⁻¹ range. The method was applied for the analysis of two silicon nitride samples.     

Counting solutions to binomial complete intersections

We study the problem of counting the total number of affine solutions of a system of n binomials in n   variables over an algebraically closed field of characteristic zero. We show that we may decide in polynomial time if that number is finite. We give a combinatorial formula for computing the total number of affine solutions (with or without multiplicity) from which we deduce that this counting problem is #P$\#P$-complete. We discuss special cases in which this formula may be computed in polynomial time; in particular, this is true for generic exponent vectors.     

流动注射蒸气发生原子吸收光谱测定痕量铜

建立了流动注射蒸气发生原子吸收光谱测定铜的新方法。使含有微量邻菲咯啉的样品溶液与硼氢化钠溶液汇合并反应生成蒸气态物质。在Ar载气下随反应液进入气液分离器分离 ,并进入石英管原子化器在 1 0 0 0℃下检测。在 5 0 0 μL进样体积下 ,铜的检出限为 1 8μg·L- 1 ,相对标准偏差为 2 6%(n =1 1 ,c=1 0 0 μg·L- 1 )。采样频率为 1 4 4样·h- 1 。分析标准参考物质大米粉和头发样品中的铜 ,结果与标准值一致     

Semi-continuous High Speed Gas Analysis of Generated Vapors of Chemical Warfare Agents

A method is presented for the continuous analysis of generated vapors of the nerve agents soman and sarin and the blistering agent sulfur mustard. By using a gas sampling valve and a very short (15 cm) column connected to an on-column injector with a “standard length” column, the system can either be calibrated or used for performing high speed gas analyses. When using a flame ionization detector, the detection limit was ca. 100 ppb (ca. 0.5–1.0 mg/m³). This technique is applied in inhalation toxicokinetic studies of nerve agents and mustard gas in the guinea pig.     

用恒温热重法测定1-己基-3-甲基咪唑苏氨酸离子液体[C6mim][Thr]蒸汽压和蒸发焓

用中和法合成了氨基酸离子液体(AAIL)1-己基-3-甲基苏氨酸盐[C₆mim][Thr],并用核磁共振氢谱(¹H NMR)和核磁共振碳谱(¹³C NMR)进行了表征。以苯甲酸为参考物质,用恒温热重法确定了AAIL[C₆mim][Thr]的蒸汽压和在平均温度下(T_av= 438.15 K)的蒸发焓(Δ^g_lH_m^? (T_av) =128.5 ± 6.0 kJ·mol^-1)。利用Verevkin等人提出的方法计算得到AAIL[C₆mim][Thr]气态和液态的恒压热容差(Δ^g_lC_pm^? = -70.8 J·K^-1·mol^-1),进而计算了不同温度的蒸发焓,其中参考温度(298.15 K)下的蒸发焓Δ^g_lH_m^? (298.15 K) = 138.4 kJ·mol^-1,只比应用我们提出的蒸发焓理论模型估算值大1.6 kJ·mol^-1,小于恒温热重法的实验误差3.0 kJ·mol^-1,说明这个蒸发焓的理论模型有一定的合理性。借助Clausius-Clapeyron方程估算了AAIL[C₆mim][Thr]的假想的正常沸点T_b= 522.07 K,以及沸点的蒸发熵Δ^g_lS_m^? (T_b) = 228.5 J·K^-1·mol^-1,进一步得到了不同温度的蒸发熵和蒸发自由能Δ^g_lG_m^? (T),其结果表明蒸发自由能随着温度的上升而减小,达到沸点温度T_b时变为零,而蒸发熵则随着温度上升而增大,是AAIL[C₆mim][Thr]蒸发过程的驱动力。     

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.