薇甘菊粉末吸附亚甲基蓝和碱性品红的性能研究

以薇甘菊为原料,经粉碎制成不同粒径的粉末吸附剂。探究其对亚甲基蓝（MB）和碱性品红（BF）的吸附性能,研究发现薇甘菊粉末吸附亚甲基蓝和碱性品红的最佳投加量分别为20和10 g/L,最佳粒径为0.3~0.45 mm,pH值为5,温度40 ℃,振荡吸附时间40 min,此条件下,薇甘菊粉末对亚甲基蓝和碱性品红的吸附量分别为4.870和9.729 mg/g。利用准一级、准二级动力学方程模拟了薇甘菊粉末吸附亚甲基蓝和碱性品红的动力学过程,结果表明：薇甘菊粉末吸附亚甲基蓝和碱性品红的过程符合准二级动力学模型。计算了吸附过程中的焓变（ΔH^⊖）、吉布斯自由能（ΔG^⊖）、熵变（ΔS^⊖）等热力学参数,薇甘菊粉末吸附亚甲基蓝和碱性品红过程中ΔG^⊖在-2.13~-1.58和-4.66~-1.63 kJ/mol之间,ΔS^⊖分别为0.034和59.25 J/（mol·K）,ΔH^⊖分别为0.0099和14.75 kJ/mol,薇甘菊粉末吸附2种染料的ΔG^⊖均小于0,ΔH^⊖、ΔS^⊖均大于0,说明薇甘菊粉末吸附2种染料的过程是一个自发的趋于无序的吸热过程。     

Interaction of ciprofloxacin hydrochloride with sodium dodecyl sulfate in aqueous/electrolytes solution at different temperatures and compositions

Interactions of ciprofloxacin hydrochloride(CPFH) with sodium dodecyl sulfate(SDS) were investigated by conductivity measurement in H_2O/electrolyte solutions(NaCl, Na_2SO_4 Na_3PO_4) over 298.15–318.15 K temperature range(with 5 K interval) considering the human body temperature. In all cases, two critical micelle concentrations(c~*) were observed which are increased in the presence of drug and decreased in the presence of salts enunciating the presence of interaction amongst the studied components. For(CPFH + SDS) system in the presence of salt, the c~*values at 303.15 K and I = 0.50 mmol·kg~(-1) followed the order: C_(NaCl)C_(Na_2SO_4)C_(Na_3PO_4). The ΔG_(1,m)~0 and Δ G_(2,m)~0values are found to be negative for all systems that show that the micellization process is thermodynamically spontaneous. For(CPFH + SDS) system in water, the Δ H_m~0 Δ S_m~0 values reveal that the micellization processes is both entropy dominated in almost all cases. In the occurrence of electrolytes, Δ H_m~0 and Δ S_m~0 values indicate that micellization processes are both entropy enthalpy restricted at upper temperature but it becomes totally entropy dependent at higher temperature. The higher positive Δ S_m~0 values indicate the enhanced hydrophobic interaction in presence of salts. The enthalpy-entropy compensation was determined from the linear relationship betweenΔ H_m~0 and Δ S_m~0 values in every state. Different transfer energies as well as compensation temperature and intrinsic enthalpy were also evaluated and the behaviors were comparable to other biological system.     

Vaporization Thermodynamics and Enthalpy of Formation of Aluminum Silicon Carbide

The vaporization thermodynamics of aluminum silicon carbide was investigated using Knudsen effusion mass spectrometry. Vaporization occurred incongruently to give Al( g ), SiC( s ), and graphite as reaction products. The vapor pressure of aluminum above (Al₄SiC₄+ SiC + C) was measured using graphite effusion cells with orifice areas between 1.1 × 10⁻²and 3.9X10⁻⁴ cm². The vapor pressure of aluminum obtained between 1427 and 1784 K using an effusion cell with the smallest orifice area, 3.9X10⁻⁴ cm², is expressed as
log p (Pa) =−(18567 ± 86) ( K/T ) + (12.143 ± 0.054)
The third-law calculation of the enthalpy change for the reaction Al₄SiC₄( s ) = 4Al( g ) + SiC( hex ) + 3C( s ) using the present aluminum pressures gives Δ H °(298.15 K) = (1455 ± 79) kJ·mol⁻¹. The corresponding second-law result is Δ H °(298.15 K) = (1456 ± 47) kJ·mol⁻¹. The standard enthalpy of formation of Al₄SiC₄( s ) from the elements calculated from the present vaporization enthalpy (third-law calculation) and the enthalpies of formation of Al( g ) and hexagonal SiC is Δ H °_f= -(221 ± 85) kJ·mol⁻¹. The standard enthalpy of formation of Al₄SiC₄( s ) from its constituent carbides Al₄C₃( s ) and SiC( c, hex ) is calculated to be Δ H °(298.15 K) = (38 ± 92) KJ·mol⁻¹.     

左旋海松酸的分离及其理化数据测试

采用胺化法从松脂中分离左旋海松酸,然后利用超声波辅助左旋海松酸粗品重结晶进行纯化,通过单因素和正交试验优化左旋海松酸分离的工艺条件,得到的最佳工艺条件为：无水乙醇用量20 mL(1 g左旋海松酸),结晶温度0 ℃,超声波频率为53 kHz,重结晶次数为2次,此条件下得到的左旋海松酸纯度达97%。超声波辅助左旋海松酸重结晶,大幅度缩短了晶体成核时间,5~6 h可得到晶型细小均匀分散的长方型片状透明晶体。通过红外光谱(FT-IR)、核磁共振(¹H NMR, ¹³C NMR)、气相色谱-质谱联用(GC-MS)表征了纯化后左旋海松酸的分子结构,依据氧弹量热法、TG-DSC法和基团贡献法分析得到左旋海松酸的标准摩尔生成焓(Δ_fH_m^?)-700.23 kJ/mol和熔化焓94.99 kJ/mol。     

Standard Enthalpy of Formation of Lanthanum Zirconate

The enthalpy of formation of lanthanum zirconate, La₂Zr₂O₇, which is shown to have a distorted pyrochlore structure, was determined. High-temperature solution calorimetry in molten lead borate was used to determine the heat of formation from the constituent oxides as −135.8 ± 6.4 kJ/mol at 974 K. Using additional data on the enthalpies of formation of the oxides and heat contents, this value was converted to a standard enthalpy of formation from the elements: Δ_fH°_298.15=−4130.4 ± 6.8 kJ/mol.     

碳酸锂在碳酸钠溶液中的溶解度与热力学

采用等温溶解平衡法开展碳酸锂在碳酸钠溶液中(278.15～358.15 K)的溶解平衡实验研究,测定平衡体系碳酸锂溶解度和平衡溶液密度,利用E-DH方程对碳酸锂溶解度实验数据进行关联,标准偏差小于0.01;利用Connaughton方程对液相密度数据进行关联,标准偏差小于2×10^-3。实验和计算研究结果表明：在同离子和盐效应协同影响下,碳酸锂在Na₂CO₃-H₂O体系中溶解度随碳酸钠浓度增加先降低后降低趋势变缓,在278.15～358.15 K温度范围内,溶解度转变折点为碳酸钠浓度约为0.1 mol·kg^-1;通过溶解热力学计算,得到碳酸锂在碳酸钠中的溶解焓变(ΔH_d)、熵变(ΔS_d)和Gibbs自由能变(ΔG_d),结果表明溶解过程为放热、熵减的非自发过程,溶解焓变和熵变随着碳酸钠浓度增加而增加,Gibbs自由能变在0.6 mol·kg^-1出现最大值,且溶解过程为熵控制过程。研究结果将为卤水提锂碳化沉锂过程设计提供基础数据。     

CO2在醚酯溶剂中的溶解度测定及热力学计算

采用恒定容积法,在温度353.15、363.15、373.15 K下,测定了CO₂在丙二醇甲醚醋酸酯(PMA)、二丙二醇甲醚醋酸酯(DPMA)、乙二醇丁醚醋酸酯(BAC)以及乙二醇苯醚醋酸酯(EPA)中的溶解度数据,压力最高可达11.73 MPa。结果表明CO₂在醚酯体系中溶解度受温度、压强的影响较大,压强一定时,CO₂在醚酯中溶解度随温度升高而减小;温度一定时,随着压强增大而增大;相同条件下,CO₂在四种醚酯中溶解度大小为PMA＜ EPA＜BAC＜DPMA。通过变形Clausius - Clapeyron方程,计算得到CO₂在醚酯溶剂中的Gibbs自由能Δ_sol G,溶解焓变Δ_sol H和熵变 Δ_sol S等热力学性质,从宏观热运动角度进一步解释了CO₂的溶解机理,为开发新型CO₂物理吸收剂提供理论支撑。     

改性超细煤粉对甲基橙的吸附行为研究

The adsorption of methyl orange onto ultrafine coal powder (UCP) and modified ultrafine coal powder (MUCP) from aqueous solutions were studied, in which the influence of contact time, dosage, temperature, pH, and methyl orange concentration in the solution were investigated. The adsorption kinetics of methyl orange by UCP and MUCP can be described by the Lagergren first-order and pseudo second-order kinetic models, respectively. The adsorption isotherms of methyl orange onto MUCP at 303, 313 and 323 K follow the Freundlich and Langmuir isotherm equation. Values of G0 for methyl orange adsorption onto MUCP are -22.55, -23.10 and -23.79 kJ•mol－1 at 303, 313, and 323 K, respectively. The values of ΔH0 and ΔS0 are -3.74 kJ•mol－1 and 61.99 J•mol－1, respectively. The adsorption process is spontaneous and exothermic.     

Removal of chromium (VI) from aqueous solutions using quaternized chitosan microspheres

In this study, quaternized chitosan microspheres (QCMS) were prepared and its Cr(VI) removal potential was investigated. Batch experiments were conducted to examine kinetics, adsorption isotherm, pH effect, and thermodynamic parameters. Equilibrium was attained within 50 min and maximum removal of 97.34% was achieved under the optimum conditions at pH 5. Adsorption data for Cr (VI) uptake by the QCMS were analyzed according to Langmuir, Freundlich, and Temkin adsorption models. The maximum uptake of Cr(VI) was 39.1 mg·g^-1. Thermodynamic parameters for the adsorption system were determinated at 293 K, 303 K, 313 K and 323 K. (ΔH°=16.08 kJ·mol^-1;ΔG°=-5.84 to -8.08 kJ·mol^-1 and ΔS°=74.81 J·K^-1·mol^-1). So the positive values of both ΔH° and ΔS° suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption.ΔG° values obtainedwere negative indicating a spontaneous adsorption process. The kinetic process was described by a pseudo-second-order rate equation very well. The results of the present study indicated that the QCMS could be considered as a potential adsorbent for Cr (VI) in aqueous solutions.     

甲基-酰基-萘在庚烷、辛烷和十二烷中溶解度的测定与关联

The solubilities of 2-methyl-6-acetylnaphthalene (2,6-MAN) and 2-methyl-7-acetylnaphthalene (2,7-MAN) in n-heptane, n-octane, and n-dodecane were measured, respectively, from 273.15 to 319.15K using an analytical method. On the basis of the thermodynamics theory of solid-liquid equilibrium, a model was derived to relate the solubilities with temperature. Using the least square method, the parameters of the model, the fusion enthalpies ΔfusH and the Margules equation coefficients A12 and A21 of 2,6-MAN and 2,7-MAN in n-heptane, n-octane, and n-dodecane—were obtained by regressing the experimental data. The average deviation of the model was 1.70%.     

拉莫三嗪-邻苯二甲酰亚胺药物共晶在有机溶剂中溶解度及三元相图测定

采用静态法测定了拉莫三嗪在正丙醇、异丙醇、正丁醇、异丁醇、丙酸乙酯、乙酸甲酯6种溶剂中的热力学行为,并采用Apelblat方程和λh方程进行了关联,其结果表明拉莫三嗪的溶解度随着温度的升高而升高,溶解行为由低到高为正丁醇>正丙醇>异丁醇>异丙醇,乙酸甲酯>丙酸乙酯,应用的方程拟合度较好,可用于单体拉莫三嗪热力学行为的预测。在此基础上,采用溶液法制备拉莫三嗪-邻苯二甲酰亚胺共晶,在298.15、303.15 K时,建立了共晶体在异丁醇、丙酸乙酯溶剂中的三元相图,结果表明同一溶剂体系内,随着温度的升高,拉莫三嗪-邻苯二甲酰亚胺共晶区域增大,有利于共晶的形成。同一温度下,拉莫三嗪-邻苯二甲酰亚胺共晶在异丁醇体系的对称性优于丙酸乙酯体系,表明拉莫三嗪-邻苯二甲酰亚胺共晶更易于在异丁醇体系中获得。     

双季戊四醇在3种混合溶剂中的固-液相平衡

采用动态平衡法,在293.15～332.80 K、常压下,测定了双季戊四醇(DPE)在水+(甲醇、乙醇、异丙醇)三种混合溶剂中的溶解度数据。结果表明：DPE在不同质量分数的水+(甲醇、乙醇、异丙醇)混合溶剂中的溶解度随体系温度升高而增大;同一温度下,其在所选取溶剂体系中的溶解度随着甲醇、乙醇或异丙醇质量分数的增大而先增大后减小。λh方程、两参数方程与Apelblat方程均能够对所测定的溶解度数据进行较好的关联;通过修正的van’t Hoff方程计算得到DPE在所选取溶剂体系中Δ_sol H ⁰、Δ_sol S ⁰和Δ_sol G ⁰均大于零,表明DPE在所选取溶剂体系中的溶解过程为吸热、熵增的非自发过程。     

三元低共熔离子液体中CO2的吸收

由N, N-二甲基乙酰胺、氯化胆碱、乙二醇或丙三醇以不同的摩尔比(1:1:3, 1:1:4)合成了一系列三元低共熔离子液体(n_DMA:n_CC:n_{ethylene glycol}=1:1:3, 1:1:4, n_DMA:n_CC:n_glycerol=1:1:3, 1:1:4)。在293.15～323.15 K温度下, 间隔10℃, 0～600.0 kPa压力范围内, 用等温饱和法测量了CO₂在三元体系中的溶解度。CO₂在体系中的溶解度随压力增大呈线性增大趋势, 随温度升高而减小。计算了亨利常数, 结果表明, CO₂在由N, N-二甲基乙酰胺, 氯化胆碱, 乙二醇以摩尔比1:1:3合成的三元体系, 温度为293.15 K下, 亨利常数最小, 最小值为2.174 MPa·kg·mol^-1。报道了关于CO₂吸收的热动力学性质, 包括焓变、熵变、Gibbs自由能变。其中, 焓变为负值, 说明此吸收为放热过程。     

Vapor Pressure, Enthalpy, Evaporation Coefficient, and Enthalpy of Activation of the Beryllium Nitride (Be3N2) Decomposition Reaction

Beryllium nitride (Be₃N₂) vaporizes congruently in the range 1640° to 1960°K by the reaction Be, N₂( c ) = 3Be( g ) + N₂( g ). The equilibrium nitrogen partial pressure, in atmospheres, at the composition for congruent sublimation is given by the expression log P _N2= [(–1.952 ± 0.038) × 10⁴] T ⁻¹+ (6.509 ± 0.207). The measured enthalpy of decomposition (370 ± 5 kcal at 298° K) yields an enthalpy of formation for Be₃N₂( c ) of –136 ± 6 kcal/mole. The upper limit to the evaporation coefficient at 1600° to 2000°K can be set as 10^–4 by comparison of equilibrium data to Langmuir data obtained with a sample of 18% porosity. The apparent enthalpy of activation for the reaction is 409 ± 7 kcal/mole at 1800°K for the porous Langmuir specimen. An expression is developed to predict the temperature dependence of the reduced apparent pressures in Knudsen studies of substances with low evaporation coefficients in terms of the enthalpy of activation. The variation in temperature dependence of the Langmuir measurements and Knudsen measurements with three different-sized orifices is consistent with predictions from this expression.     

EQUILIBRIUM CONSTANTS FOR ETHYL tert-BUTYL ETHER LIQUID-PHASE SYNTHESIS

Thermodynamic equilibrium constants for the liquid-phase synthesis of ethyl terl-butyl ether (ETBE) were determined experimentally in the temperature range 40-80°C (313-353 K) at 1.6 MPa for an initial molar ratio of ethanol to isobutene ranging from 1 to 1.5. To reach etherification equilibrium a macroporous sulphonic acid resin (K-2631, Bayer) was used as a catalyst. The thermodynamic equilibrium constant and the enthalpy, free energy, and entropy changes are given as a temperature function. At 298 K, ΔH° = -34.8 kj mol^-1, ΔG° = -11.7kJmol^-1, and ΔS° = -77.3J mol^-1 K^-1. A comparison with the values obtained for MTBE is also included.     

用密度泛函理论研究多溴二苯并噻吩的热力学性质

The thermodynamic properties of 135 polybrominated dibenzothiophenes (PBDTs) in the gaseous state at 298.15 K and 1.013×105 Pa, are calculated using the density functional theory (the B3LYP/6-311G**) with Gaussian 03. Based on these data, the isodesmic reactions are designed to calculate the standard enthalpy of formation (ΔfHө) and the standard Gibbs energy of formation (ΔfGө) of PBDTs. The relations of these thermodynamic parameters with the number and position of bromine substituents (NPBS) are discussed, and it is found that there exist good correlations between thermodynamic parameters (including heat capacity at constant volume, entropy, enthalpy, free energy, ΔfHө, ΔfGө) and NPBS. The relative stability order of PBDT congeners is proposed theoretically based on the relative magnitude of their ΔfGө. In addition, the values of molar heat capacities at constant pressure (Cp,m) for PBDT congeners are calculated.     

Investigation on molar heat capacity,standard molar enthalpy of combustion for guaiacol and acetyl guaiacol ester

The molar heat capacities(C_p) of guaiacol(CAS 90-50-1) and acetyl guaiacol ester(AGE, CAS 613-70-7) were determinated from 290 K to 350 K by differential scanning calorimetry(DSC), and expressed as a function of temperature. Two kinds of group contribution models were used to estimate the molar heat capacities of both guaiacol and AGE, the average relative deviation is less than 10%. The standard molar enthalpies of combustion of guaiacol and AGE were- 3590.0 k J·mol~(-1)and- 4522.1 k J·mol~(-1) by a precise thermal isolation Oxygen Bomb Calorimeter. The standard molar enthalpies of formation of guaiacol and AGE in a liquid state at298.15 K were calculated to be- 307.95 k J·mol~(-1) and- 448.72 k J·mol~(-1), respectively, based on the standard molar enthalpies of combustion. The thermodynamic properties are useful for exploiting the new synthesis method, engineering design and industry production of AGE using guaiacol as a raw material.     

Solubility and metastable zone width measurement of 2,4-diaminobenzenesulfonic acid in (H2SO4 + H2O) system

The equilibrium solubility of 2,4-diaminobenzenesulfonic acid and super solubility as well as metastable zone width were measured in (H₂SO₄ + H₂O) system by the laser dynamic method at elevate temperature range from 298.15 K to 338.15 K. 2,4-Diaminobenzenesulfonic acid solubility dependence on the temperature and solvent composition were correlated by the modified Apelblat equation, (CNIBS)/Redlich-Kister model and Jouyban-Acree model. The correlated results by three correlation models were in good accord with the experimental values according to relative average deviations (RD), root-mean-square deviations (RMSD), and correlation coefficients (R²). The metastable zone width increased with temperature and sulfuric acid content. The dissolution enthalpy, dissolution entropy and the Gibbs energy were calculated from the experimental values, which indicated that dissolution process of the 2,4-diaminobenzenesulfonic acid was endothermic. The solubility and calculation models of 2,4-diaminobenzenesulfonic acid in (sulfuric acid + water) system could provide the basic data to the crystallization and purifying of the 2,4-diaminobenzenesulfonic acid.     

PDMS/ZSM-5膜的制备及渗透汽化分离水中乙酸正丁酯和乙酸乙酯

为探究出适合分离水中的乙酸正丁酯和乙酸乙酯的新型渗透汽化膜材料,选用沸石ZSM-5 对聚二甲基硅氧烷(PDMS)材料进行填充改性,以聚偏氟乙烯(PVDF)为支撑层,采用刮涂法制备PDMS/ZSM-5/PVDF复合膜渗透汽化分离水中的乙酸正丁酯和乙酸乙酯。采用SEM、接触角测量仪、FTIR、TGA和XRD等对膜材料物理化学性能进行表征,考察了膜材料的溶胀行为及渗透汽化性能。结果表明,ZSM-5在 PDMS 膜中分散均匀,且没有发生化学作用,并提高了膜材料的疏水性和热稳定性。随着ZSM-5添加量的增加,膜在乙酸正丁酯和乙酸乙酯的溶胀度和待分离组分在膜材料中的扩散速率不断增加。随着进料浓度和温度的增加,渗透通量不断增大,分离因子先增大后减小。随着ZSM-5在PDMS/ZSM-5/PVDF复合膜中含量的增加,总渗透通量增加,而分离因子呈现先增加后减小的趋势。当添加量为10%（质量）时,分离因子达到最大值。对于乙酸正丁酯/水体系,渗透通量和分离因子最大值分别为319 g·m ^-2·h ^-1和131;而对于乙酸乙酯/水体系,渗透通量和分离因子最大值分别为1385 g·m ^-2·h ^-1和121。     

Determination and correlation solubility of 4-nitroimidazole in twelve pure solvents from 278.15 K to 323.15 K

In this paper, the solubility of 4-nitroimidazole in twelve pure solvents (toluene, benzene, 1,4-dioxane, acetonitrile, ethyl acetate, acetone, GBL, ethanol, methanol, n-butanol, DMF and NMP) were determined by using the laser monitoring system from 278.15 K to 323.15 K under 101.1 kPa, which are 0.00018-0.00070, 0.00021-0.00073, 0.00034-0.00092, 0.00038-0.00142, 0.00047-0.00120, 0.00126-0.00303, 0.00225-0.00517, 0.00310-0.00724, 0.00467-0.00982, 0.00453-0.01940, 0.01947-0.04652, and 0.04670-0.07452, respectively. At constant temperature, the mole fraction solubility of 4-nitroimidazole were increased as the following order: toluene < benzene < 1,4-dioxane < (ethyl acetate or acetonitrile) < acetone < GBL < ethanol < (methanol or nbutanol) < DMF < NMP, and the solubility of 4-nitroimidazole in (ethyl acetate, acetonitrile) and (methanol, n-butanol) had an intersection point at 297.55 K and 281.85 K, respectively. The solubility of 4-nitroimidazole could be increased with increasing temperature in twelve pure solvents. The ideal model, modified Apelblat equation, polynomial empirical equation, and λh equation were used to correlate the experimental values. The experimental solubility values were employed to calculate the standard dissolution enthalpy, standard dissolution entropy and Gibbs energy. The dissolution of 4-nitroimidazole could be an endothermic process in twelve pure solvents. The determination and fitting solubility of 4-nitroimidazole have important guiding significance for the purification and crystallization of its preparation process.