Thermodynamic Analysis of the Adsorption and Micellization Activity of the Mixtures of Rhamnolipid and Surfactin with Triton X-165

The surface tension of aqueous solutions of Triton X-165 with rhamnolipid or surfactin mixtures was measured. The obtained results were applied for the determination of the concentration and composition of the Triton X-165 and biosurfactants mixture at the water–air interface as well as the contribution of the particular component of the mixtures to water surface tension reduction and the mutual influence of these components on the critical micelle concentration. The determination of these quantities was based on both the commonly used concepts and a new one proposed by us, which assumes that the composition of the mixed monolayer at the water–air interface depends directly on the pressure of the monolayer of the single mixture component and allows us to determine the surface concentration of each mixture component independently of surface tension isotherms shape. Taking into account the composition of the mixed monolayer at the water–air interface, the standard Gibbs adsorption free energy was considered. The obtained results allow us to state that the concentration of both mixture components corresponding to their saturated monolayer and the surface tension of their aqueous solution can be predicted using the surfactants’ single monolayer pressure and their mole fraction in the mixed monolayer determined in the proposed way.     

Thermodynamic Behavior of Non-Ionic Tri-block Copolymers in Water at Three Temperatures

Apparent molar volumes (V _Φ) of aqueous solutions of some copolymers, based on ethylene oxide (EO) and propylene oxide (PO) units, were determined as functions of concentration at three temperatures. Viscosity measurements were also carried out on some of these systems. The effects studied include how the molecular architecture and the molecular weight affect the aggregation of the copolymer, keeping constant the EO/PO ratio. Modeling of the volumetric data yielded the partial molar volume of the copolymer in the standard (V°) and the aggregated (V _M) states, as well as the equilibrium constant for micellization and the aggregation number. Analysis of the viscosity data supported the insights obtained by modeling of the volumetric data. At a given temperature, both V° and V _M, normalized for the number of the EO and the PO units, are linearly related to the fraction of the EO in the copolymer, regardless of the copolymer nature. These correlations are powerful tools for predicting values of both V° and V _M for copolymers not yet investigated. For macromolecules having the same molecular architecture, the standard Gibbs free energies of micellization () are slightly negative within the errors of their determination, and are hardly affected by temperature changes. Also, their aggregation numbers are small. From the quantitative analysis of the viscosity data, insights were obtained that corroborated the thermodynamic findings. Finally, values of , normalized for the EO and the PO units, show that the same driving forces control the self-assembling processes for copolymers having different molecular weight but the same EO/PO ratio.     

Asphaltene Precipitation Modeling Using Fuzzy Tuning of Scaling Equations

A major concern in the petroleum industry is asphaltene precipitation, which has negative impacts on production costs and recovery. The scaling equation is the most popular approach for modeling asphaltene precipitated out of solution in crude oils. Due to different values assigned for involved coefficients in scaling equations, they might overestimate or underestimate in some region relative to each other. This study proposes an improved strategy for tuning scaling equations and compensating effects of overestimation and underestimation through fuzzy rules. This strategy, called fuzzy tuning of scaling equations (FTSE), has a parallel framework, which gains outputs of different scaling equations and then introduces them to a fuzzy model as inputs. The fuzzy model breaks down the problem into subspaces through fuzzy membership functions and solves each region separately using fuzzy rules. Aggregating results of each subspace produces final model's output (i.e., FTSE output). Results indicated that FTSE performed more satisfyingly compared with individual scaling equations performing alone.      

A Shortcut Application of a Flory‐Like Model to Asphaltene Precipitation

A model, previously developed to determine the asphaltene precipitation onset, considered that asphaltene separation is ruled by the solvent quality of the surrounding media. Here, it is shown that it is equivalent to Flory‐Huggins model, when it is hypothesized that the asphaltene concentration is always in the instability range. With this, the controversy on the use of a concentration‐dependent model to describe a phenomenon that is practically independent of concentration is by‐passed. Moreover, improvements of the model are presented, together with sensitivity analysis with respect to its parameters. Two field case applications are reported, showing that the model gives a reasonable fit.     

Renovating Scaling Equation Through Hybrid Genetic Algorithm-Pattern Search Tool for Asphaltene Precipitation Modeling

The scaling equation is the most popular mathematical modeling of asphaltene precipitation as a problematic issue in petroleum industry. There are eight adjustable coefficients in the scaling equation that govern the quality of the fit between titration data and the scaling equation model. In this study, a hybrid genetic algorithm-pattern search (GA-PS) tool was employed to extract optimal values of the involved coefficients in the scaling equation through the stochastic search. For better performance of the GA-PS tool, dimensionality of the problem was broken into two simpler parts using the divide-and-conquer principle by introducing two fitness functions. The renovated scaling equation was compared with previous works; it was shown that the proposed method outperforms previous works.      

Effect of Electrolyte on the Surface and Thermodynamic Properties of Amphiphilic Penicillins

Critical micelle concentrations and surface properties of the penicillins cloxacillin, dicloxacillin, and nafcillin in aqueous solution at 303 K and at electrolyte concentrations over the range 0.0–0.4 mol dm⁻³ were determined by surface tension measurements. A mass action model, modified for application to associating systems of low aggregation number, was used to calculate the standard Gibbs energy of micellization of these drugs at each electrolyte concentration.     

利用数轴法求解热力学问题

利用数轴法求解化学热力学中化学反应的吉布斯自由能变、焓变、熵变的问题, 把ΔH、T1ΔS、T2ΔS的数值或相对位置直接标在数轴上, 根据相对大小判断它们的正负号和反应的自发性。该方法既直观, 又方便、快捷, 更容易被学生理解和掌握运用。     

铜在空气中生成碱式碳酸铜的热力学分析

从热力学角度研究了酸度、湿度、水的存在状态不同时,单质铜在空气中生成碱式碳酸铜的电动势及其自由能变。通过计算发现:在酸性条件下,p H的大小对于反应的自发性没有影响;大气中二氧化碳溶解达到饱和时,空气湿度增加,反应的自发性略微增加;相同条件下,水由气态变为液态时,反应的自发性增幅较大。     

Micellization of dodecyldimethylethyl- ammonium bromide in aqueous solution

Specific conductivity of aqueous solutions of dodecyldimethylethylammonium bromide has been determined in the temperature range of 15-40°C. The critical micelle concentration (cmc) and ionization degree of the micelles, b, were determined from the data. Thermodynamic functions, such as standard Gibbs free energy, ΔG _m°, enthalpy, ΔG _m°, and entropy, ΔG _m°, of micellization, were estimated by assuming that the system conforms to the mass action model. The change in heat capacity upon micellization, ΔG _m°, was estimated from the temperature dependence of ΔG _m°. An enthalpy-entropy compensation phenomenom for the studied system has been found. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic stability of AuSe at temperature from (400 to 700) K by a solid state galvanic cell

The numerical values on the standard thermodynamic functions of AuSe were determined by the electromotive force (EMF) method in a solid-state galvanic cell with a superionic conductor AgI as the solid electrolyte. According to the experimental data on the EMF vs. temperature, the analytical equations for Gibbs free energy, enthalpy and entropy were obtained for the single stable polymorphic form of AuSe. The temperature-dependent relationships of Gibbs free energy of formation of AuSe and the standard thermodynamic functions of compounds within the temperature range (400 to 700) K were also evaluated. No α–β transformation was identified in the gold saturation and β-form is a metastable modification of AuSe.     

如何理解热力学基本方程dG=-SdT+Vdp的适用条件*

从热力学第一定律和热力学第二定律出发推导了热力学基本方程dG=-SdT+Vdp;然后围绕 dG=-SdT+Vdp的适用条件做细致分析,分别从简单pVT变化、相变化和化学变化等3个方面着手,逐一举例并详细解题、分析,探讨对该公式的应用条件,得出相应的结论。为学生在热力学基本方程应用过程中的问题提供新思路。     

不同标态下标准电极电势间关系的热力学解释

利用标准吉布斯自由能变化ΔrGm与标准电极电势和标准反应平衡常数间的联系,分析不同标态下电极标准电极电势间的关系。根据这一思想,以水解离平衡为例,讨论了设计原电池求化学反应平衡常数的一般方法。     

鞘氨醇与DPPC, DPPE单层膜的热力学特性及形态观察

鞘氨醇(sphingosine)是生物体内合成鞘脂的母体化合物, 是生物膜中的重要组分之一. 通过分析表面压力和平均分子面积(π-A)等温线数据分别研究了鞘氨醇与二棕榈酰基磷脂酰胆碱(DPPC)和二棕榈酰基磷脂酰乙醇胺(DPPE)二元组分单层膜的热力学特性, 并在恒定膜压下制备不同摩尔比例的混合脂膜用原子力显微镜进行观测. 实验结果表明: (1)鞘氨醇与DPPC组成的系统中, XD-Sph＝0.2, 0.4, 0.6时, 过量分子面积与过量吉布斯自由能在所研究的表面压力下表现为负值, 而当XD-Sph＝0.8时, 表现为正值; (2)鞘氨醇与DPPE组成的系统中, 当表面压力 π＜25 mN•m－1时, 过量分子面积与过量吉布斯自由能在所研究的组分比例下表现为负值, 当π≥25 mN•m－1时为正值. 混合单层膜的分子面积与表面吉布斯自由能决定了分子间的相互作用, 当为负值时分子间相互作用表现为吸引力, 出现凝聚现象; 为正值时分子间相互作用表现为排斥力, 促使单层膜出现相分离现象. 过量吉布斯自由能值越小, 单层膜的热稳定性越高. 弹性系数曲线分析和AFM图片观测进一步验证了理论分析的结果.     

规范不同均相化学反应的热力学性质表示及其关系

尝试对均相化学反应的热力学性质表述进行规范,如浓度的表示形式、不同标准状态、B组分标准状态化学势μBo、标准吉布斯自由能变化量△rGm,ao、平衡常数Kao、反应的热效应△rHm,ao等。     

LiCl-KCl-LaCl3熔盐体系中La(III)的电化学行为

在773 K条件下,研究了La（III）在LiCl-KCl熔盐中W和Ni电极上的电化学行为。La（III）还原反应是一步三电子转移的准可逆反应;通过在Ni电极上直接电沉积La的方法可以获得La-Ni金属间化合物;恒电位电解可以获得含三种金属间化合物（LaNi₅、La₇Ni₁₆和La₂Ni₃）的La-Ni合金层,并且通过X射线衍射仪（XRD）和扫描电镜-能谱分析仪（SEM-EDS）确定物相并表征结构。采用开路计时电位法估算了LaNi₅金属间化合物的标准生成吉布斯自由能。揭示了恒电位电解方法是制备La-Ni镀层合金以及提取熔盐中La的有效方法。     

Theoretical Study on Thermodynamic Properties and Stabilities of n-Silanes

Abstract

First-principle computations were performed on the n-silane series (Si_nH_2n+2, n = 1–10). The heat of formation (Δ_fH), Gibbs free energy of formation (Δ_fG), bond length, and bond dissociation energy (BDE) for both the Si?Si and Si?H bonds were predicted. The values of Δ_fH and Δ_fG from the accurate high level G3 method for lower silanes (n ≤ 5) were compared with experimental values and used as benchmarks. Thermodynamic properties derived from the G3 method in combination with the permutation reaction are in better agreement with experiments than those with the atomization reaction. The increments of the Δ_fH and Δ_fG values with an increasing SiH₂-unit for n-silanes are 40.39 and 58.93 kJ/mol on average, respectively. The length of Si?Si bond increases slightly on average as the series number increases and then tends to be a constant for higher silanes. The BDEs for both the Si?Si and Si?H bonds initially decrease for lower silanes, and then approach a constant for higher silanes. The BDEs of the Si?Si bonds are smaller than those of Si?H bonds. The higher silanes are more unstable than the lower silanes. The average BDE of Si?Si bond at the MP2 level is ca. 302 kJ/mol, which is only half the experimental BDE value of the C?C bond (618 kJ/mol).

GRAPHICAL ABSTRACT      

Catalytic and Thermodynamic Characterization of Endoglucanase (CMCase) from <Emphasis Type="Italic">Aspergillus oryzae</Emphasis> cmc-1

Monomeric extracellular endoglucanase (25 kDa) of transgenic koji (Aspergillus oryzae cmc-1) produced under submerged growth condition (7.5 U mg⁻¹ protein) was purified to homogeneity level by ammonium sulfate precipitation and various column chromatography on fast protein liquid chromatography system. Activation energy for carboxymethylcellulose (CMC) hydrolysis was 3.32 kJ mol⁻¹ at optimum temperature (55 °C), and its temperature quotient (Q ₁₀) was 1.0. The enzyme was stable over a pH range of 4.1–5.3 and gave maximum activity at pH 4.4. V _max for CMC hydrolysis was 854 U mg⁻¹ protein and K _m was 20 mg CMC ml⁻¹. The turnover (k _cat) was 356 s⁻¹. The pK _a1 and pK _a2 of ionisable groups of active site controlling V _max were 3.9 and 6.25, respectively. Thermodynamic parameters for CMC hydrolysis were as follows: ΔH* = 0.59 kJ mol⁻¹, ΔG* = 64.57 kJ mol⁻¹ and ΔS* = −195.05 J mol⁻¹ K⁻¹, respectively. Activation energy for irreversible inactivation ‘E _a(d)’ of the endoglucanase was 378 kJ mol⁻¹, whereas enthalpy (ΔH*), Gibbs free energy (ΔG*) and entropy (ΔS*) of activation at 44 °C were 375.36 kJ mol⁻¹, 111.36 kJ mol⁻¹ and 833.06 J mol⁻¹ K⁻¹, respectively.     

A differential approach to calculating osmotic equilibrium for multisolvent systems

A differential approach to the calculation of osmotic pressure of multisolvent systems within the Lewis–Randall framework is presented in this paper. Exact differential equations relating the osmotic pressure and the system composition along paths of constant solvent chemical potential are obtained and numerically solved. Although even for the simple case of an ideal solution no analytic expression for the osmotic pressure can be obtained, the system of differential equations does not pose numerical difficulties to be solved. Examples of the use of the proposed methodology are presented using the two-suffix Margules and Flory–Huggins equations, allowing an assessment of the influence of liquid-phase non-ideality on the performance of the method, and showing that it can be applied even for systems wherein liquid–liquid phase equilibrium occurs.     

气流床粉煤气化的Gibbs自由能最小化模拟

用Gibbs自由能最小化方法对粉煤气化过程进行了热力学平衡分析。对一混合煤种,在3.0 MPa和气化温度限制在1 200 ℃～1 450 ℃时,研究了氧-煤比、蒸气-煤比对气化炉出口气体组成、温度和有效气产率的影响,并由此确定了可行的操作域是氧-煤比545m3/t～605 m3/t、蒸气-煤比为152.64 kg/t～313.92 kg/t及其对应的工艺指标。从操作域中选择有代表性的工艺条件为氧-煤比578 m3/t、蒸气-煤比为187 kg/t,对应的气化炉出口温度1 358 ℃,CO+H2干基体积分数为91.5%,有效气产率为2.123(CO+H2)m3/kg。同时,研究了碳转化率和热损失对气化工艺指标的影响,其影响是显著的。