DFT Calculation on polychlorinated phenarsazines: Their gas phase thermodynamic functions and the implications of Cl substituted position

The thermodynamic properties of 136 polychlorinated phenarsazines (PCPAZs) have been calculated by density functional theory at the B3LYP/6‐31G* level. Then, isodesmic reactions are designed to calculate Δ_fH° and Δ_fG° of PCPAZs. The relations of these thermodynamic parameters with the number and position of Cl atom substitution (N_PCS) are discussed and a relative stability order of PCPAZs is theoretically proposed according to the relative magnitude of their Δ_fG°. In addition, the values of molar heat capacities at constant pressure from 200 to 1000 K for PCPAZs are calculated, and the temperature dependence relations of this parameter are obtained using the least‐squares method.     

Simple Method for Prediction of the Standard Gibbs Free Energy of Formation of Energetic Compounds

A reliable simple method for prediction of the standard Gibbs energy of formation (Δ_fG^θ) of energetic compounds containing nitroaromatic, acyclic, and cyclic nitramine, nitrate ester, and nitroaliphatic compounds is introduced herein. The method is based on the contribution of elemental composition (Δ_fG_elem^θ) and the correcting function for the presence of additive and non‐additive molecular fragments (Δ_fG_corr^θ). In presence of some molecular moieties, Δ_fG_corr^θ may increase or decrease the value of Δ_fG_elem^θ, depending on the intermolecular interactions. The experimental root‐mean‐square error (RMSE) of the novel correlation (22.7 kJ mol⁻¹) is quite good. For some energetic compounds, where the computed values of two complex models of the quantitative structure‐property relationship (QSPR) theory were available, the experimental RMSE developed by the new method is smaller than the values obtained by QSPR method.     

Theoretical Study on Thermodynamic and Detonation Properties of Polynitrocubanes

We investigated the heat of formation (Δ_fH) of polynitrocubanes using density functional theory B3LYP and HF methods with 6‐31G*, 6‐311+G**, and cc‐pVDZ basis sets. The results indicate that Δ_fH firstly decreases (nitro number m=0–2) and then increases (m=4–8) with each additional nitro group being introduced to the cubane skeleton. Δ_fH of octanitrocubane is predicted to be 808.08 kJ mol⁻¹ at the B3LYP/6‐311+G** level. The Gibbs free energy of formation (Δ_fG) increases by about 40–60 kJ mol⁻¹ with each nitro group being added to the cubane when the substituent number is fewer than 4, then Δ_fG increases by about 100–110 kJ mol⁻¹ with each additional group being attached to the cubic skeleton. Both the detonation velocity and the pressure for polynitrocubanes increase as the number of substituents increases. Detonation velocity and pressure of octanitrocubane are substantially larger than the famous widely used explosive cyclotetramethylenetetranitramine (HMX).     

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.     

Study on adsorption behavior between Cr(VI) and crosslinked amphoteric starch

Crosslinked amphoteric starches (CASs) with quaternary ammonium cationic and carboxymethyl anionic groups were prepared by a hemidry reaction. Their adsorption behavior for Cr(VI) was investigated, and was found to follow the Langmuir isotherm. The adsorption process was found to be dependent on initial pH, concentration of Cr(VI), dose of CAS, and temperature. The adsorption capacity decreased with increasing degree of substitution of anionic groups. The thermodynamic study indicated that the adsorption process was exothermic, and the enthalpy changes (ΔH^θ), the entropy changes (ΔS^θ), and free energy changes (ΔG^θ) for CASs were determined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 263–267, 2003     

Synthesis of crosslinked oxidized starch and its adsorption behavior for calcium ion

Cornstarch, after crosslinking with epichlorohydrin (4%, v/w, dry basis of the starch), was oxidized with hydrogen peroxide over the catalyst Cu(II). The newly synthesized products were applied to examine the calcium ion removal activity from water, under various conditions. Removal efficiency of calcium ion from aqueous solution increased proportionally with carboxyl content and the dose of crosslinked oxidized starch in the solution. Ionization of carboxyl groups in starch was necessary for the effective calcium removal. When the pH of the solution was adjusted below 4.0, the starch was no longer an effective calcium‐sequestering agent. Adsorption isotherm models were developed, wherein the best fit was obtained in the Langmuir model. Thermodynamic study indicated that the adsorption process was exothermic, and the enthalpy change (ΔH^θ), the entropy change (ΔS^θ), and free energy change (ΔG^θ) of the adsorption process were calculated with adsorption isotherm data and basic thermodynamic relations. It was assessed that adsorption occurred by strong electrostatic interactions with the negative adsorption enthalpy (ΔH^θ). The regeneration and reusability of oxidized starch were also assessed and were found to retain the adsorption capacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1539–1546, 2006     

Equilibrium of benzidine inclusion adsorption on cyclodextrin copolymer

Insoluble β‐cyclodextrin (β‐CD) copolymer was prepared by reacting β‐CD with hexamethylene diisocyanate, and its inclusion adsorption behavior was investigated. The physical and chemical properties of CD copolymer were characterized by SEM, FTIR, DSC, TGA, XRD, and BET N₂ adsorption. The effects that shaking time and temperature exerted on the inclusion adsorption of benzidine on CD copolymer have been studied at relative low initial benzidine concentration. The procedure of the inclusion adsorption could be described by the Freundlich equation, and the thermodynamic constants ΔH^θ, ΔS^θ and ΔG^θ were obtained simultaneously. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Interaction Study of Anionic Surfactant with Aqueous Non‐Ionic Polymers from Conductivity,Density and Speed of Sound Measurements

In the present study, we have investigated in detail the interactions of the anionic surfactant sodium dodecyl sulfate (SDS) with aqueous polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP) and various PEG + PVP mixtures at 293.15, 303.15 and 313.15 K by applying conductivity, density and speed of sound techniques. From experimentally measured data, the critical micelle concentration (CMC) values, standard free energy of micellization (ΔG_m^o), standard enthalpy of micellization (ΔH_m^o), standard entropy of micellization (ΔS_m^o), isentropic compressibilities (κ_s), apparent molar volumes (?_v) and apparent molar isentropic compressions (?_k) of SDS in aqueous polymer mixtures have been calculated. The nature of the process of micellization has been evidenced from the magnitude of ΔG_m^o, ΔH_m^o and ΔS_m^o values. The trends of variations obtained in the various parameters have been explained in terms of the electrostatic as well as hydrophobic interactions pertaining in SDS?PEG/PVP?water systems.     

Polymeric surfactants for enhanced oil recovery. IV—Thermodynamic properties of ethoxylated alkylphenol formaldehyde polymeric surfactants

The thermodynamic properties of some low molecular weight ethoxylated alkylphenol formaldehyde polymeric surfactants have been investigated. Surface tension as a function of concentration of the surfactants in aqueous solutions was measured at 28, 38, 48 and 58°C, using the spinning drop technique. From these measurements, the minimum area per molecule at the aqueous solution/air interface (A_min) was determined. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic, ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad, ΔS_ad) for these polymeric nonionics were calculated. Micellization is more sensitive to ethylene oxide chain length while adsorption is more dependent on the length of the alkyl chain.     

多溴代二苯并呋喃/噻吩热力学性质的定量构效关系

多溴代二苯并呋喃(PBDFs)是剧毒环境污染物,主要来源于溴系阻燃剂的燃烧和高温裂解过程,其性质与其结构有关;多溴代二苯并噻吩(PBDTs)的结构与其非常相似。通过计算多溴代二苯并呋喃和多溴代二苯并噻吩254个分子的原子特征值,利用分子图形学技术获得了一种新的连接性指数——路径指数mP,采用多元回归分析方法建立了PBDFs的分子总能量(ET)、标准焓(H0)、自由能(G0)、标准熵(S0)和恒容热容(c0v)以及PB-DTs的标准焓(H0)、自由能(G0)、标准生成焓(ΔfH0)和标准生成吉布斯自由能(ΔfG0)的定量结构-性质相关模型,相关性良好(r20.995),利用Jackknifed法检验了模型的稳定性和预测能力,Jackknifed检验的相关系数r2均在0.995以上,对标准熵预测的相对平均误差为0.52%,预测结果和文献值基本吻合。     

Thermodynamic aspects of the bovine serum albumin adsorption onto N,N′‐ diethylaminoethyl dextran microbeads

Adsorption of proteins on solid surfaces is widely studied because of its importance in various biotechnological, medical, and technical applications, e.g., biosensor cardiovascular implants and chromatography. Adsorption thermodynamics has been studied on the microbeads of N,N′‐diethylaminoethyl (DEAE) dextran anion exchanger for bovine serum albumin at 25, 30, 35 40, and 45°C. As a result some thermodynamic parameters like Freundlich constants, thermodynamic equilibrium constant (K_D), standard free energy changes (ΔG_assoc), standard entropy changes (ΔS_assoc), and standard enthalpy change (ΔH_assoc) have been evaluated. Using the linear Van't Hoff plot, the ΔH_assoc value of the system for the interaction of BSA adsorbed crosslinked DEAE dextran microbeads was determined as 12.5 kJ/mol. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

A method of estimating the standard gibbs free energy of formation

Standard Gibbs free energy of formation (ΔG_f⁰), an important property needed in design calculations has been estimated using molar refraction, R_M. The linear relationships derived between ΔG_f⁰ and R_M tested with the data on 8 series of hydrocarbons at 228 compounds yielded average deviations comparable to the methods cited in recent literature. The method can be used as an alternative to the existing ones, because of its simplicity combined with reasonable accuracy.     

Haematoxylin sorption onto yak hair: kinetic and thermodynamic studies

The kinetic and thermodynamic behaviours of haematoxylin sorption onto yak hair as a model system were investigated. It was found that the sorption kinetics of haematoxylin on hair followed a pseudo‐second‐order kinetic model. The equilibrium sorption capacity increased as the temperature increased from 303 to 313 K, but dropped gradually as the temperature increased beyond 313 K. The maximum equilibrium sorption capacity was 24.04 mg g^?1 at T = 313 K. Meanwhile, the sorption isotherm data were ingood agreement with the Freundlich isotherm, presenting high coefficients (R² > 0.99). The free energy change (ΔG), enthalpy change (ΔH), and entropy change (ΔS) terms for haematoxylin dyeing were also determined, the negative values of ΔG and ΔH obtained indicated that the haematoxylin dye sorption process is a spontaneous and an exothermic one. Also, positive values of ΔS showed an increase in disorder of the system of haematoxylin sorption onto hair. Haematoxylin could be a good candidate as a natural green dye for hair fibre.     

Taming the Beast: Measurement of the Enthalpies of Combustion and Formation of Triacetone Triperoxide (TATP) and Diacetone Diperoxide (DADP) by Oxygen Bomb Calorimetry

Low‐melting paraffin wax was successfully used as a phlegmatizing agent to perform semi‐micro oxygen bomb calorimetry of spectroscopically pure samples of the sensitive explosive peroxides TATP and DADP. The energies of combustion (Δ_cU) were measured and the standard enthalpies of formation (Δ_fH°) were derived using the CODATA values for the standard enthalpies of formation of the combustion products. Whilst the measured Δ_fH° of DADP (Δ_fH°=−598.5 ± 39.7 kJ mol⁻¹) could not be compared to any existing literature value, the measured Δ_fH° value of TATP (Δ_fH°=+151.4 ± 32.7 kJ mol⁻¹) did not correlate well with the only existing experimental value and confirmed that TATP is an endothermic cyclic peroxide.     

Polymerization of acrylic bone cement investigated by differential scanning calorimetry: Effects of heating rate and TCP content

The polymerization reaction of a bone cement (standard Surgical Simplex-P Radiopaque) upon heating has been investigated by differential scanning calorimetry (DSC). The effects of the addition of tricalcium phosphate (TCP) on the rate and the heat of polymerization during DSC heating were evaluated. The rate and polymerization heat (ΔH) were characterized by the initial curing temperature (T_i), peak temperature (T_p), completing curing temperature (T_f), the curing range (ΔT = T_f ? T_i) and the area of the DSC exotherm. It was found that T_i, T_p, T_f, ΔT, and ΔH all increase with increasing heating rate. Increasing TCP content also induced increases in T_i, T_p, T_f, ΔT, and ΔH. From the kinetic analysis, the polymerization of acrylic bone cement was found to be a first order reaction. The effects of heating rate and TCP contents on the rate and the heat of polymerization could be explained based on the frequency factor and the activation energy extracted from the kinetic analysis. Increases in both heating rate and TCP content depressed the frequency factor and the activation energy.     

A thermodynamic study of the binding of human serum albumin onto N,N′‐diethylaminoethyl dextran microbeads

Adsorption of proteins on solid surfaces is widely studied because of its importance in various biotechnological, medical, and technical applications, e.g., biosensors, cardiovascular implants, and chromatography. Adsorption thermodynamics has been studied on the microbeads of N,N′‐diethylaminoethyl (DEAE) Dextran anion exchanger for the human serum albumin (HSA) at 25, 30, 35, 40, and 45°C. As a result, some thermodynamic parameters like Freundlich constants, thermodynamic equilibrium constant (K_D), standard free energy changes (ΔG_assoc), standard entropy changes (ΔS_assoc), and standard enthalpy change (ΔH_assoc) have been evaluated. Using the linear Van't Hoff plot, ΔH_assoc value of the system for the interaction of bovine serum albumin (BSA)‐adsorbed crosslinked DEAE dextran microbeads was determined as 20.650 kJ/mol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3942–3947, 2006     

Predictions of nucleation theory applied to ehrenfest thermodynamic transitions: II. The effects of pressure and stress

This paper is a sequel to an earlier one on the applicability of classical nucleation theory to second-order transitions in the Ehrenfest sense (1). In each case the approach was to obtain the critical size r_c and energy barrier ΔG_c for the growth of a nucleus of β-phase in an α-phase matrix by a Maclaurin series expansion of the free-energy-density g = (G_β ? G_α)/v_β as a function of θ (in BC-I) and of ΔP and Δσ in this paper where θ = (T ? T_t) is the degree of undercooling and ΔP and Δσ are analogous terms for the hydrostatic pressure shift and tensile stress shift away from the equilibrium transition. The expansion coefficients were determined by the use of thermodynamic relationships. For second-order transitions, r_c = 4γv_β T_t/ΔC_pθ², r_c = 4γ/Δβ(Δp)², and r_c = 4γ/Y_αY_β(Δσ)², respectively, for the three cases. The terms ΔC_p, Δβ, and ΔY denote the differences in heat capacity, compressibility, and Young's modulus, e.g., ΔY = Y_β ? Y_α. The interfacial energy γ_αβ is denoted by γ. The activation energy barriers for the cases developed in this paper were ΔG_c = (16π/3)γ³/(Δβ)² (Δp)⁴ and ΔG_c = (64π/3)γ³Y_α²Y_β²/(ΔY)²(Δσ)⁴. More complicated expressions are given in the paper for the r_c and ΔG_c for first-order transitions. In the long run, these expressions may prove more useful than the ones for second-order because of the modifications expressions for the kinetics of transformations.     

Some thermodynamic properties of tetrafluoroethene-hexafluoropropene copolymers

Copolymers of tetrafluoroethene (TFE) with hexafluoropropene (HFP) have been prepared in the 0-14mol% HFP composition range. Their melting temperatures (T_m), enthalpies (ΔH_f) and entropies (ΔS_f) of first and second fusion, and crystallinities (X) according to x-ray diffraction(x.r.d.) and differential scanning calorimetry (d.s.c.) have been determined. The results indicate that ΔH_f/X_x.r.d of the polymer crystals decreases with higher HFP content.     

A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

Thermodynamic parameters of amitriptyline hydrochloride–additives at cloud point: effects of the ethanol–water mixed media

Abstract

Addition of organic solvents is known to change the properties of amphiphiles through modification of bulk phase. Amitriptyline hydrochloride (AMT) is a tricyclic amphiphilic drug which is usually used as an antidepressant. In drug delivery, the cloud point (CP) of the drug is an important parameter. This article discusses the effects of ethanol–water (EtOH–WR) compositions on the energetic parameters, such as changes in Gibbs energy of clouding (Δ_sG⁰), enthalpy of clouding (Δ_sH⁰), and entropy of clouding (TΔ_sS⁰) of AMT-additive systems. Monovalent alkali halide salts, cationic conventional surfactants, and gemini surfactants were used as additives in the EtOH–WR mixed media whose compositions were varied between 0 and 15% (w/w). The Δ_sG⁰ values are positive for all the additives and the values decrease with the rise in mole fractions of the additives. The Δ_sH⁰ and TΔ_sS⁰ were noted to be positive except for KF in 15% EtOH–WR mixed media.