The Measurement of the Gibbs Energy of Transfer Between Oil and Water Using a Nano‐Carbon Paste Electrode

The use of nano‐carbon paste electrodes for the measurement of Gibbs energies of transfer between oil and aqueous phases is reported. In this method the oil of interest is used as the binder for the nano‐carbon paste electrodes and the molecule of interest is dissolved in the organic or aqueous phase. Voltammetry is performed over a period of time and used to monitor the transfer of the molecule between the two phases. The method is illustrated for the transfer of ferrocenemethanol between water and oil using the ferrocenemethanol / ferroceniummethanol (FcCH₂OH/FcCH₂OH⁺) redox couple. Three pairs of voltammetric peaks were observed in a 0.1 M KCl solution when the nano‐carbon paste electrode was modified by dissolution of FcCH₂OH in the binder oil: P1 [E=0.23 V, 0.17 V vs. Ag/AgCl (1 M KCl)], P2 [E=0.36 V, 0.32 V vs. Ag/AgCl (1 M KCl)] and P3 [E=0.55 V, 0.46 V vs. Ag/AgCl (1 M KCl)]. These are assigned to the FcCH₂OH species existing in the aqueous solution [FcCH₂OH(aq)/FcCH₂OH⁺(aq)], originating in the oil (o) [FcCH₂OH(o)/FcCH₂OH⁺(aq)] and to oxidation of adsorbed (ads) material on the nano‐carbon [FcCH₂OH(ads)] respectively. When supporting electrolyte containing the anions Cl^?, NO₃^? or SCN^? was used, an expulsion of the oxidised ferrocene occurred and the difference in midpoint potentials (E_mid) between the peaks P1 and P2 observed in these experiments allowed the calculation of the Gibbs energy (ΔG°) of transfer of ferrocenemethanol from water to oil. The average ΔG° value thus obtained was (?12.7±0.2) kJ mol^?1. For more hydrophobic anions (X^?=PF₆^?, AsF₆^?), the electron transfer is coupled to the transfer of the anion into the oil and the ΔG° for the transfer of the ion pair of FcCH₂OH⁺ and X^? ions from water to oil was found to be ?1.3 and ?3.9 kJ mol^?1 for PF₆^? and AsF₆^? respectively.     

石蜡或聚丁二烯填充型高吸油树脂的合成及其性能比较

以过氧化二苯甲酰 (BPO)为引发剂、二甲基丙烯酸乙二酯 (EGDMA)为化学交联剂、甲基丙烯酸十二酯 (DMA)和苯乙烯 (St)为单体、石蜡 (Paraffin)或聚丁二烯 (PB)为填充剂 ,用悬浮聚合法合成了填充型高吸油树脂 .研究了单体配比、填充剂用量以及化学交联度对树脂吸油性能及凝胶分率的影响 .对石蜡和PB填充的高吸油树脂进行比较 ,发现PB填充的高吸油树脂中存在物理交联 ,而石蜡填充的树脂中不含物理交联 ;PB填充的高吸油树脂随PB用量的增加 ,吸油倍率提高 ,凝胶分率上升 ,脱油速率增大 ;而石蜡填充的树脂随石蜡用量的增加 ,吸油倍率提高 ,但凝胶分率和脱油速率变化不大     

苯酚的电化学氧化及测定

本文研究了在硼砂介质中，苯酚及其衍生物 的电化学行为，利用苯酚在－０．５Ｖ吸附富集，再进行氧化溶出，建立了测定苯酚的新方法。     

Control of n-alkanes crystallization by ethylene-vinyl acetate copolymers

The crystallization of paraffins from their solution at low temperature was investigated in the presence of ethylene-vinyl acetate (EVA) copolymers that allow the control of the size of the crystals. Depending on the type of solvent and distribution of the paraffin lengths, the mechanisms of crystal formation and growth are different. Precipitation of the EVA prior to the paraffins leads to the nucleation of a large number of crystals, whereas the adsorption of EVA on the surface of the growing crystals slows down the crystal growth. EVA can act either as a nucleating agent or as a growth inhibitor. These two mechanisms were identified from the analysis of the temperature of crystallization (cloud point), the chemical composition of the crystals, and the observations of the crystal habit. The EVA was able to co-crystallize with the paraffins in crystals of an orthorhombic structure and the melting enthalpies of the crystalline paraffin did not depend significantly on their neighborhood. The energies of interaction between the different paraffinlike components are close to each other, so that minor changes of the experimental conditions may lead to dramatic effects. This is the basic rationale for the large behavioral diversity observed in these systems.     

A Study of Nickel Electrodeposition on Paraffin‐Impregnated Graphite Electrode

The aim of the present work was to elucidate the mechanism of electrolytic deposition of Ni on paraffin‐impregnated graphite electrode (PIGE). This process is influenced by H₂ evolution, which occurs in the same potential region. On the basis of the results obtained by linear and cyclic voltammetry, elimination voltammetry with linear scan (EVLS) was used to evaluate both processes. H₂ Evolution alone was studied in sulfate supporting electrolyte, and the previously suggested mechanism for this process according to Volmer–Heyrovsky was confirmed by EVLS. It was found that both the Ni²⁺ concentration and pH affect the polarization behavior of PIGE significantly. Two separated cathodic peaks were observed at low Ni²⁺ and high H⁺ concentrations, and the separation was better at higher scan rates. EVLS confirmed the most‐probable mechanism of Ni deposition as being controlled by slow transfer of the first electron under formation of [NiOH]⁺ as an intermediate. EVLS also indicated slow reduction of H⁺ preceding the reduction of Ni²⁺. The same was confirmed by studying the anodic dissolution at different switching potentials. The results were complemented by scanning electron microscopy (SEM).     

Metal–Organic Framework Crystal–Glass Composite Membranes with Preferential Permeation of Ethane

Metal–organic framework (MOF) glass is an easy to process and self-supported amorphous material that is suitable for fabricating gas separation membranes. However, MOF glasses, such as ZIF-62 and ZIF-4 have low porosity, which makes it difficult to obtain membranes with high permeance. Here, a self-supported MOF crystal–glass composite (CGC) membrane was prepared by melt quenching a mixture of ZIF-62 as the membrane matrix and ZIF-8 as the filler. The conversion of ZIF-62 from crystal to glass and the simultaneous partial melting of ZIF-8 facilitated by the melt state of ZIF-62 make the CGC membrane monolithic, eliminating non-selective grain boundaries and improving selectivity. The thickness of CGC membrane can be adjusted to fabricate a membrane without the need of a support substrate. CGC membranes exhibit a C₂H₆ permeance of 41 569 gas permeation units (GPU) and a C₂H₆/C₂H₄ selectivity of 7.16. The CGC membrane has abundant pores from the glassy state of ZIF-62 and the crystalline ZIF-8, which enables high gas permeance. ZIF-8 has preferential adsorption for C₂H₆ and promotes C₂H₆ transport in the membrane, and thus the GCG membrane exhibits ultrahigh C₂H₆ permeance and good C₂H₆/C₂H₄ selectivity.     

INDUCTION OF CRYSTALLIZATION OF SPECIFIC CALCIUM OXALATE HYDRATES IN MICELLAR SOLUTIONS OF SURFACTANTS

ABSTRACT

The influence of octaethylene glycol mono-n-hexadecyl ether (C₁₆EO₈) and sodium dodecyl sulphate (SDS) on the crystallization of calcium oxalate from 0.3 mol dm^?3 sodium chloride solutions has been investigated. The critical micellar concentration (CMC) of C₁₆EO₈ in water and 0.3 mol dm^?3 NaCl was determined by surface tension measurements (CMC_H2O=CMC_NaCl = 7.2.10^?6 mol dm^?3). The kinetics of precipitation of calcium oxalate was followed by Coulter counter, and solid phases were characterized by polarized microscopy, thermal analysis and X-ray powder diffraction patterns. Under the precipitation conditions employed, the thermodynamically stable monohydrate, CaC₂O₄?H₂O (COM) was the predominant crystalline form. In the presence of micellar solutions of C₁₆EO₈ precipitation of this phase was facilitated as evidenced by higher initial precipitation rates and higher precipitate volume and number of particles, as compared to the controls. Micellar solutions of 50S retarded precipitation but induced crystallization of calcium oxalate dihydrate, CaC₂O₄?(2+×)H₂O (COD, x≤0.5). Thus at c(SDS>CMC the precipitates contained ≥85 mass % COD. The results are discussed in relation to previously reported data on the precipitation of calcium oxalate in the presence of dodecyl ammonium chloride     

A Quartz Crystal Microbalance Characterization of Metal‐Oil Interfaces and Interactions with Wax Molecules

The solid‐liquid interface between stainless steel and model petroleum fluids is investigated at isothermal conditions using a quartz crystal microbalance. AISI 316 (Fe/Cr18/Ni10/Mo3) stainless steel is chosen to represent the metal surface. Paraffin components dissolved in dodecane constitute the petroleum fluid phase. Commercial macro‐crystalline and micro‐crystalline waxes provide primarily linear and branched paraffin components, respectively. Paraffin solubility conditions are established through a van't Hoff relationship. Model fluids prepared with the single‐component alkanes n‐C₃₆ or n‐C₃₀ paraffin provide well‐defined solubility conditions. Monitored changes in resonance frequency and energy dissipation of the quartz crystal resonator immersed in the model fluids confirm that no continual deposition of paraffin components occurs at isothermal conditions. Solid paraffin crystals dispersed in solution show no adherence to the stainless steel surface. The absence of attractive interactions between the stainless steel surface and the dispersed paraffin crystals suggests that a surface adsorption and/or surface nucleation mechanism is responsible for the formation of incipient paraffin wax deposits under nonquiescent conditions.     

Stabilization of Paraffin Emulsions Used in the Manufacture of Chipboard Panels by Liquid Crystalline Phases

Paraffin emulsions are commonly used in the manufacture of chipboard panels to provide resistance to water and humidity. The quality and performance of chipboards are improved with the use of paraffin emulsions stabilized by mixed surfactant systems, although little is known about the basic colloidal chemistry of such systems and their implications in the manufacturing and processing of the chipboard panels. In the present work, the stability and the phase behavior of paraffin emulsions stabilized by a mixture of anionic and nonionic surfactants, are described. Stability is studied by applying thermal and ultracentrifugation cycles, and also by rheology (steady state and dynamic determinations). A significant increase of stability is observed at high {anionic surfactant/(anionic surfactant+nonionic surfactant)} ratios. Phase behavior studies have demonstrated the presence of hexagonal liquid crystalline structures at high ionic surfactant/nonionic surfactant ratios and the presence of lamellar structures at low ratios. The stability of emulsions could be related to phase behavior, and, thus, providing a qualitative tool to predict stability.     

固体石蜡碳糊—磷钼酸根电极的研制与应用

研究了以固体石蜡作粘和剂的碳糊电极,在磷钼酸溶液中活化一定时间后,该电极对1.0×10~(-6)～5.0×10~(-4)mol·L~(-1)的磷钼酸有能斯特响应,斜率约为30mV,检出限为3.2×10~(-7)mol·L~(-1).电极的稳定性和选择性较好,已用于矿石、水样中磷的测定,结果满意.