ADSORPTION OF COBALT ONTO GRAPHITE NANOCARBON–IMPREGNATED ALGINATE BEADS: EQUILIBRIUM,KINETICS, AND THERMODYNAMICS STUDIES

A novel adsorbent was developed impregnating graphite nanocarbon (GNC) into alginate beads (AB) for efficient cobalt (Co(II)) removal from an aqueous solution. Physicochemical and spectroscopic properties of graphite nanocarbon–impregnated alginate beads (ABGNC) were characterized and compared with those of AB. Co(II) adsorption on ABGNC was quantitatively evaluated by determining kinetics and thermodynamics parameters. The Co(II) adsorption capacity onto ABGNC was highest at neutral pH condition. Increasing the temperature from 288 to 318 K resulted in a 2.5-fold higher Co(II) adsorption onto AB, while thermal dependence of Co(II) adsorption on ABGNC was not found. Kinetic studies showed an applicability of the pseudo-second-order kinetic model for both AB and ABGNC. Monolayer adsorption was the dominant mechanism of Co(II) adsorption on both AB and ABGNC. Thermodynamic studies revealed that Co(II) adsorption was an endothermic and spontaneous process. Positive values of entropy indicate randomness in solid/aqueous phases, and mean free energy (E _a ) fits in the range of chemisorption.     

THE EXTRACTION OF CATIONIC RUTHENIUM COMPLEXES FROM AQUEOUS MEDIA BY α-TIN(IV) HYDROGEN PHOSPHATE

ABSTRACT

The ruthenium species [Ru(NH₃)₆]³⁺ was adsorbed by the surface of (α-Sn(HPO₄)₂.2H₂O [SnP]) α-tin(IV) hydrogen phosphate. The ruthenium(II)-containing cation [Ru(NH₃)₆]²⁺, however, has been directly intercalated into (SnP). Since the corresponding ruthenium(III) complex cation was not so intercalated, a new self-catalysed intercalation mechanism involving labile ammonia ligands from the ruthenium(II) has been proposed. At high loadings, guest ruthenium(II) species were oxidised to ruthenium(III).     

THE SEPARATION OF NEPTUNIUM AND PLUTONIUM FROM NITRIC ACID USING n-OCTYL(PHENYL)-N,N DIISOBUTYLCARBAMOYLMETHYLPHOSPHINE OXIDE EXTRACTION AND SELECTIVE STRIPPING†

The extraction of neptunium and plutonium in several oxidation states was studied as a function of nitric acid concentration for 0.1M n-octyl(phenyl)-N, N-diisobutylcarbamoyl -methylphosphine oxide in 1.4M tributylphosphate with dodecane diluent. Np(V) is only weakly extractable over the range of acid concentrations studied while Np(IV) and Np(VI) are highly extractable. Pu(IV) and Pu(VI) are also highly extractable while Pu(III) was extracted but with lower efficiency. An Fe(II) reductant was used to reduce neptunium to Np(IV) and plutonium to Pu(III) for the initial extraction. Pu(III) was then stripped with dilute HNO₃ in the presence of a holding reductant leaving the Np(IV) in the organic phase. Neptunium may then be recovered to an aqueous phase with one of a number of complexing agents.     

MODELING OF ELEMENTARY PROCESS KINETICS FOR METHANOL SYNTHESIS (Ⅱ )A TRANSIENT KINETIC MODEL OF METHANOL SYNTHESIS FROM CO/CO_2/H_2

在基元过程序列结构判识的基础上,以傅立叶变换红外光谱仪(FTIR)气体池作为检测器,采用动态响应技术,进行了合成甲醇过程瞬态动力学的实验研究,得到了微型反应器尾气中各主要物种的浓度对反应器进料浓度阶跃变化的动态响应数据。基于瞬态速率模型对实验数据的拟合,得到了由H_2/CO/CO_2合成甲醇初步的瞬态动力学关系。     

STUDIES ON THE RELATIONSHIP BETWEEN THE NETWORK STRUCTURE AND THE MECHANICAL PROPERTIES OF RUBBER VULCANIZATES (H) THE REINFORCEMENT OF ELASTOMERS BY CARBON BLACK FILLERS AND ITS CHARACTERIZATION

A satisfactory account of reinforcement of rubber through the application of the theory of elasticity forits vulcanizates with carbon black fillers has been obtained. A statistical theory of reinforcement by carbonblack fillers and its characterization was developed. Three methods for     

STUDIES ON KINETICS OF DESORPTION OF CO_2 FROM HOT CARBONATED POTASH SOLUTION WITH DETA (DIETHYLENETRIAMINE) AS A CATALYST

Under atmosphe()e press()ne, rates of deseption of CO() from unmod()ed carbonated potash solutior (27 wt%)and modified carbonated potash solution(27 wt%) containing DETA as a catalyst, have been measured in a laboratory stirred reactor. Experiments were carried out with concentrations of DETA from 0—40g/L and temperatures from 90—104℃The results, show that the desorption of CO_2 from hot carbonated solutions with and without the addition of DETA, may be considered a pseudo-first order reversible reaction, and that the desorption of CO_2 from carbonated potash solution calalysed by DEIA is in agreement with the mechanism of simultancous reactions of CO_2 with amine molecules and with hydroxyl ions in solution. Mathematical models for desorptions rate cocflicient have been cstablished, and optimum concentration of DETA is proposed.     

STUDIES ON VAPOR-LIQUID AND LIQUID-LIQUIDVAPOR EQUILIBRIA FOR THE TERNARY SYSTEM METHANOL-METHYL METHACRYLATEWATER (Ⅱ) TERNARY SYSTEM

Isothermal P-x data for homogeneous, and P-x'-x" data for partially miscible mixtures for the ternary system methanol-methyl methacrylate-water have been determined at 25, 35, 45, 55 and 60℃. By using a modified UNIQUAC model and binary parameters only, the predicted ternary phase equilibrium data were found to be in good agreement with the experimental results, indicating the adequacy of using binary model parameters in computing vapor-liquid and liquid-liquid-vapor equilibria covering pressures ranging from reduced to atmospheric.     

STUDIES ON THE RELATIONSHIP BETWEEN THE NETWORK STRUCTURE AND THE MECHANICAL PROPERTIES OF RUBBER VULCANIZATES (Ⅰ) THEORY OF ELASTICITY FOR RUBBER VULCANIZATES WITH CARBON BLACK FILLERS IN LARGE DEFORMATION

A model structure formed by the combination of crosslinked, trapped entanglement and carbon black-polymer chain networks has been developed for rubber vulcanizates with carbon black fillers. Based on thisstructure and the proposed mechanism of large deformation, the elastic free energy     

THE SWELLING BEHAVIOR OF (W/O)/W LIQUID SURFACTANT MEMBRANE (Ⅰ) ADSORPTION OF SURFACTANT AT THE INTERFACE AND THE SWELLING CAUSED BY EMULSIFICATION

The concept of effective concentration of surfaetant in membrane phase has been proposed,considering the high ad-sorption density of the surfactant at the droplet interfaces in LSM system.The effective concentration of surfactant,C_2,can be estimated by Eq.(7)—(9).The swelling caused by emulsification during the initial dispersion process was investigated.The swelling rate wasmeasured by a density method.A model for estimating the“Emulsification”swelling rate,F_(se),has been proposed,basedon a mechanism of swelling due to the entrainment of water resulted from the interracial turbulence and emulsification inthe initial dispersion process.It has been found that Eq.(26)gives excellent fit to the experimental data of Fujinawa,etal.and of the authors.     

STUDIES ON VAPOR-LIQUID AND LIQUID-LIQUID-VAPOR EQUILIBRIA FOR THE TERNARY SYSTEM METHANOL-METHYL METHACRYLATEWATER (Ⅰ) THREE BINARY SYSTEMS

Isothermal P-x data tor the binary systems methanol-methyl methacrylate and methanol-water, and isothermal P-x'-x" data for the binary system methyl methacrylate-water have been determined at 25, 35, 45, 55 and 60℃. Based on the maximum likelihood principle, the modified UNIQUAC model pa rameters for these binary systems were obtained by fitting the experimental data. Vapor compositions were then calculated, and the results were compared with literature data.     

COBALT–NICKEL SEPARATION: THE EXTRACTION OF COBALT(II) AND NICKEL(II) WITH BIS(2-ETHYLHEXYL) PHOSPHINIC ACID (PIA-8) IN TOLUENE

The extraction behaviour of cobalt(II) and nickel(II) from sulfate solutions with bis(2-ethylhexyl) phosphinic acid (PIA-8) in toluene has been studied. Quantitative extraction of Co(II) was observed at pH 5.0–5.9 while that of Ni(II) at pH 6.8–7.0 with 0.03 M PIA-8 in toluene. The difference in pH_0.5 for Co(II) and Ni(II) was 1.9. The stoichiometry of the extracted species were determined by slope analysis method. The extraction reaction proceeds by cation exchange mechanism and the extracted species were Co · R₂(HR)₂ and Ni · R₂ · 2(HR)₂. Temperature dependance of the extraction equilibrium constants were determined to estimate the apparent thermodynamic functions (ΔG, ΔS and ΔH). The method was used for separation of cobalt(II) and nickel(II). Cobalt(II) was separated from nickel even at 1:20 (Co:Ni) ratio. The separation of cobalt(II) from nickel(II) was favoured with the increase in temperature.     

PREPARATION AND ADSORPTION PROPERTIES OF THE POLYSTYRENE RESIN HAVING DIETHYLENETRIAMINE-N,N′- BIS(METHYLENEPHOSPHONATE) GROUP

Styrene-divinylbenzene copolymer beads containing diethylenetriamine-N,N′-bis(methylenephosphonate) group have been synthesized. The adsorption properties, of the present resin for some trivalent and bivalent metal ions have been examined. The selectivity sequence of the present resin at pH lower than 2.0 is as follows: Ga(III)> A1(III)> Sm(III)>Cu(II)>Co(II)>Zn(II)>Ca(II). The present resin reveals remarkable selectivity for the trivalent metal ions. The selective concentration of In(III) Ga(III) and Sm(III) from an acidic aqueous solution has been demonstrated by using a column of the present resin.     

KINETIC MODELING OF HYDROISOMERIZATION OF C\-8AROMATICS(Ⅰ)MODELING AND ESTIMATION OF RELATIVE RATE CONSTANTS BY THE WEI-PRATER METHOD

1 Introduetlon To date,most kinetie investigations ofC一aromaties hydroisomerization over bifunetionaleatalysts have been eoneerned with reaetjon meehanisms.R6bsehl巨ger et al.[,]studied thehydroisomerization kineties under sPecifie eonditions,and ProPose…     

THE EXTRACTION OF SELECTED ACTINIDES IN THE ( III) (IV) AND ( VI) OXIDATION STATES FROM HYDROCHLORIC ACID BY Oπ D( iB) CMPO: THE TRUEX-CHLORIDE PROCESS∗

The extraction of tetravalent Th, Np, and Pu and hexavalent U from hydrochloric acid was studied using octyl(phenyl)-N,N-diiso-butylcarbamoylmethylphosphine oxides, 0π D(iB)CMP0 or CMPO, dissolved in tetrachloroethylene (TCE). A 0·5 MCMPO solution in TCE was found to be an extremely effective extractant for the tetravalent actinides and U(VI) from moderate to concentrated HC1. Extractant dependencies of the distribution ratios of Th(IV), U(VI), and Pu(IV) were 3rd, 2nd, and 3rd power, respectively, indicating the following species: ThCl₄’3CMPO, UO₂Cl₂2CMP0, and PuCl₄»3CMPO. The distribution ratios of a variety of non-actinide elements, including selected alkali, alkaline earths, Al, transition and post-transition metal ions were also measured from 2 Mand 6 M_ HC1. Based on the distribution ratios of tri-, tetra-, and hexavalent actinides from chloride media, a generic actinide extraction/recovery process was developed for the removal of actinides from chloride salt wastes. The process is called TRUEX-Chloride.     

PREPARATION OF (Ni/W)-γ-Al2O3 MICROSPHERES AND THEIR APPLICATION IN ADSORPTION DESULFURIZATION FOR MODEL GASOLINE

A kind of desulfurization adsorbent, (Ni/W)-γ-Al₂O₃ microsphere, was prepared by a new method of in situ chemical reduction. The adsorbent consists of active components (transition metals Ni and W) and a carrier (γ-Al₂O₃). Ni and W in γ-Al₂O₃ microspheres are fine in size and can be distributed homogeneously on the surface and inside of the γ-Al₂O₃ carrier. The desulfurization of the adsorbent made by the in situ chemical reduction method was carried out in model gasoline. Its desulfurization capacity increases 23% in comparison with that made by the conventional impregnation method. The composition and configuration of adsorbents were analyzed by scanning electron microscopy (SEM), electron energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). The in situ chemical reduction method offers a new and promising method for preparation of desulfurization adsorbents containing active components.     

USE OF THE AEROSIZER® AERODYNAMIC PARTICLE SIZE ANALYZER TO CHARACTERIZE AEROSOLS FROM PRESSURIZED METERED-DOSE INHALERS (pMDIs) FOR MEDICATION DELIVERY

The Aerosizer^® aerodynamic particle size analyzer is widely used for the rapid assessment of medical aerosols. Its real-time capability to make measurements offers a significant advantage in terms of user convenience compared with aerodynamic particle size analysis by cascade impactor or multi-stage liquid impinger. However, the present study has highlighted a limitation in its use in the measurement of aerosols from many types of pressurized metered-dose inhaler (pMDI) in which the measured total number concentration exceeds about 10¹⁰ particles m^-3. The causes are complex, but appear primarily to be associated with the loss of electrical signals from individual particle-detection beam interactions, associated with timer insensitivity of the signal correlation system. This phenomenon occurs where several particles are present simultaneously within the measurement zone. Subsequent processing of the time-of-flight data may result in significant distortion of the reported size distribution, including in extreme cases the absence of portions of the data where the AUTOCOMBINE feature is used to create the full size distribution from the low and high detection sensitivity sub-ranges.     

RHEOLOGICAL BEHAVIOR OF POLYMER MELTS (Ⅱ) MULTIPLE ENTANGLEMENT MODEL FOR PREDICTING THE DEPENDENCE OF VISCOELASTIC BEHAVIOR ON DEFORMATION STATE AND PRIMARY MOLECULAR WEIGHTS AND THEIR DISTRIBUTION

In accordance with the memory function of Gaussian chain constraints in entangled polymermelts a set of material functions related to a certain"test flow"are formulated from the O-W-Ftype constitutive equation by the appropriate selection of the Cauchy-Green and Finger tensors.Thedependences of these material functions on the strain rate and the dependences of the linearviscoelastic functions on the primary molecular weight distribution and the entanglement sites sequencedistribution on polymer chain are derived from a multiple-entanglement model and a couple of mech-anisms of relaxation for the loop and terminal entanglement sites.When the primary polymer chainsare modelled with the Lansing-Kraemer molecular distribution function,a set of new relationshipsamong linear viscoelastic functions(η_0,ψ_(10)~0,η_(ext)~0 and τ_1)and the molecular weights and their distributionare formulated.These functions and relationships are verified with experimental data.     

A NEW METHOD FOR ACHIEVING DROPWISE CONDENSATION (Ⅲ) DETERMINATION OF DROPWISE CONDENSATION HEAT TRANSFER COEFFICIENT AND LIFETIME TEST OF THE NEW SURFACE

Heat transfer characteristics of the new surfaces were determined through temperature measurements, and the results were compared with dropwise condensation (DWC) studies from various sources.Duration tests for DWC were carried out on two different surfaces, giving a duration of perfect DWC over 15000 hours.     

MOLECULAR MODELLING AND SPECTROSCOPIC STUDIES OF THE INTERACTIONS BETWEEN CHELATING AND ELECTRON-DONOR METAL EXTRACTANTS: THE SYSTEM TRI-N-OCTYLPHOSPHINE OXIDE - 3-PHENYL-4-BENZOYL-ISOXAZOL-5-ONE ( ‘HPBI‘ ) IN WET TOLUENE AND CHLOROFORM.

ABSTRACT

IR, NMR (^H, ¹³C and ³¹P) and electronic spectroscopies have been used to study the tautomeric forms of 3-phenyl-4-benzoyl-isoxazol-5-one, "HPBI", and its interaction with tri-rc-octylphosphine oxide, ‘TOPO’, in wet toluene or benzene, and in chloroform. These metal extracting media have been compared with analogous solutions containing l-phenyl-3-methyI-4-acyI-pyrazoI-5-oIs. The spectroscopic results are compared with those of molecular modelling studies. Spectroscopic criteria that allow a choice between the various tautomeric forms of pyrazolones or isoxazolones are briefly reviewed.

In the solid, in wet toluene, benzene or chloroform solutions, HPBI mainly exists as a fi-keto-enol chelate, quite different from its tautomeric form in methanol, which is most probably a diketone-enamine. Molecular modelling studies show that the energy difference between the chelated 5-hydroxy- and 5-one- tautomeric forms of the free molecule is rather low. They cannot be discriminated by spectroscopy

As shown by UV and PMR spectroscopies, the interaction of TOPO with HPBI is stronger than with 4-acyl-5-hydroxypyrazoles (acyl: lauroyl, benzoyl, thenoyl). The most likely tautomeric form for HPBI in the H-bonded [TOPO.HPBI] moiety is the diketone-enamine (b’). Accordingly, molecular modelling studies show that the R3PO-H-NHPBI hydrogen bond is 0.15A shorter than the R3PO-H-OHPBI one, when comparing two isomeric forms of the 1:1 [TOPO.HPBI]complex.