Studies of photoconductivity in β-Apo-8′ carotenal

The photoconductive properties of a carotenoid polyene,β-Apo-8′ carotenal in polycrystalline form has been studied. The growth of the photocurrent shows an overshoot in the growth-time curve before steady state value is attained. This behaviour of photocurrent is proposed to be due to higher value of recombination coefficient than trapping coefficient. From the temperature dependence study it is observed that the steady state photocurrent, at first increases with increase of temperature, attains a maximum at a particular temperatureT _max and then decreases with temperature. TheT _max value agrees with the temperature above and below which steady state photocurrent is attained differently. Monomolecular and bimolecular recombination processes at two temperature regimes are proposed to account for the observed behaviour. The dependence of photocurrent with excitation light intensity and wavelength study provide information on the carrier generation processes. The fast decay of photocurrent have been observed at different temperatures and from this study the decay constant is calculated and it is found to be temperature independent.     

Morphological and kinetics study of PEO/PVC blends

The kinetics of spherulite radial growth and the morphology of the compatible system PEO/PVC have been studied by optical microscopy. The usual spherulite radial growth behaviour has been found for compatible blends with PEO content higher than 70%. For lower composition, distortion of the usual spherulite morphology has been observed; the anomalies have been attributed to partial miscibility of the components.     

Hydrogen incorporation in Ni–P films prepared by electroless deposition

Electroless NiP films, with 12 to 16 wt % P, were deposited from a moderately acid solution. Thermogravimetric analysis indicates the presence of occluded hydrogen in the layers, which desorbs upon heating. The amount of incorporated hydrogen decreases when the pH of the solution or the nickel sulfate concentration is increased; by contrast it increases with hypophosphite concentration. Cyclic voltammetry, using an electrochemical quartz crystal microbalance, confirms the existence of parasitic reactions, namely the reduction of protons of the solvent during the cathodic process and oxidation of hydrogen during the dissolution of the layers. This behaviour is in qualitative agreement with the proposed reaction scheme.     

Kinetic behaviour of muscle LDH immobilized in nylon tubing

Immobilization was carried out of the lactate dehydrogenase (LDH) from rabbit muscle (EC 1.1.1.27), cross-linked through the bifunctional reactive glutar-aldehyde on to nylon tubing (1 m long, 53cm² internal surface area). Immobilized LDH inactivation kinetics are of first order (t_1/2 = 3·6 years, k = 5·4,e^?4 day^?1 to 5°C). The smaller effect of pH on activity than in the case of LDH in solution can be explained on the basis of limitation to proton diffusion towards the support. A limiting effect to free external diffusion of the substrate towards and products from the support was also observed, an effect which seems to determine the effective kinetic behaviour of immobilized LDH. The apparent optimum temperature is centred around 40°C, observing a clear inactivation (thermal denaturation) above this temperature. In the temperature range studied (10–40°C), the co-existence was seen of a kinetic control accompanied by another control, involving diffusional transport of substrates and products, on the global activity of the immobilized enzyme. This makes the Arrhenius profiles curvilinear. Both graphic and statistical non-linear regression analysis of the kinetic data—rate, v, versus substrate concentration [S]—carried out under conditions in which the diffusional limitations can be considered negligible (high recirculation flow rate), permitted investigation of the intrinsic kinetic behaviour of immobilized LDH. In this sense, it can be deduced that the rate equation to which these data seem to be fitted is of the polynomial quotient type in [S] of minimum degree 2:2. Although the diffusional limitations have a marked effect on the type of global kinetics shown by immobilized LDH, temperature was not found to affect its v[S] behaviour. The experimental evidence obtained thus indicates that the rate equation in the 10-40°C temperature range continues to be a rational equation of at least degree 2:2 in [S].     

KINETICS OF HYDROCARBON GAS GENERATION FROM MARINE KEROGEN AND OIL: IMPLICATIONS FOR THE ORIGIN OF NATURAL GASES IN THE HETIANHE GASFIELD, TARIM BASIN, NW CHINA

In this paper we derive kinetic parameters for the generation of gaseous hydrocarbons (C_1‐5) and methane (C₁) from closed‐system laboratory pyrolysis of selected samples of marine kerogen and oil from the SW Tarim Basin. The activation energy distributions for the generation of both C_1‐5 (Ea = 59‐72kcal, A = 1.0×10¹⁴ s^?1) and C₁ (Ea = 61‐78kcal, A = 6.06×10¹⁴ s^?1) hydrocarbons from the marine oil are narrower than those for the generation of these hydrocarbons from marine kerogen (Ea = 50‐74kcal, A = 1.0×10¹⁴ s^?1 for C_1‐5; and Ea = 48‐72kcal, A=3.9×10¹³ s^?1 for C₁, respectively). Using these kinetic parameters, both the yields and timings of C_1‐5 and C₁ hydrocarbons generated from Cambrian source rocks and from in‐reservoir cracking of oil in Ordovician strata were predicted for selected wells along a north‐south profile in the SW of the basin. Thermodynamic conditions for the cracking of oil and kerogen were modelled within the context of the geological framework. It is suggested that marine kerogen began to crack at temperatures of around 120°C (or 0.8 %Ro) and entered the gas window at 138°C (or 1.05 %Ro); whereas the marine oil began to crack at about 140 °C (or 1.1 %Ro) and entered the gas window at 158 °C (or 1.6%Ro). The main geological controls identified for gas accumulations in the Bachu Arch (Southwest Depression, SW Tarim Basin) include the remaining gas potential following Caledonian uplift; oil trapping and preservation in basal Ordovician strata; the extent of breaching of Ordovician reservoirs; and whether reservoir burial depths are sufficiently deep for oil cracking to have occurred. In the Maigaiti Slope and Southwest Depression, the timing of gas generation was later than that in the Bachu Arch, with much higher yields and generation rates, and hence better prospects for gas exploration. It appears from the gas generation kinetics that the primary source for the gases in the Hetianhe gasfield was the Southwest Depression.     

Models for the formation of poly(butylene terephthalate): effect of water on the kinetics of the titanium tetrabutylate-catalysed reactions: 3

In an effort to investigate the mechanism of catalysis of titanium tetrabutoxide on the polycondensation of poly(butylene terephthalate), alcoholysis and hydrolysis reactions were studied with the aid of model molecules. The retarding effect of water has also been taken into account. Appropriate kinetic equations are derived and discussed and the results compared with experimental data obtained at different molar ratios of reactants.     

Vinyl acetate monomer—a pilot plant study

The kinetics of the reaction of acetic acid and acetylene over zinc acetate-activated carbon catalyst was investigated over a wide range of process variables in a pilot reactor. Although various catalytic reaction mechanisms were postulated, the rate of reaction was most satisfactorily correlated by a mechanism of surface reaction between charged adsorbed acetic acid and acetylene, which assumes that the rate controlling step was the irreversible charged adsorption of acetylene and acetic acid.     

活性炭中甲烷水合物的生成动力学

在温度275．75－279．95K和压力5．6－9．6MPa的静置条件下，测定了14组甲烷水合物在活性炭中的生成动力学数据（压力－时间关系），分析了甲烷水合物在活性炭中生成的物理过程，结合边界层理论和结晶学原理，提出了单液膜传质控制机理的生成动力学模型，并求得了解析解,使用Levenberg-Marquardt方法拟合模型参数，模型预测值与实验值符合良好。     

Residue curve maps for reactive distillation systems with liquid-phase splitting

A model has been developed to study the effects of chemical kinetics on the residue curve maps (RCM) for reactive distillation systems with liquid phase splitting. In the model, chemical reaction can occur in both or only one of the two liquid phases. The heating policy V/V₀=H/H₀ is applied so that the kinetic effect can be described by a single parameter, the Damköhler number Da. The effects of reaction kinetics on pseudohomogeneous and heterogeneous mixtures have been compared. The properties of their RCMs are the same outside, but are fully different inside the liquid-liquid (L-L) region if they have different chemical equilibrium curves. Inside the L-L region, the chemical equilibrium curve coincides to a unique reactive liquid-liquid tie line in case that the pseudohomogeneous chemical equilibrium curve intersects with the L-L envelope. When the reaction occurs in only one of the two liquid phases, the residue curves inside the L-L region are strongly affected by the L-L envelope, especially at high Da. In the present paper, first an illustrative arbitrary reaction system, and then the reaction of cyclohexene with water to cyclohexanol are analysed with respect to their RCMs.     

Development and characterization of magnetorheological polymer gels

Magnetorheological materials have been used in many applications in recent years. To develop new materials, polyurethane and silicone polymer gels were investigated. Rheology is qualitatively controlled for each system by controlling the concentration of reactants and diluents. The resulting polymers have solid, gel, or liquid states, depending on the crosslinking and dilution. The gels were characterized through kinetic analysis. Differential scanning calorimetry (DSC) was used with analysis methods to find the kinetic properties for diluted and undiluted polyurethane systems. Heat of reaction, order of reaction, preexponential constant, and activation energy were obtained from the experimental DSC data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2733–2742, 2002