Temperature compensation in the oscillatory bray reaction

The influence of temperature on the oscillatory frequency of the hydrogen peroxide-iodate ion reaction is found to be two-sided: (i) the period length decreases with increasing temperature in most of the instances studied, (ii) or in some cases an opposite change is observed. A temperature-independent period length (temperature compensation) is also discovered experimentally in a rather wide temperature interval at a narrow concentration range of reactants both in a batch configuration and under flow conditions. A simple model was considered to simulate this behavior. Opposing effects of the composite reactions of the model on the calculated period length with changing temperature are shown to be responsible for temperature compensation or overcompensation.     

Emulsion stabilization and inversion using a pH- and temperature-sensitive amphiphilic copolymer

We describe how a versatile amphiphilic diblock copolymer can form oil-in-water (o/w) or water-in-oil (w/o) emulsions depending on pH and temperature. At high pH and temperature, this copolymer is mostly hydrophobic and forms w/o emulsions. Its spontaneous curvature is greatly increased upon pH and/or temperature lowering (due to protonation and/or hydration, respectively), which allows the formation of o/w emulsions. Conductivity measurements and confocal fluorescence micrographs evidence the two kinds of structures obtained over a wide range of pH and temperature. We also show how the emulsion type can be reversibly switched along a temperature scan under stirring. The lower stability of the w/o emulsions as compared to the o/w ones is attributed to a lack of electrostatic repulsion. The importance of the copolymer architecture and conformation with regards to droplet stability is discussed.     

Fermentation alcoolique

The control of alcoholic fermentation is necessary to obtain a quality wine.The overall dynamic and phenomenological modelling already applied to the simulation of this type of reaction enables us to suggest, in this study, a simple model (of which two variants), are relatively satisfactory.The first variant does not take into account the variation of the ambient temperature; the model translates exactly the first phase of the experimental curve or the moment when highest temperatures are measured. The relaxation phase is less well described because of influence of variation of the ambient temperature is relatively important.The second one considers the system depending on the ambient temperature, the model is correct for the relaxation phase too (the reaction temperature decreases, it nears the ambient temperature).The advantage of this model: It permits one to determine the reaction enthalpy and the kinetic parameters.

     

Study of temperature distribution of sliding block with asperity surface

In this study, a numerical thermal model is developed for sliding block contact under various loads, sliding velocities and surface roughness. The temperature distributions are shown for perfectly insulated thermal conditions along noncontact surfaces. For a particular five‐peaks contact model, the maximum temperature at the central peak is slightly lhigher than the others. The temperature profile decreases as the distance to the symmetry axis increases, and then decreases dramatically at the noncontact area. It is clear to see that the maximum temperature locates at the symmetry central peak of the asperity contact area instead of the leading head of the smooth surface. The maximum temperature rise parameter increases as the pressure, sliding velocity and asperity roughness increased or conductivity decreased. This phenomenon becomes obvious for cases at high pressure, velocity and roughness and low conductivity. Particularly, the influence of roughness is not significant for low velocity. Similar results are found for the maximum temperature rise parameter difference between peaks or peaks/valleys. The simulation results of this asperity surface sliding block contact model are able to provide essential information for the components of microelectro—mechanical systems (MEMS) and biochemical reaction mechanism. Copyright © 2011 John Wiley & Sons, Ltd.     

Microwaves and sorption on oxides: a surface temperature investigation

Microwave heating is not the same as conventional heating, and it is believed that this difference, the "microwave effect," may be interpreted to be due to selective, local heating. The temperature at the surface where sorption occurs is "effectively" greater than the measured solid or gas temperature. In these studies, measurements of the amounts of adsorption as functions of the partial pressures of a specific adsorbate in the presence of microwave irradiation were related to the conventional adsorption isotherms. Equating the adsorbate pressure required to achieve a specific coverage (an isostere) in the presence of microwave irradiation to the amount adsorbed for a conventional isotherm allowed for an estimate of the "effective" surface temperature in the presence of microwaves. It was found that the effective surface temperature increased when using adsorbates having a higher permittivity or when increasing the microwave power. The implication of this change in the surface energy for specific species in the presence of microwaves is discussed.     

Estimation of the Combined Effect of Temperature and Carbon Dioxide Pressure on Dissolved Calcium Carbonate Concentration in Oilfield Brines

Calcium carbonate, or calcite, scale is frequently encountered in oilfield operations. In a reservoir, when brine is produced, it is disturbed because the brine is moved to lower temperature and pressure areas. The dissolved concentration of calcium carbonate is greatly influenced by temperature and the partial pressure of carbon dioxide gas over the water. The net result of a drop in temperature and pressure may therefore be an increase or a decrease in the calcium carbonate saturation ratio as determined by the temperature change relative to the pressure change. In this article, a simple Arrhenius-type function is developed to estimate the combined effect of temperature and carbon dioxide pressure on calcium carbonate dissolved concentration in oilfield brines. Estimations are found to be in excellent agreement with reported data in the literature with average absolute deviation being less than 2%. The tool developed in this study can be of immense practical value for engineers to have a quick check of combined effect of temperature and carbon dioxide pressure on calcium carbonate dissolved concentration at various conditions without opting for any field or experimental trials. In particular, engineers would find the approach to be user friendly with transparent calculations involving no complex expressions.     

Thermal stress development of liquid silicone rubber seal under temperature cycling

Liquid Silicone Rubber (LSR) is commonly used as gasket or seal material in many industrial applications. The temperature dependent material property of polymeric rubbers will result in stress relaxation/creep. The development of compressive stress in LSR between two clamping metal plates under temperature cycling is discussed in this paper. It is found that (a) in addition to stress relaxation, thermal expansion or contraction of the material contributes the most in the observed stress variation during temperature change, and (b) the stiffness of LSR appears to change according to temperature history.     

A new high temperature gas chromatograph incorporating a temperature programmable direct injector

A high temperature gas chromatograph has been developed which is capable of operating at column oven temperatures up to 500°C. In addition, the detector can operate at temperatures up to 500°C, and the injector up to 450°C. The injector on this instrument is a temperature programmable direct injector, designed specifically to introduce labile or high molecular weight samples into the GC without molecular weight discrimination. The design of this GC and injector will be described, and high temperature applications will be discussed.     

A model for quantitatively describing linear velocity programming in capillary SFC

Summary Linear velocity in capillary SFC is commonly controlled by restricting capillaries. In this paper, a model is described that quantitatively predicts the linear velocity of a supercritical fluid in SFC using tapered or ceramic frittype restrictors. In this model, the flow from the restricting capillary is assumed to be an isentropic expansion. The variation of the linear velocity as a function of pressure, temperature and cross-sectional area of the restricting aperture was predicted by this model. This predictive capability is important to the use of gradient programming in capillary SFC. Finally, the ideal variable restrictor for gradient programming was found to be one that could reversibly increase or decrease the linear velocity independent of the pressure, temperature, and/or density conditions used to create the gradient.     

Determining the temperature to initiate the explosion of a propellant

Summary Gun propellants are per definition instable substances. During their lifetime a slow decomposition process is going-on. During this decomposition process the heat that is generated accelerates the process, which could result to an unsafe situation, or an unexpected explosion of the material. The temperature to initiate the explosion of a propellant is of importance for the storage conditions of such a substance. The method used so far to evaluate this temperature is based on an extrapolation of the Kissinger equation at zero heating rate. A new proposal is the use of the invariant kinetic parameters (IKP) method to determine the iso-kinetic temperature and extrapolating it to zero heating rate as an alternative method. The results are discussed for some examples.     

Relation between the melting temperature and the temperature of maximum density for the most common models of water

Water exhibits a maximum in density at normal pressure at 4 degrees above its melting point. The reproduction of this maximum is a stringent test for potential models used commonly in simulations of water. The relation between the melting temperature and the temperature of maximum density for these potential models is unknown mainly due to our ignorance about the melting temperature of these models. Recently we have determined the melting temperature of ice I(h) for several commonly used models of water (SPC, SPC/E, TIP3P, TIP4P, TIP4P/Ew, and TIP5P). In this work we locate the temperature of maximum density for these models. In this way the relative location of the temperature of maximum density with respect to the melting temperature is established. For SPC, SPC/E, TIP3P, TIP4P, and TIP4P/Ew the maximum in density occurs at about 21-37 K above the melting temperature. In all these models the negative charge is located either on the oxygen itself or on a point along the H-O-H bisector. For the TIP5P and TIP5P-E models the maximum in density occurs at about 11 K above the melting temperature. The location of the negative charge appears as a geometrical crucial factor to the relative position of the temperature of maximum density with respect to the melting temperature.     

Organic Fluorine Compounds and Their Uses as Molecular MR-Based Temperature Sensors

The interest in fluorinated substances has increased significantly in recent decades due to their diverse properties and possible uses. An important analytical method in this context is NMR spectroscopy, which provides information on the structure as well as on intermolecular interactions or generally on changes in the environment of the nucleus under consideration. A physical quantity that is of great importance in most studies is temperature. However, this is not always easy, e. g. in shielded systems or within an organism. However, the application potential in chemical reactors or in medical diagnosis and therapy is very high and for this reason 13 fluorinated organic compound were chosen for a first ¹⁹F NMR signal temperature sensitivity examination for determination of local temperatures in solution. Polyfluorinated molecules with separate ¹⁹F MR signals are particularly suitable for temperature determination. Those can be serve as internal error-correcting thermometers without the need of a reference substance. Under these conditions, a ¹⁹F MR signal shift of up to 0.03 ppm/K was detectable. Fluorine position and chemical environment were very important for the temperature sensitivity.     

用于气/固吸附的微分吸附热测定装置

本文介绍了一套吸附热测定装置, 它是对法国SETARAM高温量热计进行了适当变动后而建成的。用它可以测定在室温～800 K范围内气/固吸附的微分吸附热。在实验过程中, 吸附量是用光标微压计进行测量。用电标定法代替标准物质法来测定该装置的热定量因子, 这更适合于在恒温条件下的吸附热测定。用这套装置测定了吡啶在HY分子筛上于不同温度下的吸附热。     

A method for experimental determination of the temperature dependence of relaxation times in dielectrics

A new method is suggested for the experimental determination of the dependence of the relaxation times on the temperature in dielectrics for which the time–temperature superposition principle is valid. The method makes possible the determination of this dependence for a separate relaxation process (for instance, for the β-relaxation process) over a wide temperature range by means of comparatively simple mathematical operations which are only slightly sensitive to experimental errors. Two or more discharge-current curves, measured with temperatures increasing in an arbitrary way with time, are used for this purpose.     

Deviation from van't Hoff dependence in RP-LC induced by tautomeric interconversion observed for four compounds

The most encountered situations in reversed-phase liquid chromatography for temperature dependence of retention are those obeying the linear equation known as the van't Hoff plot. When studying compounds that are involved in structural modifications, it is likely that the temperature dependences of their retention factors do not follow this rule. It is the aim of this paper to report some particular cases when compounds involved in tautomeric interconversion have a different retention behavior with temperature: a deviation from the linearity of ln k on 1/T, or, in certain temperature ranges, temperature increase leading to a retention increase. Examples of compounds exhibiting deviation from the van't Hoff temperature dependence are piroxicam, drotaverine, vincamine, and epivincamine. A simple thermodynamic model relying on tautomeric equilibria in mobile phase is proposed for these compounds, which gives a polynomial dependence between ln k and 1/T.     

固定床天然气与煤共气化火焰区温度影响因素的研究

用实验室固定床反应器模拟合成气制备炉，考察了该工艺中不同因素对火焰区温度的影响。实验中首先确定了使火焰区温度最低时的甲烷和氧气相对入口位置，然后在此条件下分别考察了进料中H2O/O2和CH4/O2摩尔比变化对火焰区温度的影响。结果表明，甲烷和氧气相对入口位置平齐时火焰区温度最低，火焰区温度均随进料中CH4/O2和H2O/O2摩尔比的增大而降低。     

空间展布体系中由化学反应-扩散-热传导耦合导致的温度场对称破缺

分析了由于化学反应-扩散-热传导耦合而导致的非等温非均匀体系中温度场对称破缺.研究结果表明,在一定的边界条件下,甚至是单组分化学反应-扩散-热传导体系,温度场的这种自组织进程也不可避免.作为温度场结构的一个范例,进一步从解析解及计算机模拟两个方面研究了小展布非等温的Lindeman模型;结果表明,温度场出现时空自组织的阈值不仅与本征参数有关,而且与体系的边界条件及外控约束相关,揭示出了诱发或避免这种温度场时空自组织之途径.     

Development of a calorimetric sensor for medical application

A calorimetric sensor has been developed for local and direct measurement of calorific dissipations in different parts of the human body. The constructed prototype has a detection surface of 36 cm². In this paper, a deconvolution method is proposed to reconstruct the dissipated power. The advantage of this method is that: to determine the dissipated power, it is not necessary to correct the baselines to calculate either the areas of the calorimetric signal or that of the dissipated power in the temperature control because the proposed method takes into account, apart from the calorimetric signal, the thermostat temperature and the ambient temperature.     

Influence of fillers on mechanical properties of ATH filled EPDM during ageing by gamma irradiation

The presence of a significant content of fillers accelerates the degradation of ATH filled EPDM subjected to gamma irradiation at room temperature. Above the melting temperature of the EPDM, this induces a decrease in the apparent mechanical reinforcement of the fillers. This also promotes de-cohesion mechanisms which leads to an increase in the strain at break with irradiation dose. It is not clear whether the use of a filler treatment attenuates this accelerating effect or not; however, part of this treatment remains efficient at a high dose and seems also to delay but not suppress the occurrence of de-cohesion mechanisms at large strain. Moreover, at room temperature, i.e. below the melting temperature, all the consequences of ageing by gamma irradiation are strongly attenuated by the presence of a semi-crystalline microstructure, the morphology of which is not too strongly modified by irradiation.