Advanced kinetic tools for the evaluation of decomposition reactions

Summary An advanced kinetic study on the thermal behaviour of pyrotechnic ignition mixtures has been carried out by differential scanning calorimetry using different B/KNO3 mixtures (50:50, 30:70, 20:80) as a model reaction. The experimental conditions applied (isochoric conditions/closed crucibles and isobaric conditions/open crucibles) as well as the composition of the mixtures noticeably influences the relative thermal stabilities of the energetic materials. The kinetic study focused on the prediction of the thermal stability of the different mixtures both in extended temperature ranges and under temperature conditions at which ordinary investigation would be very difficult. Using advanced numerical tools [1], thermal ageing and influence of the complex thermal environment on the heat accumulation conditions were computed. This can be done for any surrounding temperature profile such as isothermal, non-isothermal, stepwise, modulated, shock, adiabatic conditions and additionally for temperature profiles reflecting real atmospheric temperature changes (yearly temperature profiles of different climates with daily minimal and maximal fluctuations). Applications of accurate decomposition kinetics enabled the determination of the time to maximum rate under adiabatic conditions (TMR_ad) with a precision given by the confidence interval of the predictions. This analysis can then be applied for the examination of the effects of the surrounding temperature for safe storage or transportation conditions (e.g. determination of the safe transport or storage temperatures).     

Physico-chemical properties of deuteriated compounds 3rd communication. The viscosity of n-heptane

The kinematic viscosity of mixtures of perdeuteriated and protiated heptane has been measured between 15° and 35° and is given in polynomial form as a function of concentration and temperature. Using the McAllister equation to describe viscosity [4], it can be shown that the interactions between molecules containing the same or different isotopic species differ slightly.     

Crystallization kinetics of polymer–diluent mixtures. Influence of benzophenone on the spherulitic growth rate of isotactic polystyrene

As an extension of earlier work on the crystallization kinetics of isotactic polystyrene, the spherulite growth rate in mixtures of isotactic polystyrene and benzophenone has been measured over a concentration range extending from pure polymer to a mixture containing about 30% benzophenone. The glass transition temperature has been measured over the entire range from pure polymer to pure benzophenone. For the mixtures the dependence of the growth rate on temperature is similar to that of the undiluted polymer. The addition of benzophenone causes a shift of the crystallization range to lower temperatures. For mixtures containing up to about 20% benzophenone, the maximum in the growth rate increases with increasing content of benzophenone. On addition of more benzophenone, the maximum rate is depressed. Taking into account the glass transition temperature of the mixtures, the influence of benzophenone on the melting point of isotactic polystyrene, and the volume fraction of polymer, we can describe the influence of benzophenone on the growth rate in a semiquantitative way.     

Phase transitions in DNA-linked nanoparticle assemblies: a decorated-lattice model

We use decorated-lattice models to explore the phase behavior of two types of DNA-linked colloidal mixtures: systems with identical nanoparticles functionalized with two different DNA strands (mixture Aab) and mixtures involving two types of particles each one functionalized with a different DNA strand (mixture Aa-Ab). The model allows us to derive the properties of the mixtures from the well-known behavior of underlying spin-n Ising models with temperature and activity dependent effective interactions. The predicted evolution of the dissolution profiles for the colloidal assemblies as a function of temperature and number of single DNA strands on a nanoparticle M is in qualitative agreement with that observed in real systems. According to our model, the temperature at which the assemblies dissolve can be expected to increase with increasing M only for concentrations of colloids below a certain threshold. For more concentrated solutions, the dissolution temperature is a decreasing function of M. Linker-mediated interactions between Aa and Ab particles in the Aa-Ab mixture render the phase separation involving disordered aggregates metastable with respect to a phase transition between a solvent-rich and an ordered phase. The stability of the DNA-linked assembly is enhanced by the ordering of the colloidal network and the ordered aggregates dissolve at higher temperatures. Our results may explain the contrasting evolution of the dissolution temperatures with increasing probe size in Aab and Aa-Ab mixtures as observed experimentally.     

Reaction‐induced phase separation in epoxy/polysulfone/poly(ether imide) systems. I. Phase diagrams

Epoxy–aromatic diamine formulations are simultaneously modified with two immiscible thermoplastics (TPs), poly(ether imide) (PEI) and polysulfone (PSF). The epoxy monomer is based on diglycidyl ether of bisphenol A and the aromatic diamines (ADs) are either 4,4′‐diaminodiphenylsulfone or 4,4′‐methylenebis(3‐chloro 2,6‐diethylaniline). The influence of the TPs on the epoxy–amine kinetics is investigated. It is found that PSF can act as a catalyst. The presence of the TP provokes an increase of the gel times. Cloud‐point curves (temperature vs. composition) are shown for epoxy/PSF/PEI and epoxy/PSF/PEI/AD initial mixtures. Phase separation conversions are reported for the reactive mixtures with various TP contents and PSF/PEI proportions. On the basis of phase separation and gelation curves, conversion–composition phase diagrams at constant temperature are generated for both systems. These diagrams can be used to design particular cure cycles to generate different morphologies during the phase separation process, which is discussed in the second part of this series. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3953–3963, 2004     

High-temperature liquid chromatography. Part II: Determination of the viscosities of binary solvent mixtures—Implications for liquid chromatographic separations

This paper is the second in a series of consecutive publications, explaining the concept of high temperature liquid chromatography under various important aspects. The second publication deals with the determination of the viscosity of binary solvent mixtures used in reversed phase liquid chromatography in a temperature range between 25 and 250 °C. In literature, only limited data of the temperature dependent viscosities of liquid solvents or binary solvent mixtures can be found. Therefore, the viscosities of the pure solvents as well as the binary mixtures had to be determined experimentally up to 250 °C. The viscosity data were used to estimate the pressure drop in a capillary connecting a high-temperature HPLC system with a mass spectrometer. The solvent perturbation could be avoided by adjusting the diameter of the transfer capillary to the viscosity and vapour pressure of the mobile phase. The viscosity data were also used to show that a significant gain in analysis speed is theoretically feasible. This factor clearly depends on the nature of the solvent system, because for mixtures with a large viscosity maximum at ambient temperature, this effect is most pronounced.     

Solvent gradient operation of simulated moving beds. I. Linear isotherms

The simulated moving bed (SMB) is a multi-column chromatographic separation process, which--with respect to the single-column preparative batch process--allows for a continuous separation with larger productivity and smaller solvent consumption at the same time. The benefits of this process have been shown for several different applications in fine chemistry, particularly for the separation of enantiomers. In general, SMBs are operated under isocratic conditions. However, separation performance can be further improved by applying some sort of gradient mode operation, in order to optimize the operating conditions of each individual section of the unit. This can be achieved by tuning the retention behavior of the solutes to be separated along the unit, namely by enforcing weak adsorption conditions in sections 1 and 2, and strong adsorption conditions in sections 3 and 4. This can be achieved by applying a temperature gradient (high temperature in section 1, and low temperature in section 4), a pressure gradient (e.g. in the supercritical SMB, when pressure is high in section 1, and low in section 4), or a solvent gradient, which is the aim of this work. In the solvent gradient mode the mobile phase consists of a mixture of two or more solvents. To different mobile phase compositions corresponds a different retention behavior of the solutes, i.e. different adsorption isotherms. In this work we study a closed loop SMB unit with solvent mixtures of two different compositions entering the unit at the feed and desorbent inlet ports, respectively. Thereby two different mobile phase compositions are established in sections 1 and 2, and sections 3 and 4, respectively. To optimize this process the equilibrium theory design criteria for non-linear SMBs are extended to describe this operation mode. It is shown how the region of separation is derived and how the optimal operating conditions can be found. Finally the solvent gradient mode is compared with the isocratic mode in terms of productivity and solvent consumption.     

胆甾液晶／聚合物多组分体系的结构与性能研究（Ⅲ）──ChN／poly（MMA－CO－BMA）混合体系的形态结构

应用Ｘ射线衍射、偏光显微镜及电子显微镜研究了胆甾液晶与甲基丙烯酸甲酯（ＭＭＡ）─甲基丙烯酸丁酯（ＢＭＡ）无规共聚物共混体系的形态结构。研究了体系的结晶态及液晶态的行为和共聚物含量及组成对光学织构的影响。     

Relaxation dynamics in glycerol-water mixtures. 2. Mesoscopic feature in water rich mixtures

The relaxation dynamics of water-rich glycerol-water mixtures is studied by broadband dielectric spectroscopy (BDS) at 173-323 K and differential scanning calorimetry (DSC) at 138-313 K. These data indicate the existence of the critical concentration of 40 mol % glycerol. In the studied temperature range for water-rich glycerol mixtures, the two states of water (ice and interfacial water) are observed in addition to water in the mesoscopic 40 mol % glycerol-water domains. The possible kinetics of water exchange between different water states is discussed in order to explain the mechanism of the broad melting behavior observed by DSC.     

Molecular theory of phase equilibria in model and real associated mixtures III. Binary solutions of inert gases and n-alkanes in ammonia and methanol

Using new molecular models of ammonia and methanol and thermodynamic perturbation theory, the global phase diagrams of model mixtures of these compounds with a van der Waals fluid, representing a simple nonpolar fluid, have been calculated. The global phase diagram of these mixtures is much richer than that of corresponding aqueous mixtures. More types of critical line behavior are found, including the presence of van Laar points and a small region where the mixtures exhibit a closed liquid-liquid immiscibility loop (Type VI phase behavior). The individual mixture components are characterized by two molecular parameters, which can be adjusted to their critical temperature and critical volume; the mixture model itself contains no adjustable parameters. It is shown that the theory gives qualitatively correct predietions of mixtures with n-alkanes. This includes the prediction of Type III critical line behavior for small and large values of the ratio of the critical temperatures of the components, and Type II over a large range of conditions, including the presence or absence of absolute or limited azeotropy, and temperature and pressure extrema of critical lines and their dependence on the number of carbon atoms.     

Effect of temperature on pH measurements and acid-base equilibria in methanol-water mixtures

The knowledge of the acid-base equilibria in water-solvent mixtures of both common buffers and analytes is necessary in order to predict their retention as function of pH, solvent composition and temperature. This paper describes the effect of temperature on acid-base equilibria in methanol-water solvent mixtures commonly used as HPLC mobile phases. We measured the delta-correction parameter (delta = sw pH - ss pH = Ej - log sw(gamma)oh) between two pH scales: pH measured in the solvent concerned and referred to the same standard state, ss pH, and the pH measured in that solvent mixture but referred to water as standard state, sw pH, for several methanol compositions in the temperature range of 20-50 degrees C. These determinations suggest that the delta-term depends only on composition of the mixture and on temperature. In water-rich mixtures, for which methanol is below 40% (w/w), delta-term seems to be independent of temperature, within the experimental uncertainties, whereas for methanol content larger than 50% (w/w) the delta-correction decreases as temperature increases. We have attributed this decrease to a large increase in the medium effect when mixtures have more than 50% methanol. The pKa of five weak electrolytes of different chemical nature in 50% methanol-water at 20-50 degrees C are presented: the effect of temperature on pKa was large for amines, pyridine and phenol, but almost no dependence was found for benzoic acid. This indicates that buffers can play a critical role in affecting retention and selectivity in HPLC at temperatures far from 25 degrees C, particularlyfor co-eluted solutes.     

Mutual diffusion in binary mixtures of ionic liquids and molecular liquids by dynamic light scattering (DLS)

The present study shows that dynamic light scattering (DLS) is capable of measuring mutual diffusion coefficients for binary mixtures of ionic liquids (ILs) with different molecular liquids over the complete composition range. Evidence is given that the light scattering signals are related to true molecular binary diffusion. The method stands out due to its ability to work non-invasively in macroscopic thermodynamic equilibrium with reasonable accuracy and within convenient measurement periods. Compared with other techniques, mixtures with distinctly higher viscosities can be probed. For exemplary binary mixtures of 1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][EtSO(4)]) with acetone, acetonitrile, dichloromethane, ethanol, or water as well as of 1-ethyl-3-methylimidazolium methanesulfonate ([EMIM][MeSO(3)]) with acetone, water, or methanol, mutual diffusivity data were measured over a wide range of composition at a temperature of 293.15 K. In general, the mutual diffusivity increases with increasing mole fraction of the molecular liquid and similarities to aqueous solutions of classical inorganic salts can be found. The characteristic behavior of the mutual diffusion coefficients is influenced by the nature of the chosen molecular liquid. For IL water mixtures, low light scattering intensities were observed despite the large refractive index difference of the pure components. The reason for this behavior may be the existence of water clusters in the mixtures. Additional measurements for IL acetone mixtures at temperatures ranging from 278.15 K to 323.15 K showed that the temperature dependence of the mutual diffusivity can be represented by Arrhenius functions and is increasing for decreasing mole fractions of acetone.     

Temperature depending light scattering measurements of aqueous gelatin and alginate solutions and their mixtures

Highly diluted solutions of an alkaline treated pig bone gelatin and a seaweed alginate of Macrocystis pyrifera have been investigated by means of static light scattering at various temperatures. With these results the thermodynamic properties found by other authors and us before can be verified. Furthermore, diluted mixtures of both polymers with different ratios of composition have been investigated. These measurements show that both polymers in all mixtures behave quasi-binarily in the investigated temperature range. They maintain their association phenomena of the pure polymer solutions.     

Speed of flame propagation in CH<Subscript>3</Subscript>Cl + Cl<Subscript>2</Subscript> mixtures during combustion initiated by continuous UV radiation

Flame propagation in a closed tube over mixtures of chloromethane and chlorine of different compositions following ignition by continuous UV radiation is studied. It is found that the rate of combustion in all mixtures except limiting ones grows along with the propagation of the flame front up to its maximum values at nearly 1/3 the tube length and then slows. In limiting mixtures, the speed’s behavior is completely different. It is greatest near the source of UV light and gradually slows with distance from the source. The high speed in the initial section is due to the effect of UV light. The temperature of combustion is lowest in limiting mixtures, and the rate of chlorine molecule photodissociation at this temperature is comparable to and even faster than that of their thermal dissociation. The light in these mixtures thus contributes substantially to the initiation of the chemical reaction. It is concluded that when limiting mixtures are ignited by UV pulses, the speed of flame propagation falls markedly as it proceeds without the influence of radiation, and the character of changes in the speed’s behavior becomes identical to those for other mixtures.     

Understanding fragility in supercooled Lennard-Jones mixtures. I. Locally preferred structures

The existence of systematic variations of isobaric fragility in different supercooled Lennard-Jones binary mixtures is revealed by molecular dynamics simulations. The connection between fragility and local structures in the bulk is analyzed by means of a Voronoi construction. It is found that clusters of particles belonging to locally preferred structures form slow, long-lived domains, whose spatial extension increases with decreasing temperature. As a general rule, a more rapid growth, upon supercooling, of such domains is associated with a more pronounced super-Arrhenius behavior, and hence to a larger fragility.     

Quantitative determination by temperature dependent near-infrared spectra

Near-infrared (NIR) spectra are sensitive to the variation of experimental conditions, such as temperature. In this work, the relationship between NIR absorption spectra and temperature was quantitatively analyzed and applied to the quantitative determination of the compositions in mixtures. It was found that, for the solvents such as water and ethanol, a quantitative spectra-temperature relationship (QSTR) model between NIR spectra and temperature can be established by using partial least squares (PLS) regression. Therefore, the temperature of a solution can be predicted by using the model and NIR spectrum. Furthermore, it was also found that the difference between the predicted results of different solutions is a quantitative reflection of concentration. The variation of intercept in the relationship of the predicted and measured temperature can be used to determine the concentration of the compositions. The mixtures of water, methanol, ethanol and ethylenediamine in a concentration range of 5-80% (v/v) were studied. The calibration curves are found to be reliable with the correlation coefficients (R) higher than 0.99. Both the QSTR and calibration model may extend the application of NIR spectroscopy and provide novel techniques for analytical chemistry.     

Thermo-osmosis of sorbable gases in porous media : Part II. Cascades

The theoretical basis of mixture separation by thermo-osmosis has been developed for two different experimental arrangements. In the first of these two vessels are connected only by a membrane across which a temperature gradient is maintained. Expressions were obtained for the separation factor of binary mixtures in terms of heats of transport, for pressure and composition changes across the membrane, and for determining the heat of transport of each component. In the second arrangement the vessels are connected via the membrane and also by a capillary of appropriate geometry, so that in the steady state there is a constant circulation of each component of the mixture. Expressions have again been derived for the steady state separation factor, and pressure and composition differences for binary mixtures.