Kinetics of the reaction of the TEMPO radical with alkylarenes

The kinetics of the reaction of the stable radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) with a series of alkylarenes containing primary and secondary benzyl C—H bonds was studied by ESR, and the reaction rate constants were determined. The scheme of the process under study was examined, and the applicability boundaries of the simplification during analysis were shown. The selectivities of TEMPO and the more reactive cumylperoxyl radical were compared.     

Dependence of Thermal Decomposition Rate Constant on Temperature of Reaction

On the basis of results of kinetic investigates of many compounds general temperature dependence of Gibbs free energy of activated complexes created in thermal decomposition processes and the reaction rate constant were calculated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal properties of oxide glasses

Glasses with the composition Li₂O·2SiO₂·nTiO₂ and Li₂O·2SiO₂·nZrO₂, where n=0, 0.03, 0.062, 0.1, were prepared and the onset and peak temperatures have been determined by DTA. From these characteristic temperatures, the kinetic parameters describing the nucleation and crystal growth have been obtained by isoconversional methods. The kinetic parameters have been used for the calculation of nucleation and crystal growth times for individual glasses so determining the order of glass stability at reheating. The stability of glasses increases with the content of TiO₂ or ZrO₂ where the increase is higher for ZrO₂. Within the concentration range under study, the increase of both times with the metal oxide concentration is quadratic. It has been discussed that the crystallization kinetics does not obey the Arrhenius law and, therefore, when using the evaluation methods based on this law, the results should not be extrapolated outside the temperature range of the measurements.     

Dosimetric properties of commercial grade plexiglas as a possible routine dosimeter for radiation processing

Dyed and undyed polymethylmethacrylate (PMMA) are commercially available for high dose dosimetry in radiation processing applications. In order to investigate the properties of the locally available clear perspex as a subsitute routine dosimeter, we have looked into the optical and dosimetric properties of clear perspex sheets with a thickness of 2 mm.

The selected wavelength used for read out was 314 nm. Absorption spectra obtained showed a sharp cutoff at 260 nm wavelength. Post-irradiation studies at different doses indicate that the optical density decrease with storage time. No significant dose rate dependence in the range of 1.1 to 11 kGy/hr has been observed. The temperature response of the said clear perspex in the range of 0–30°C during irradiation has also been determined.

Comparison of the optical density versus dose for the local clear perspex against that of red perspex from Harwell, at an absorbed dose of 25 kGy, as obtained in our gamma irradiator, IR-136, showed a difference of 3%. The reproducibility of the local clear PMMA has been observed to be also less than 3% in an absorbed dose range of 5 to 50 kGy.     

Some considerations concerning the temperature dependence of the bulk crystallization rate constants of polymeric materials

The experimentally estimated ‘normalized’ rate constants of the bulk crystallization of poly(L-lactic acid) and natural rubber at different temperatures have been used in order to test different equations describing the temperature dependence of the normalized crystallization rate constants. Ten of these expressions are variants of the well-known Turnbull-Fisher relationship k = k₀ exp[-U*/R(T - T_∞)] exp[K_g/T(ΔT)f] which differ essentially by the assumed number of fixed parameters [one or two Williams, Landel, and Ferry (WLF) constants i.e., U* = C₁ and/or C₂]. Two additionally used equations are expressions derived on the basis of the above mentioned general relation, which introduce T_g instead of T_∞ = T_g - C₂ as the low temperature limit of crystallization and two energies of activation, for nucleation and crystal growth, respectively. It is shown that the temperature dependence of the normalized bulk crystallization rate constants is more accurately described if three parameters (beside k₀, U*, and K_g or the respective activation energies) are assumed to be adjustable and when instead of the widely accepted expression for the low temperature limit, T_∞ = T_g - C₂(K) with C₂ = 51.6 or 30°C, respectively, T_g (i.e., C₂ = 0°C) is considered. A qualitative explanation for this finding is suggested in terms of the increasing mobility of the crystallizing segments at temperatures above T_g, taking into account that generally the glass transition is considered to be a ‘freezing in’ process. © 1997 John Wiley & Sons, Inc.     

Direct optical observation of the formation of some aliphatic alcohol radicals. A pulse radiolysis study

The kinetics of the reactions of hydroxyl radicals and hydrogen atoms with some aliphatic alcohols in aqueous solutions were studied using pulse radiolysis. Based on the increase in optical absorption in the UV region, the rate constants for the reaction of hydroxyl radicals and hydrogen atoms with methanol, ethanol, 2-propanol ort-butyl alcohol were determined to be 9.0 × 10⁸, 2.2 × 10⁹, 2.0 × 10⁹,6.2×l0⁸ and 1.1 × 10⁶, 1.8 × 10⁷, 5.3 × 10⁷, 2.3 × 10⁵ dm³ mol⁻¹ s⁻¹ respectively. The bimolecular decay rate constants for the alcohol radicals produced in methanol and ethanol were evaluated to be 2.4 × 10⁹ and 1.5 × 10⁹ dm³ mol⁻¹s⁻¹. The values observed are in fairly good agreement with those reported earlier.     

Probing the Hydrogen Bonding Structure in the Rieske Protein

The use of the far‐infrared spectral range presents a novel approach for analysis of the hydrogen bonding in proteins. Here it is presented for the analysis of Fe? S vibrations (500–200 cm^?1) and of the intra‐ and intermolecular hydrogen bonding signature (300–50 cm^?1) in the Rieske protein from Thermus thermophilus as a function of temperature and pH. Three pH values were adequately chosen in order to study all the possible protonation states of the coordinating histidines. The Fe? S vibrations showed pH‐dependent shifts in the FIR spectra in line with the change of protonation state of the histidines coordinating the [2Fe? 2S] cluster. Measurements of the low‐frequency signals between 300 and 30 K demonstrated the presence of a distinct overall hydrogen bonding network and a more rigid structure for a pH higher than 10. To further support the analysis, the redox‐dependent shifts of the secondary structure were investigated by means of an electrochemically induced FTIR difference spectroscopic approach in the mid infrared. The results confirmed a clear pH dependency and an influence of the immediate environment of the cluster on the secondary structure. The results support the hypothesis that structure‐mediated changes in the environment of iron? sulfur centers play a critical role in regulating enzymatic catalysis. The data point towards the role of the overall internal hydrogen bonding organization for the geometry and the electronic properties of the cluster.     

Comparison of the Temperature Effect on the π∗←n and π∗←π Electronic Transition Bands of NO<Subscript>3</Subscript><Superscript>−</Superscript>(aq)

The effect of temperature on the π∗←π transition band in the UV absorption spectrum of NO₃⁻(aq) centered at ≈200 nm was studied in the temperature range 10–70 ^∘C. The observed temperature independence of this band was in contrast to the significant influence of temperature on the nitrate π∗←n transition reported recently by us. However, taking into account the electronic states involved in both the transitions, it was concluded that this finding was in accordance with our previous assumption that interconversion between spectrally distinct (with respect to π∗←n band) nitrate species included the rupture/formation of hydrogen bond(s) in the hydration shell of the nitrate ion.     

Reactions of CO2 with H, H2 and deuterated analogues

Combining a temperature variable 22-pole ion trap with a cold effusive beam of neutrals, rate coefficients k(T) have been measured for reactions of CO₂⁺ ions with H, H₂ and deuterated analogues. The neutral beam which is cooled in an accommodator to T_ACC, penetrates the trapped ion cloud with a well-characterized velocity distribution. The temperature of the ions, T_22PT, has been set to values between 15 and 300 K. Thermalization is accelerated by using helium buffer gas. For reference, some experiments have been performed with thermal target gas. For this purpose hydrogen is leaked directly into the box surrounding the trap. While collisions of CO₂⁺ with H₂ lead exclusively to the protonated product HCO₂⁺, collisions with H atoms form mainly HCO⁺. The electron transfer channel H⁺ + CO₂ could not be detected (<20%). Equivalent studies have been performed for deuterium. The rate coefficients for reactions with atoms are rather small. Within our relative errors of less than 15%, they do not depend on the temperature of the CO₂⁺ ions nor on the velocity of the atoms (k(T) lays between 4.5 and 4.7 × 10⁻¹⁰ cm³ s⁻¹ with H as target, and 2.2 × 10⁻¹⁰ cm³ s⁻¹ with D). For collisions with molecules, the reactivity increases significantly with falling temperature, reaching the Langevin values at 15 K. These results are reported as k = α (T/300 K)^β with α = 9.5 × 10⁻¹⁰ cm³ s⁻¹ and β = −0.15 for H₂ and α = 4.9 × 10⁻¹⁰ cm³ s⁻¹ and β = −0.30 for D₂.     

Extrapolation of accelerated thermooxidative tests to lower temperatures applying non-Arrhenius temperature functions

Extrapolations of the accelerated thermooxidative tests, based on the Arrhenius and two non-Arrhenius temperature functions, have been tested for 26 data sets. The data cover a wide range of materials from polyolefins and other polymers to biodiesel, edible oils and dried milk. It has been found that the extrapolation from high-temperature data to ambient temperature based on the Arrhenius temperature function leads to the estimations of unrealistically long durability. The best estimations corresponding most with experience are obtained for the extrapolation based on the temperature function k(T)=A _kexp(DT).     

Molecular Dynamics Studies of the Kinetics of Phase Changes in Clusters IV： Crystal Nucleation from Molten （NaCl）256 and （NaCl）500 Clusters

Molecular dynamics computer simulation based on the Born-Mayer-Huggins potential function has been carried out to study the effects of duster size and temperature on the nucleation rate of sodium chloride dusters in the temperature range of 580 K to 630 K. Clusters with 256 and 500 NaCl molecules have been studied and the results have been compared with those obtained from 108 molecule dusters. The melting point (MP) of the clusters were observed to increase with the size of the clusters and can be well described by a linear equation MP =1107(37)-1229(23)N^-1/3(N is the number of molecules in the duster).The nucleation rate was found to decrease with increasing the duster size or temperature. Various nucleation theories have been used to interpret the nucleation rates obtained from this molecular dynamics simulation. It is possible to use a constant diffuse interface thickness to interpret the nucleation rate from the diffuse interface theory in the temperature range of this study. However, the interfacinl free energy estimated from classical nucleation theory and diffuse interface theory increases too fast with increasing the temperature while that from Gran-Gunton theory does not change with changing temperatures.The sizes of critical nuclei estimated from all the theories are smaller than those estimated from our simulations.