Kinetics of radiation polymerization of vinyl benzoate

Abstract

Vinyl benzoate was polymerized by γ-radiation from a cobalt-60 source and the kinetics of polymerization were studied at several temperatures. The results showed that the rate of polymerization was proportional to I^0.66 , where I is the radiation dose rate. The net activation energy for the polymerization reaction, (E_p -1/2 E_t ), was found to be 3.62 kcal, where E_p and E_t are the activation energies for the propagation and termination stages of the reaction. The radical yield measured by the loss of DPPH in the solution after irradiation was G=5.0, while the G (Radical) effective in initiating polymerization was 0.94. The ratio of the rate constants, k² _p/k_t = 5.8 × 10^?4 at 60° and 1.59 × 10^?4 at 25° The rate of polymerization was higher than that of styrene but lower than that of vinyl acetate under comparable conditions.     

An experimental investigation of substituent effects on the formation of 2,3‐dihydroquinazolin‐4(1H)‐ones: a kinetic study

The effect of different substituents on the kinetics of the reactions between 2‐amino‐benzamide and some of benzaldehyde derivatives have been spectrally investigated in the presence of formic acid. The proposed mechanism were challenged due to the determination of rate‐determining step (RDS) and also, to obtain the general rate law of the reaction. For all substituents, the reactions followed the second‐order kinetics and the partial orders of reactions were recognized with respect to each reactant. Electron withdrawing substituents on benzaldehyde ring increased the rate of reaction. Kinetic values (k and E_a) and associated activation parameters (ΔH^?, ΔG^? and ΔS^?) of the reactions were determined. Both the Arrhenius and the Eyring equations were used to calculate activation energy. Comparison of magnitude of and T showed that the reactions were enthalpy controlled. Isokinetic plots for the reactions were plotted and linear relationship between and recognized that relative contribution of enthalpy and entropy to the overall free energy was the same in the reactions.     

Spectroscopic search for the free carrier screening of the excitonic binding

A spectroscopic determination of the energy gap E_g and the exciton energy E_x in highly excited Ge at T = 5–20K is presented. Within 0.05 meV we observe no shift of E_g and E_x up to electron-hole densities of 10¹⁴?10¹⁵ cm^?3. In this range all previous theories predict a sizeable band renormalization (ΔE_g ≈?0.3 meV to ? 2 meV).     

In-beam spectroscopy of231Pa

Information on energy levels and onE 2 andM 1 matrix elements in²³¹Pa has been obtained using conversion-electron and gamma-ray spectroscopy following the²³²Th(p, 2n)²³¹Pa reaction and Coulomb excitation of the radioactive target²³¹Pa by⁴He and³²S ions. The results are analyzed in the framework of the rotational model, applied to the rotational band built on the 1/2^?[530] Nilsson state whose 3/2^? member forms the ground state of this nucleus. The deviations of the level energies from the rigid-rotor values can be described by Coriolis couplings. The analysis of the Coulomb-excitation process shows that a constant set of rotational parameters Q₀, g_R, g_K, andb can fairly well account for the measured line intensities.     

The dehydration kinetics of gypsum at high pressure and high temperature

An in situ dehydration kinetics study of gypsum under water-saturated condition was performed in the temperature and pressure ranges of 383–423?K and 343–1085?MPa by using a hydrothermal diamond anvil cell and Raman spectroscopy. Kinetic analysis shows that the dehydration rate k increases with pressure, suggesting a negative pressure dependence on dehydration rate. The elevation of temperature can contribute to the dehydration. The n values increase with pressure, indicating that the nucleation process becomes slower relative to the growth process. According to the n values of ～1.0, the dehydration of gypsum is dominated by an instantaneous nucleation and diffusion-controlled growth mechanism. The obtained average activation volume ?V is equal to 5.69?cm³/mol and the calculated activation energy E_a and the pre-exponential factor A are 66.9?kJ/mol and 4.66?×?10⁵?s^?1. The activation energy may be dependent upon grain size, shape, temperature and pressure, and surrounding water.     

Kinetics of isothermal decomposition of unirradiated and γ-irradiated zirconium acetylacetonate

In this study, isothermal decomposition of unirradiated and γ-irradiated zirconium acetylacetonate Zr(acac)₄ using 10³ kGy absorbed γ-ray dose was carried out in static air. The isothermal operating temperatures were selected to be 150, 170, 190 and 210°C. The kinetics of the decomposition were followed using both model-fitting and model-free approaches. The results of the model-fitting approach with regard to the investigated data showed that the decomposition behaviour was best described by a first-order (F1) reaction model. The analysis of the data using the model-free approach signified the dependency of activation energy E _a on the extent of conversion (α). Pre-γ-irradiation of zirconium acetylacetonate Zr(acac)₄ with 10³ kGy absorbed γ-ray dose had no significant effect on the thermal decomposition behaviour of Zr(acac)₄. The thermodynamic and kinetic parameters of the decomposition process were calculated and evaluated.     

Magnetic field effects on the hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol as studied by a picosecond laser flash photolysis technique

The hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol at 265 K has been studied with a newly developed picosecond laser flash photolysis apparatus under magnetic fields of 0–1.7 T. The decay rate constant of the radical pair generated was found to increase from 3.42 × 10⁹ s^?1 to 4.15 × 10⁹ s^?1 with increasing the magnetic field from 0 to 1.7 T. The observed magnetic field effects can be explained by the Δg mechanism. Using the simple kinetics model with the Δg mechanism, the rate constant of the escape process from the pair (k _esc) and two rate constants for the T-S spin conversion process (k _T-S) at 0 and 1.7 T were found to be 1.97 × 10⁹ s^?1, 1.45 × 10⁹ s^?1, and 2.12 × 10⁹ s^?1, respectively. From the magnetic field dependence on k _T-S, the difference in the g values of the 4-methoxybenzophenone ketyl and phenylthiyl radicals was estimated to be 0.0087.     

Adsorption and decomposition of formic acid on the NiO(111)-p(2 × 2) surface: TPD and steady state kinetics studies

The adsorption and decomposition of formic acid on NiO(111)-p(2 × 2) films grown on Ni(111) single crystal surface were studied by temperature-programmed desorption (TPD) spectroscopy. Exposure of formic acid at 163 K resulted in both molecular adsorption and dissociation to formate. The adsorbed formate underwent further dissociation to H₂, CO₂ and CO. H₂ and CO₂ desorbed at the same temperatures of 340, 390 and 520 K, while CO desorbed at 415 and 520 K. The desorption features varied with the formic acid exposure. Two reaction channels were identified for the decomposition of formate under equilibrium with gas-phase formic acid with a pressure of 2.5 × 10⁻⁴Pa, one preferentially producing H₂ and CO₂ with an activation energy of 22 ± 2 kJ mol⁻¹ and the other preferentially producing CO and H₂O with an activation energy of 16 ± 2 kJ mol⁻¹. The order of both reaction paths was 0.5 with respect to the pressure of formic acid.     

Crystallization kinetics and thermal stability of Se98-x Zn2In x chalcogenide glasses

In this paper, we report on the non-isothermal crystallization kinetics of Se_{98 ?x} Zn₂In _x (0 ≤ x ≥ 10) chalcogenide glasses. The onset crystallization activation energy E _c, peak crystallization activation energy E _p and overall crystallization activation energy E have been determined by different approaches. The values of E _c, E _p and E have minima at a composition corresponding to 6 at% In. However the stability factor S and the crystallization rate constant stability factor K have a maximum and a minimum, respectively, at in the same composition. The nucleation and growth order parameter n, and the dimension order parameter m, are also determined and discussed for the present glasses.     

Thermal stability and crystallization kinetics of Ge–Se–Cd glasses

The effect is reported of varying cadmium concentration on the glass transition, thermal stability and crystallization kinetics of Ge₂₀Se_{80? x} Cd _x (x = 2.5, 5, 7.5 and 10 at. %) glasses. Differential scanning calorimetry results under non-isothermal conditions for the studied glasses are reported and discussed. The values of the glass transition temperature (T_g ) and the peak temperature of crystallization (T_p ) were found to be dependent on heating rate and Cd content. From the heating rate dependence of T_g and T_p , the values of the activation energy for glass transition (E_g ) and the activation energy for crystallization (E_c ) were evaluated and their composition dependence discussed. The thermal stability of the glasses was evaluated using various thermal stability criteria such as ΔT, H_g and S. The stability calculations emphasize that the thermal stability decreases with increasing Cd content.     

Phase transformations in calcite from electrical impedance measurements

The phase transformation in calcite I-IV-V and calcite ? aragonite have been characterized by electrical impedance measurements at temperatures 600–1200°C and pressures 0.5–2.5?GPa in a piston cylinder apparatus. The bulk conductivity σ has been measured from Argand plots in the frequency range 10⁵–10^?2?Hz in an electric cell representing a coaxial cylindrical capacitor. The synthetic polycrystalline powder of CaCO₃ and natural crystals of calcite were used as starting materials. The transformation temperature T_c was identified from resistivity-temperature curves as a kink point of the activation energy. At pressure above 2?GPa in ordered phase calcite I, the activation energy E _σ is c. 1.05?eV, and in disordered phase calcite V E _σ is c. 0.75?eV. The pressure dependence of T_c for the rotational order–disorder transformation in calcite is positive for pressures <1?GPa and negative for pressures >1?GPa. The transformation boundary of calcite 1–IV is observed only during first heating in samples after a long annealing at low temperatures. The activation energy of calcite I???IV decreases gradually from 1.8 to 1.05?eV with the pressure increase from 0.5 to 2?GPa. The kinetics of calcite ? aragonite transformation has been monitored by measuring a time-variation of the electrical resistance of a calcite sample at 10³?Hz in the stability P-T field of aragonite. The variation of the impedance correlates with the degree of phase transformation, estimated from X-ray powder diffraction studies on quenched products of experiments. The kinetics of calcite ? aragonite transformation may be fitted to the Avrami kinetics with the exponent m???1–1.5.     

Method of Hoogenstraaten as a tool for obtaining the trap parameters of general-order thermoluminescence glow peaks

The Hoogenstraaten method is a technique that uses various heating rates for obtaining the activation energy E (eV) in the case of first-order thermoluminescence glow peaks. This method can also be used for obtaining E (eV) for all types of glow peaks regardless of their kinetics order (b). The present work shows that the intercept of the Hoogenstraaten relation, which is usually used for obtaining the frequency factor S (s ^?1) of the first-order glow peak, can be used as a very good approximation to obtain the pre-exponential factor S ^{′ ′} (s ^?1) in the case of general-order glow peaks, when one uses Hoogenstraaten’s method to obtain E (eV). In addition, the present work suggests a numerical method for obtaining the kinetics order of the general-order glow peak. The method depends on the activation energy E (eV) obtained by the Hoogenstraaten method and the above-mentioned approximation for obtaining the pre-exponential factor S ^{′ ′} (s ^?1). An independent evaluation of the suggested methods for obtaining the trap parameters, the activation energy E (eV), the pre-exponential factor S ^{′ ′} (s ^?1) and the kinetics order (b) is illustrated here by taking a numerically computed glow peak and applying a one-trap and one-recombination-center model.     

A two-center model of the concerted molecular decomposition of unsaturated compounds

A semiempirical model of the concerted decomposition of unsaturated compounds (olefins, alcohols, acids, and ethers) and aliphatic esters into two molecules is suggested. The model considers the decomposition reaction as a single-step transfer of the hydrogen atom in one reaction center and the dissociation of a C-C or C-O bond in the other accompanied by a shift of π electrons in the cyclic six-membered transition state. Each elementary event in such a concerted reaction is characterized by its own activation energy, E _abs for the transfer of H, E _>d for bond dissociation, and E _π for the shift of π bonds. The E _abs and E _d activation energies were calculated by the method of intersecting parabolas. The spectrum of activation energies (sets of the E _abs, E _d , and E _π values) for each of 45 decomposition reactions was calculated with the use of experimental data. The contribution of enthalpy to the activation energy of each event was estimated.     

Selective Etching of N‐Doped Graphene Meshes as Metal‐Free Catalyst with Tunable Kinetics,High Activity and the Origin of New Catalytic Behaviors

New N‐doped reduced graphene oxide (N‐RGO) meshes are facile fabricated by selective etching of 3–5 nm nanopores, with controllable doping of N dopants at an ultrahigh N/C ratio up to 15.6 at%, from pristine graphene oxide sheets in one‐pot hydrothermal reaction. The N‐RGO meshes are illustrated to be an efficient metal‐free catalyst toward hydrogenation of 4‐nitrophenol, with new catalytic behaviors emerging in following three aspects: (i) tunable kinetics following pseudofirst order from commonly observed pseudozero order; (ii) strikingly improved activity with 26‐fold increased rate constant (1.0 s⁻¹ g⁻¹ L); (iii) no induction time required prior to reaction due to depressed back conversion, and dramatically decreased apparent activation energy (E_a) (17 kJ mol⁻¹). The origin of these new catalytic properties can be assigned to the synergetic effects between graphitic N doping and structural defects arising from nanopores. Deeper understanding unveils that the concentration of graphitic N is inverse proportion to E_a, while the pyrrolic N has no impact on this reaction, and oxygenate groups hampers it. The porous nature allows the N‐RGO meshes to conduct catalyze reactions in continuous flow fashion.     

Negative Ions,Ozone, and Metastable Components in dc Oxygen Glow Discharge

In a dc glow discharge in oxygen, the concentrations of minor components of O₂(a¹Δ_g), O₂(b¹ Σ_g), O₃, O(¹D), as well as nagative ions and electrons have been measured. Balance equations have been derived which describe satisfactorily the stationary concentrations of these components as functions of gas pressure and discharge current. For the first time, the rate constants of important aeronomical reactions (a) O^? + O₂(a¹Δ_g) → O₃ + e, (b) O₂^? + O₂(a¹Δ_g) → 2O₂ + e and (c) e + O₃ → O₂^? +O have been measured as functions of gas temperature T and mean energies of ions E_i and electron E₆: K_a = (2.5 ± 0.5) · 10^?9 · (T/300)^{4 ± 0.4}· (E_i/0.04)^{?2.6 ± 0.4} cm³/s for T = 385?605 K and E_i = 0.10 ? 0.66 eV; K_b = (1.0 ± 0.3) · 10^?10 · (T/300)^{?2 ± 0.5} · (E_i/0.04)^{0.23 ± 0.05} cm³/s for T = 330?605 K and E_i = 0.09 + 1.5 eV; K_c for E_e = 0.8÷5 eV.     

Time resolved measurements of methanol decomposition on Ni(100) utilizing laser induced desorption

A new method utilizing laser induced desorption (LID) is used to study the decomposition of methanol on Ni(100) in real time. The dependence of the rate of decompositition on surface coverage and on surface temperature is measured. The decomposition rate decreases during reaction in a manner characteristic of a self-poisoned reaction. The rate data are fit to a model in which the energy barrier to reaction increases in proportion to the coverage of the CH₃O product. The energy barrier obtained is 9 kcal mol^?1 plus 4 kcal mol^?1 monolayer^?1 of CH₃O. The frequency factor of 2 × 10⁹ s^?1 suggests there is significant entropy barrier to decomposition. Substitution of deuterium for the alcoholic hydrogen alters de decomposition rate appreciably and identifies the breaking of the OH bond as the rate determining step.     

N2(B3IIg) Quenching by Ethanol

The reaction rate values for the molecular nitrogen B³II_g state quenching by ethanol for vibrational quantum numbers v′ = 4–12 have been evaluated from the change of N₂ first positive system spectrum at ethanol addition to a high speed, microwave produced, plasma flow. The wall influence is avoided using a 0.9 m large reaction chamber. Computed N₂(B³II_g) quenching rate values are comprised between 0.9 × 10^?10 and 1.4 × 10^?10 cm³ · s^?1, being smaller than the corresponding gaskinetics rate.     

Raman scattering investigations of KY3F10

Single crystals of the fluoride compound KY₃F₁₀ (O_h⁵) were studied by Raman scattering from 40 to 950 K. Group theory analysis predicts 3A_1g + 4E_g + 6F_2g Raman-active modes, but the experimental spectra show two F_2g modes missing. Over the whole temperature range the frequency shifts are negligible whereas the line widths show a strong increase with temperature. Both reversible and irreversible line width behaviour are exhibited for different temperature runs, indicating a complex microscopic phenomenon underlying the creation of defects responsible for these line widths and their interaction with the different phonon modes. An approximate activation energy for defect creation of ΔE ≈︁ 0.3 eV can be obtained from the temperature behaviour of the line widths. This activation energy may be connected with the high-temperature ionic conduction mentioned previously for this crystal.     

Thermal Cross‐Linking of Poly(Vinyl Methyl Ether). III. Rheological Kinetics of Cross‐Linking Reaction

Abstract

The kinetics of the thermally activated cross‐linking reaction of poly(vinyl methyl ether) (PVME) were investigated rheologically by evaluating the viscoelastic material functions such as elastic storage modulus, G′, viscous loss modulus, G″ and complex dynamic viscosity, η*, during the curing process, both isothermally and nonisothermally. The isothermal kinetics reaction was described using a phenomenological equation based on the Malkin and Kulichikhin model, which was predicated originally for the isothermal curing kinetics of thermosetting polymers followed by differential scanning calorimetery (DSC) and was found to be applicable for rheokinetic reactions as well. An excellent representation of the data was obtained using this model; the rate of the reaction was found to be second order regardless of the temperature, which is in good agreement with literature data. The temperature dependence of the cross‐linking rate constant was described by an Arrhenius plot with an apparent activation energy equal to 60–62 kJ mol^?1, in reasonable agreement with the value obtained previously from the temperature dependence of gel time, t _gel. The nonisothermal kinetics reaction rate was described by a model that included the classical rate equation, the Arrhenius equation, and the time–temperature relationships. The apparent activation energy obtained nonisothermally was found to be frequency independent and equal to 72 kJ mol^?1, in very good agreement with the value obtained isothermally from the temperature dependence of t _gel in part II.     

A tem study of the crystallization behavior in amorphous vacuum condensed Er—Cu thin films

The isothermal crystallization of amorphous, vacuum condensed Er_0.6Cu_0.4 thin films was investigated in situ by transmission electron microscopy. Heterogeneous nucleation of ErCu crystallites was observed to occur on the thin rare-earth oxide layer which is inevitably formed on the external surface of the thin film exposed to the ambient atmosphere. The crystalline particles exhibited preferential growth in the direction parallel to the surface of the film. The crystallization process is interface controlled and characterized by a constant nucleation and constant growth rate. The kinetics of transformation were anslyzed in terms of Avrami's equation. The kinetic exponent n in Avrami's equation is equal to 2.9 in good agreement with the theoretical value for two-dimensional, interface-controlled growth. The experimental date allowed to derive the values of ΔE = 581 kJ.mole^?1 for the overall activation energy of the crystallization reaction, Δ_cr = 151 kJ.mole^?1 for the energy of critical nucleus formation and ΔE_m = 143 kJ.mole^?1 for the activation energy of atomic motion.