Book review: Kinetics of diffusion controlled chemical processes

1991 ◽  
Vol 65 (3-4) ◽  
pp. 823-824
Author(s):  
George H. Weiss
Clay Minerals ◽  
1990 ◽  
Vol 25 (3) ◽  
pp. 313-327 ◽  
Author(s):  
A. P. W. Hodder ◽  
B. E. Green ◽  
D. J. Lowe

AbstractThe kinetics of clay formation in buried paleosols developed from late Quaternary rhyolitic tephra layers near Rotorua, New Zealand, can be described in terms of a combination of parabolic and linear kinetics, reflecting the hydration of glass, and the formation of clay minerals, respectively. Such a model is consistent with the formation of clay minerals showing an Arrhenian temperature dependence and suggests, on the basis of calculated activation energies, that the process of formation of Al-rich allophane (imogolite) is diffusion controlled, whereas the rate of formation of Si-rich allophane is controlled by the chemical processes at the site of reaction.


Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1686
Author(s):  
Andrey Galukhin ◽  
Roman Nosov ◽  
Ilya Nikolaev ◽  
Elena Melnikova ◽  
Daut Islamov ◽  
...  

A new rigid tricyanate ester consisting of seven conjugated aromatic units is synthesized, and its structure is confirmed by X-ray analysis. This ester undergoes thermally stimulated polymerization in a liquid state. Conventional and temperature-modulated differential scanning calorimetry techniques are employed to study the polymerization kinetics. A transition of polymerization from a kinetic- to a diffusion-controlled regime is detected. Kinetic analysis is performed by combining isoconversional and model-based computations. It demonstrates that polymerization in the kinetically controlled regime of the present monomer can be described as a quasi-single-step, auto-catalytic, process. The diffusion contribution is parameterized by the Fournier model. Kinetic analysis is complemented by characterization of thermal properties of the corresponding polymerization product by means of thermogravimetric and thermomechanical analyses. Overall, the obtained experimental results are consistent with our hypothesis about the relation between the rigidity and functionality of the cyanate ester monomer, on the one hand, and its reactivity and glass transition temperature of the corresponding polymer, on the other hand.


From a study of the u. v., visible, near i. r. and e. s. r. spectra induced by γ -irradiation at 77°K in glassy MTHF and in glassy MTHF containing various additives and from a study of controlled temperature increases on these spectra, the following conclusions are drawn. (1) The primary products of the radiolysis are electrons ( e - ) and positive ions ( MTHF + ) which undergo a rapid ion-molecule reaction to give O CH 3 radicals ( R ⋅). (2) e - can either be trapped in the glassy MTHF matrix or can be captured by either napththalene, ferric chloride, carbon tetrachloride, nitrous oxide or trans -stilbene if these substances are present. (3) The e - T are bleachable by light or heat and disappear independently of the radicals R⋅ without either augmentation of R⋅ or the production of any new radical species. (4) e - T and R⋅ disappear thermally and independently by second-order reactions, the rate constants being K e - + e - (M -1 S -1 ) = 10 12⋅4±1⋅1 exp ─ [0⋅85 ± 0⋅10 kcal/mole/ R ( T ─ 75)] and K R˙ + R˙ (M -1 S -1 ) = 10 13⋅3±1⋅4 exp ─ [1⋅20 ± 0⋅15 kcal/mole/ R ( T ─ 75)]. These rate expressions suggest that both reactions are diffusion controlled at low temperatures in the glassy phase. (5) The kinetics of the thermal bleaching of e - T indicate that the electrons migrate distances of about 150 Å from their parent positive ions before being trapped in the matrix. (6) The effect of FeCl 3 in reducing the formation of e - T at 77°K and its lack of effect on the thermal bleaching of e - T suggests that the reaction e - + FeCl 3 → FeCl 2 + Cl - only occurs before the electron is thermalized.


1991 ◽  
Vol 238 ◽  
Author(s):  
G. J. Shiflet

ABSTRACTStresses are introduced in crystals at interphase boundaries where steps improve the registry of atoms. A model and mathematical analysis based on an approach previously taken by van der Merwe and Shiflet1–4 of the problem incorporating a coherent step are presented. Computed distributions of stresses, strains, dilatation and energy density in the form of contours and nets are given for a coherent monatomic step. It is concluded that the maximum stresses are quite large and the fields decay fairly rapidly with distance from the steps, the gradient of dilatation around steps will significantly affect diffusion kinetics of impurities and the strain energy seems too low to significantly enhance chemical processes.


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