Kinetics of the Reaction between Silver and Nitric Acid

1962 ◽  
Vol 15 (2) ◽  
pp. 181 ◽  
Author(s):  
JJ Batten
Keyword(s):  
Activation Energy ◽  
Nitric Acid ◽  
Induction Period ◽  
Acid Concentration ◽  
Maximum Rate ◽  
Kcal Mole ◽  
Temperature Range ◽  
Induction Rate ◽  
Rate Of Dissolution ◽  
Kinetics Of

The rate of dissolution of silver gauze in nitric acid at various concentrations and temperatures was measured in a static system. The solution process was measured by the weight of silver dissolved in various time intervals. In general, induction periods were observed, but after this period the dissolution proceeded with an appreciable velocity. To examine the influence of acid concentration and temperature on the kinetics of the reaction, the duration of the induction period, the rate of dissolution during this period, and the subsequent maximum rate were taken as kinetic parameters of the reaction. The induction rate was found to be highly dependent on the initial acid concentration (approx. seventh power), whereas over most of the concentration range accessible to study, the maximum rate was proportional to the square of the concentration. It was also observed that increase in temperature sharply increases the induction rate, but has little effect upon the subsequent maximum rate over most of the temperature range studied. The activation energy of the induction rate was greater than 20 kcal/mole, whereas that of the maximum rate was about 4 kcal/mole over most of the temperature range studied. This difference in the activation energy during and after the induction period is explained by a shift in the mechanism controlling the rate of the process from a chemical reaction at the surface to a diffusion process.

The kinetics of the ordering process in triclinic NaAlSi3O8

1960 ◽  
Vol 32 (249) ◽  
pp. 436-454 ◽  
Author(s):  
J. D. C. McConnell ◽  
Duncan McKie
Keyword(s):  
Activation Energy ◽  
Kinetic Analysis ◽  
Vapour Pressure ◽  
Polymorphic Transformation ◽  
Water Vapour Pressure ◽  
Kcal Mole ◽  
Temperature Range ◽  
Self Diffusion ◽  
Dry Heating ◽  
Kinetics Of

SummaryA kinetic analysis is presented of the data of MacKenzie (1957) on the hydrothermal treatment of NaAlSi3O8 under isobaric, isothermal conditions in the temperature range 450° C. to 1000° C.The analysis indicates the existence of a smeared polymorphic transformation in the temperature range around 600° C. The activation energy for the transformation is about 60 kcal. mole−1 and has been equated with the process of self-diffusion involved in Al-Si ordering in the structure. Some dry-heating experiments and the influence of varying water vapour pressure are discussed.

Kinetics of the thermal reactions of ethylene. Part I

1968 ◽  
Vol 46 (14) ◽  
pp. 2415-2426 ◽  
Author(s):  
M. L. Boyd ◽  
T-M. Wu ◽  
M. H. Back
Keyword(s):  
Activation Energy ◽  
Molecular Weight ◽  
Free Radical ◽  
Induction Period ◽  
Pressure Range ◽  
Kcal Mole ◽  
Radical Chain ◽  
Thermal Reactions ◽  
Chain Polymerization ◽  
Kinetics Of

The pyrolysis of ethylene has been studied in the temperature range 500–600 °C and the pressure range 15–60 cm. The main products were ethane, propylene, butene, butadiene, and a polymer of molecular weight corresponding to C8 or higher. Small amounts of methane, butane, unsaturated C5, unsaturated C6, and benzene were also measured. Of the main products, propylene, butene, and butadiene showed an induction period, as long as several minutes at the lowest temperature. The order with respect to ethylene of ethane, propylene, and butene was close to two and the activation energy of the rates was approximately 40 kcal/mole. The results have been interpreted in terms of a free radical chain polymerization. It is suggested that the polymer formed is unstable and decomposes to yield the products for which an induction period was observed.

Kinetics of the Solid State Reaction between MoO3 and SrCO3

1972 ◽  
Vol 27 (6) ◽  
pp. 1020-1022 ◽  
Author(s):  
G. Flor ◽  
V. Massarotti ◽  
R. Riccardi
Keyword(s):  
Activation Energy ◽  
Solid State ◽  
Apparent Activation Energy ◽  
Solid State Reaction ◽  
Diffusion Mechanism ◽  
Optical Observations ◽  
Kcal Mole ◽  
Temperature Range ◽  
Kinetics Of

AbstractThe solid state reaction MoO3 + SrCO3 → SrMoO4+ CO2 has been studied on mixtures of powdered reagents. Thermogravimetric measurements in the temperature range 412° -498 °C have been made on different mixtures and under different atmospheres. Moreover, optical observations and conductometric measurements have been carried out. The results show that the reaction is governed by a diffusion mechanism with an apparent activation energy of (60 ± 1) kcal/mole and that the main diffusing species is the Mo6+ ion.

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

The slow oxidation of methane

1956 ◽  
Vol 235 (1201) ◽  
pp. 158-173 ◽  
Keyword(s):  
Activation Energy ◽  
Hydrogen Peroxide ◽  
Induction Period ◽  
Hydrofluoric Acid ◽  
Pressure Rise ◽  
Pressure Change ◽  
Kcal Mole ◽  
Gaseous Products ◽  
Oxidation Of Methane ◽  
Reproducible Manner

Mixtures of methane and oxygen behave in a reproducible manner at temperatures of 440 to 520°C and initial pressures of 100 to 350 mm when reacting in Pyrex vessels freshly cleaned with hydrofluoric acid. The apparent order of the reaction ranged from 2∙3 to 2∙6 and the overall activation energy from 29 to 41 kcal/mole. Analyses of the products formed have been made, together with measurements of pressure change. Formaldehyde is formed from the commencement of the reaction including the induction period, but its concentra­tion reaches a maximum near the stage where the pressure rise is a maximum, and then falls off. Hydrogen peroxide is also formed, less rapidly in the earliest stage, but its rate of formation overtakes that of formaldehyde and it reaches an even higher concentration. No other peroxides were detected, nor was methanol found. Hydrogen was present in the gaseous products. These observations are not in full accord with some of the conclusions derived from earlier investigations.

Vulcanization of Rubber in the Presence of N,N-Diethyl-2-Benzothiazolylsulfenamide as Accelerator

1960 ◽  
Vol 33 (2) ◽  
pp. 361-372 ◽  
Author(s):  
B. A. Dogadkin ◽  
O. N. Beliatskaya ◽  
A. B. Dobromyslova ◽  
M. S. Feldshtein
Keyword(s):  
Induction Period ◽  
Maximum Rate ◽  
Initial Period ◽  
Pure Oxygen ◽  
Butadiene Rubber ◽  
Sulfur Vulcanization ◽  
Analogous Manner ◽  
Chemical Crosslinks ◽  
Main Period ◽  
Kinetics Of

Abstract 1. The vulcanization of rubber in the presence of N,N-diethyl-2-benzothiazolylsulfenamide is characterized by an S-shaped curve for the addition of sulfur with an initial induction period in the reaction. The modulus and number of crosslinks are changed in an analogous manner to the structure of the vulcanizate. 2. The energy of activation of the addition of sulfur in the initial period is equal to 30 kcal per mole as against 14 kcal per mole in the main period. 3. The induction period is increased if the sodium-butadiene rubber is purified from alkali. 4. Molecular oxygen present in the compound being vulcanized decreases the induction period and increases the rate of the addition of the sulfur in the main period. An induction period is not observed when vulcanization is carried out in an atmosphere of pure oxygen. 5. The interaction of N,N-diethyl-2-benzothiazolylsulfenamide with rubber (in the absence of sulfur) at vulcanization temperatures is accompanied by the formation of MBT, diethylamine, and the addition of the elements of the accelerator to the rubber. The kinetics of this process were studied. 6. The interaction of N,N-diethyl-2-benzothiazolyl sulfenamide with rubber leads to the formation of chemical crosslinks between the molecules of rubber (the effect of vulcanization). 7. The change of N,N-diethyl-2-benzothiazolyl sulfenamide under the conditions of normal sulfur vulcanization has the same character as in the interaction of it with rubber. The kinetics of the formation of MBT have a maximum which coincides with the maximum rate of the addition of sulfur to the rubber. 8. A mechanism is presented for the vulcanization and acceleration actions of N,N-diethyl-2-benzothiazolyl sulfenamide which provides for the extraction of hydrogen by the accelerator radicals from the molecular chains of the rubber with the formation of MBT, diethylamine and polymer radicals which are able to interact with the sulfur.

Insect blood-brain barrier: a radioisotope study of the kinetics of exchange of a liposoluble molecule (n-butanol)

1976 ◽  
Vol 64 (1) ◽  
pp. 119-130
Author(s):  
M. V. Thomas
Keyword(s):  
Activation Energy ◽  
Temperature Sensitivity ◽  
Nerve Cord ◽  
Previous Investigation ◽  
Time Course ◽  
Kcal Mole ◽  
Similar Time ◽  
Kinetics Of ◽  
Butanol Concentration ◽  
Good Agreement

About 90% of the butanol uptake by the cockroach abdominal nerve cord washed out with half-times of a few seconds, in good agreement with an electrophysiological estimate, and the temperature sensitivity suggested an activation energy of 3 Kcal mole-1. The remaining activity washed out far more slowly, with a similar time course to that observed in a previous investigation which had not detected the fast fraction. Its size was similar to the non-volatile uptake, and was considerably affected by the butanol concentration and incubation period. It apparently consisted of butanol metabolites, which could be detected by chromatography.

The role of formaldehyde in the oxidation of ethylene

1952 ◽  
Vol 212 (1110) ◽  
pp. 291-311 ◽  
Keyword(s):  
Activation Energy ◽  
Ethylene Oxide ◽  
Induction Period ◽  
Maximum Rate ◽  
Reaction Scheme ◽  
Stationary Concentration ◽  
Rate Of Reaction ◽  
A Minor ◽  
Close Parallelism

The oxidation of ethylene at temperatures in the region of 400° C has been studied manometrically and analytically, and compared with the oxidation of formaldehyde under similar conditions. The observations of previous authors have been confirmed and extended with particular reference to the factors controlling the maximum rate of reaction. The oxidation of ethylene is closely dependent on the development of formaldehyde, which shows the behaviour to be expected of an agent for degenerate branching. There is a close parallelism between the variation of the activation energy of the oxidation of ethylene from 25 kcal at 350° C to 53 kcal at 550° C and of formaldehyde from 21 kcal at 350° C to more than 40 kcal at 500° C. Formaldehyde is produced in the oxidation of ethylene and attains a maximum concentration which is proportional to the ethylene pressure and independent of the oxygen pressure. The addition of formaldehyde to the reaction mixture reduces or removes the induction period without affecting the maximum rate of the reaction. Ethylene oxide plays a minor but significant part; it attains a stationary concentration in the reaction but is less effective than formaldehyde in reducing the induction period. A reaction scheme based on that proposed by Axford & Norrish (1948) for the oxidation of formaldehyde has been developed; it accounts satisfactorily for the observed facts.

Kinetics of the addition of acids to olefins with and without boron fluoride catalysis

1967 ◽  
Vol 45 (1) ◽  
pp. 11-16 ◽  
Author(s):  
G. A. Latrèmouille ◽  
A. M. Eastham
Keyword(s):  
Activation Energy ◽  
Acetic Acid ◽  
Apparent Activation Energy ◽  
Trifluoroacetic Acid ◽  
Similar Rate ◽  
Ethylene Dichloride ◽  
Kcal Mole ◽  
Rate Law ◽  
Boron Fluoride ◽  
Kinetics Of

Isobutene reacts readily with excess trifluoroacetic acid in ethylene dichloride solution at ordinary temperatures to give t-butyl trifluoroacetate. The rate of the reaction is given, within the range of the experiments, by the expression d[ester]/dt = k[acid]2[olefin], and the apparent activation energy is about 6 kcal/mole. The rate of addition is markedly dependent on the strength of the reacting acid and is drastically reduced in the presence of mildly basic materials, such as dioxane. The boron fluoride catalyzed addition of acetic acid to 2-butene can be considered to follow a similar rate law, i.e. d[ester]/dt = k[acid·BF3]2[olefin], but only if some assumptions are made about the position of the equilibrium [Formula: see text]since only the 1:1 complex is reactive.

Chemical Vapor Deposition of SiO2 from Ozone-Organosilane Mixtures near Atmospheric Pressure

1992 ◽  
Vol 282 ◽  
Author(s):  
K. V. Guinn ◽  
J. A. Mucha
Keyword(s):  
Activation Energy ◽  
Chemical Vapor Deposition ◽  
Vapor Deposition ◽  
Atmospheric Pressure ◽  
Chemical Vapor ◽  
Zero Order ◽  
Kcal Mole ◽  
Consumption Ratio ◽  
Zero Order Kinetics ◽  
Kinetics Of

ABSTRACTThe kinetics of deposition of SiO2 by the reaction of tetramethylsilane (TMS) with ozone (O3) has been studied over the temperature range 180 – 380° C and compared with available data for the same process using tetraethoxysilane (TEOS). Both processes exhibit the same activation energy (17 kcal/mole) below 300 ° C which falls-off at higher temperatures due to transport limitations. Transition from first- to zero-order kinetics occurs with increasing concentrations of TMS and O3, which gives an overall O3/TMS consumption ratio of 10 at 258° C and5 at 325° C. TEOS is estimated to be 5 times more reactive than TMS above 300° C and over 10 times more reactive in the kinetically-limited regime below 300° C. Results suggest that O3-induced SiO2 deposition proceeds via surface reactions and is limited by heterogeneous decomposition of ozone.

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