The Kinetics of the Reaction 2C3H6 → C3H5 + C3H7

1973 ◽  
Vol 51 (17) ◽  
pp. 2934-2939 ◽  
Author(s):  
M. Simon ◽  
M. H. Back
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Radical Scavenger ◽  
A Value ◽  
Kinetics Of

An attempt has been made to measure the rate constant for the bimolecular process[Formula: see text]using acetaldehyde as a radical scavenger. The rate constant obtained may be expressed as follows:[Formula: see text]This activation energy corresponds to a value of 36 kcal/mol for ΔHf(allyl).

KINETICS OF THE DECOMPOSITIONS OF ETHANE AND PROPANE SENSITIZED BY AZOMETHANE: THE DECOMPOSITION OF THE NORMAL PROPYL RADICAL

1966 ◽  
Vol 44 (24) ◽  
pp. 2927-2940 ◽  
Author(s):  
M. C. Lin ◽  
K. J. Laidler
Keyword(s):  
Activation Energy ◽  
Satisfactory Agreement ◽  
Rate Constant ◽  
Dissociation Energy ◽  
Low Temperatures ◽  
Heats Of Formation ◽  
Kcal Mole ◽  
Energy Diagram ◽  
A Value ◽  
Kinetics Of

The azomethane-sensitized pyrolysis of ethane was studied at low temperatures from 280 to 350 °C. Measurements were made of initial rates of formation of methane, nitrogen, and butane. From the rate of nitrogen production the rate constant for the azomethane decomposition into 2CH3 + N2 was[Formula: see text]A similar study of the propane decomposition, at temperatures from 260 to 300 °C, led to the value[Formula: see text]in satisfactory agreement. The rate of decomposition of the n-propyl radical into CH3 and C2H4 was obtained by comparing the rates of formation of C2H4 and n-C6H14; the rate constant was[Formula: see text]The activation energy of 31.4 kcal/mole, together with that of 8.9 kcal/mole for the reverse reaction obtained by Brinton, leads to a value of 20.3 kcal/mole for the dissociation energy of n-CH3—CH CH2 at 0 °K, and to a value of 22.8 at 25 °C. The corresponding values for the heats of formation 2of the n-propyl radical are 28.4 kcal/mole at 0 °K, and 23.1 kcal/mole at 25 °C. The dissociation energy of n-CH3CH2CH2—H is deduced to be 99.4 kcal/mole at 0 °K and 99.9 kcal/mole at 25 °C. An energy diagram is constructed for the various reactions of n-C3H7 and i-C3H7.

The kinetics of the reaction between O 2 ( 1 ∆ g ) and ozone

1970 ◽  
Vol 317 (1530) ◽  
pp. 407-416 ◽  
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Room Temperature ◽  
Published Data ◽  
Temperature Range ◽  
A Value ◽  
Kinetics Of

The kinetics of the reaction O 2 ( 1 ∆ g ) + O 3 k 2 → 2O 2 + O have been investigated in the temperature range 195 to 439 K by using the kinetic photo­ionization technique to follow [O 2 ( 1 ∆ g )]. In Arrhenius form, the rate constant, k 2 ,'is given by k 2 = 4.0 ± 1.5 x 10 8 exp (13000 /RT) 1 mol -1 s -1 (joule units) ( = 4.0 ± 1.5 x 10 8 exp (3100/RT) 1 mol -1 s -1 (calorie units)). At room temperature (292 K) k 2 = 2.1 ± 0.3 x 10 6 1 mol -1 s -1 . The activation energy of 13 ± 1.6 kJ mol -1 suggests that there is virtually no barrier to the reaction other than that provided by its endothermicity (12.1 kJ mol -1 ). The results are used to derive, from pre­viously published data, a value of the rate constant for the reaction O + O 3 k 3 → 2O 2 of 4 ± 2 x 10 6 1 mol -1 s -1 at room temperature.

scholarly journals Analysis of the Kinetics of Swimming Pool Water Reaction in Analytical Device Reproducing Its Circulation on a Small Scale

Sensors ◽  
2020 ◽  
Vol 20 (17) ◽  
pp. 4820 ◽  
Author(s):  
Wojciech Kaczmarek ◽  
Jarosław Panasiuk ◽  
Szymon Borys ◽  
Aneta Pobudkowska ◽  
Mikołaj Majsterek
Keyword(s):  
Activation Energy ◽  
Water Quality ◽  
Rate Constant ◽  
Reaction Rate ◽  
Reaction Rate Constant ◽  
Small Scale ◽  
Pool Water ◽  
Swimming Pool Water ◽  
Kinetics Of ◽  
Analytical Device

The most common cause of diseases in swimming pools is the lack of sanitary control of water quality; water may contain microbiological and chemical contaminants. Among the people most at risk of infection are children, pregnant women, and immunocompromised people. The origin of the problem is a need to develop a system that can predict the formation of chlorine water disinfection by-products, such as trihalomethanes (THMs). THMs are volatile organic compounds from the group of alkyl halides, carcinogenic, mutagenic, teratogenic, and bioaccumulating. Long-term exposure, even to low concentrations of THM in water and air, may result in damage to the liver, kidneys, thyroid gland, or nervous system. This article focuses on analysis of the kinetics of swimming pool water reaction in analytical device reproducing its circulation on a small scale. The designed and constructed analytical device is based on the SIMATIC S7-1200 PLC driver of SIEMENS Company. The HMI KPT panel of SIEMENS Company enables monitoring the process and control individual elements of device. Value of the reaction rate constant of free chlorine decomposition gives us qualitative information about water quality, it is also strictly connected to the kinetics of the reaction. Based on the experiment results, the value of reaction rate constant was determined as a linear change of the natural logarithm of free chlorine concentration over time. The experimental value of activation energy based on the directional coefficient is equal to 76.0 [kJ×mol−1]. These results indicate that changing water temperature does not cause any changes in the reaction rate, while it still affects the value of the reaction rate constant. Using the analytical device, it is possible to constantly monitor the values of reaction rate constant and activation energy, which can be used to develop a new way to assess pool water quality.

A Theoretical and Experimental Investigation of the Kinetics of Ring Closure of the 3-Methyl-3-azahex-5-enyl Radical

1995 ◽  
Vol 48 (12) ◽  
pp. 2047 ◽  
Author(s):  
EW Della ◽  
AM Knill
Keyword(s):  
Activation Energy ◽  
Experimental Investigation ◽  
Force Field ◽  
Activation Barrier ◽  
Ring Closure ◽  
Force Field Calculations ◽  
Arrhenius Parameters ◽  
A Value ◽  
Kinetics Of

Evaluation of the Arrhenius parameters for ring closure of the 3-methyl-3-azahex-5-enyl radical is reported. Cyclization of the radical is found to occur with high regioselectivity giving the exo -trig product exclusively with an activation energy of 22 kJ mol-1 and log A value of 11.1. The experimental activation barrier compares favourably with that determined by force field calculations which predict a value of 21 kJ mol-1. The 3-methyl-3-azahex-5-enyl radical is therefore found to undergo ring closure some 70 times faster than the parent hex-5-enyl radical, in accord with predictions based upon geometrical considerations.

scholarly journals The combination of carbon monoxide–haem with apoperoxidase

1969 ◽  
Vol 114 (4) ◽  
pp. 719-724 ◽  
Author(s):  
Charles Phelps ◽  
Eraldo Antonini
Keyword(s):  
Activation Energy ◽  
Carbon Monoxide ◽  
Rate Constant ◽  
Binding Sites ◽  
Order Process ◽  
First Order ◽  
Effects Of Ph ◽  
Kinetics Of

1. Static titrations reveal an exact stoicheiometry between various haem derivatives and apoperoxidase prepared from one isoenzyme of the horseradish enzyme. 2. Carbon monoxide–protohaem reacts rapidly with apoperoxidase and the kinetics can be accounted for by a mechanism already applied to the reaction of carbon monoxide–haem derivatives with apomyoglobin and apohaemoglobin. 3. According to this mechanism a complex is formed first whose combination and dissociation velocity constants are 5×108m−1sec.−1 and 103sec.−1 at pH9·1 and 20°. The complex is converted into carbon monoxide–haemoprotein in a first-order process with a rate constant of 235sec.−1 for peroxidase and 364sec.−1 for myoglobin at pH9·1 and 20°. 4. The effects of pH and temperature were examined. The activation energy for the process of complex-isomerization is about 13kcal./mole. 5. The similarity in the kinetics of the reactions of carbon monoxide–haem with apoperoxidase and with apomyoglobin suggests structural similarities at the haem-binding sites of the two proteins.

Ruthenium and iron complexes of dipicolinic acid: Synthesis, solution properties and kinetics of electron transfer reactions with ascorbate ions

1983 ◽  
Vol 36 (12) ◽  
pp. 2377 ◽  
Author(s):  
NH Williams ◽  
JK Yandell
Keyword(s):  
Redox Potential ◽  
Rate Constant ◽  
Dipicolinic Acid ◽  
Acid Synthesis ◽  
Equilibrium Mixture ◽  
A Value ◽  
Inert Electrode ◽  
Ph Range ◽  
Kinetics Of ◽  
Kinetics Of Reduction

Standard potentials of the redox couples [bis(pyridine-2,6-dicarboxylate)MIII]-/2- ([M(dipic)2]-/2-, where M = Fe, Ru, Co) have been determined at 25�C, and ionic strength 0.1M (NaClO4 or KNO3). Kinetics of reduction of the oxidized complexes by ascorbate have also been examined under the same conditions. The [Fe(dipic)2]-/2- potential was found to be 355 � 5 mV. Reduction of [Fe(Fe(dipic)2]- in the pH range 4-6 was shown to occur by reaction with ascorbate monoanion (HA-) with a rate constant of (2.2 � 0.2) × 103 1. mol-1 s-1, and ascorbate dianion(A2-) with a rate constant of (7 � 1) × 108 1. mol-1 s-1. K [Ru(dipic)2] has been synthesized. Spectroscopic and analytical evidence suggest that it is a simple six-coordinate species in the solid and in non-aqueous solvents, but that in water it exists as an equilibrium mixture of at least two species. The redox potential for this mixture was found to be 270 � 10 mV. The major component of this mixture is reduced by A2- with a rate constant of (4.7 � 0.1) × 1081.mol-1 s-1. A value of 747 � 5 mV was measured for the redox potential of the cobalt couple, although equilibration of this system with the inert electrode could be achieved only by using [Fe(bpy)2(CN)2] as a mediator. Kinetics of reduction of [Co(dipic)2]- by ascorbate were complex and not reproducible.

THE REACTION BETWEEN CYANATE AND HYPOCHLORITE

1956 ◽  
Vol 34 (4) ◽  
pp. 489-501 ◽  
Author(s):  
M. W. Lister
Keyword(s):  
Activation Energy ◽  
Ionic Strength ◽  
Rate Constant ◽  
Hypochlorous Acid ◽  
Effect Of Temperature ◽  
Slow Step ◽  
True Activation Energy ◽  
Rate Of Reaction ◽  
Different Temperatures ◽  
Kinetics Of

The reaction between sodium hypochlorite and potassium cyanate in the presence of sodium hydroxide has been examined. The main products are chloride, and carbonate ions and nitrogen; but, especially if much hypochlorite is present, some nitrate is formed as well. The rate of reaction is proportional to the cyanate and hypochlorite concentrations, but inversely proportional to the hydroxide concentration: the rate constant is 5.45 × 10−4 min.−1 at 65 °C, at an ionic strength of 2.2. The rate constant increases somewhat as the ionic strength rises from 1.7 to 3.5. The effect of temperature makes the apparent activation energy 25 kcal./gm-molecule. The kinetics of the reaction suggest that the slow step is really a reaction of hypochlorous acid and cyanate ions, and possible intermediate products of this reaction are suggested. Allowing for the different extent of hydrolysis of hypochlorite at different temperatures, the true activation energy is found to be 15 kcal./gm-mol., which is consistent with the observed rate of reaction.

Correlation analysis of reactivity in the addition of substituted benzylamines to β-nitrostyrene

1996 ◽  
Vol 74 (4) ◽  
pp. 625-629 ◽  
Author(s):  
Neeta Jalani ◽  
Seema Kothari ◽  
Kalyan K. Banerji
Keyword(s):  
Activation Energy ◽  
Correlation Analysis ◽  
Rate Constant ◽  
Steric Hindrance ◽  
Nucleophilic Addition ◽  
Regression Coefficients ◽  
Nucleophilic Attack ◽  
Arrhenius Activation Energy ◽  
First Order ◽  
Kinetics Of

The kinetics of addition of a number of ortho-, meta-, and para-substituted benzylamines to β-nitrostyrene (NS) in acetonitrile have been studied. The reaction is first order with respect to NS. The order with respect to the amine is higher than one. It has been shown that the reaction follows two mechanistic pathways, uncatalyzed and catalyzed by the amine. The Arrhenius activation energy for the catalyzed path is negative, indicating the presence of a pre-equilibrium (k1, k−1) leading to the formation of a zwitterion. The values of the rate constant, k1, for the nucleophilic attack have been determined for 28 benzylamines. The rate constant k1 was subjected to correlation analysis using Charton's LDR and LDRS equations. The polar regression coefficients are negative, indicating the formation of a cationic species in the transition state. The reaction is subject to steric hindrance by ortho substituents. Key words: nucleophilic addition, benzylamines, correlation analysis, kinetics, alkene.

scholarly journals The kinetics of colour degradation, chlorophylls and xanthophylls loss in pistachio nuts during roasting process

2019 ◽  
Author(s):  
Ali Dini ◽  
Soudeh Khanamani Falahati-Pour ◽  
Khosro Behmaram ◽  
Nasser Sedaghat
Keyword(s):  
Activation Energy ◽  
B Value ◽  
Order Kinetic ◽  
Air Velocity ◽  
Carotenoid Concentration ◽  
Hot Air ◽  
A Value ◽  
Pistachio Nuts ◽  
Roasting Temperature ◽  
Kinetics Of

Abstract Objectives Colour is amongst the parameter which is used for process control during roasting. Materials and Methods In this study, the effects of hot air roasting temperature (120, 130, 145, 160, and 170°C) and hot air velocity (0.6, 1.3, and 2 m/s) on colour change kinetics of pistachio nuts were investigated by employing image analysis and simultaneously chlorophylls and xanthophylls (lutein and β-carotenoid) concentration were determined by spectrophotometric measurement method. Results We found that roasting temperature and hot air velocity had significant effect on colour changes. There is a correlation between a- and b-value with chlorophylls and xanthophylls concentration, respectively. The roasting temperature was found to be the main factor affecting colour development. The variations in the pigments concentration and colour parameters of pistachio nuts were adequately simulated by quadratic and cubic polynomials. The changes in L-, b-values, and xanthophylls degradation were well-fitted to the first-order kinetic model while a-value and chlorophylls degradation followed the zero-order kinetic. The activation energy was determined at 113.9, 116.7, and 117.2 kJ/mol with R2 ≥ 99.9 and 191, 195, and 163.2 kJ/mol with R2 ≥ 99.5 and 73.7, 71.3, and 81.6 kJ/mol with R2 ≥ 99.9 for L-, b-, and a-value in hot air velocity of 0.6, 1.3, and 2 m/s, respectively. Conclusions Activation energy of chlorophylls and xanthophylls degradation were in the range of the activation energy for the yellowness (b-value) and redness (a-value) reactions.

Determination of Recrystallization Kinetics and Activation Energy of Grain Growth Process of Cu-14Al-4Ni Shape Memory Alloy

2015 ◽  
Vol 1765 ◽  
pp. 127-132 ◽  
Author(s):  
Emmanuel P. R. Lima ◽  
Pedro C. de Lima ◽  
Marcelo Nava
Keyword(s):  
Activation Energy ◽  
Shape Memory Alloy ◽  
Shape Memory ◽  
Grain Growth ◽  
Growth Process ◽  
Treatment Time ◽  
Mechanical Tests ◽  
A Value ◽  
Kinetics Of

ABSTRACTThe non-ferrous shape memory alloys have, normally, two problems that hinder its use in industrial scale: the natural aging and grains growth. The first degrades the memory effect, while the second, observed during the processing of alloy, modifies the temperatures which the transformations occur. Thus, the study of kynetic of recrystallization is important for enabling the control of hardened state in function of treatment time, without causing excessive grain growth. Therefore, the objective of this study is to determine the kinetics of recrystallization of Cu-14Al-4Ni shape memory alloy, based on an empirical law of the formation of Jonhson-Mehl-Avrami, as well as their activation energies for grain growth process according to the empirical Arrhenius law. The alloy was vacuum melted in an induction furnace. After casting, the bulk samples of the alloy were homogenized for 24 hours, solubilized and hot rolled followed by water-quenching to initiate the recrystallization. Then, different samples were annealed at temperatures close to the peak, start and end of the DSC curve. Following the heat treatments, the samples were submitted to mechanical tests and the values of the properties were correlated to the fraction transformed for determination of recrystallization’s kinetic. For the characterization of the grain growth process, analyses in optical microscopy were accomplished and all annealed samples were examined by statistical metallography and the grain sizes were measured. After measurements, the ln[-ln(1-Yrec)] x ln(t) and the ln [D-Do] x 1/T diagrams were plotted to determine the parameters of Jonhson-Mehl-Avrami equation and the activation energy of the process, respectively. The results showed that the equation of the recrystallized fraction follows the empiric law of the formation of Jonhson-Mehl-Avrami for the considered property, as well as, also showed that the alloy Cu-14Al-4Ni is extremely sensitive to temperature variation in which the alloy is treated, having a dual kinetics of grain growth. In the first domain, between 670 and 710°C, the diagram provides a value for the activation energy equal to 39.32 KJ/mol, in the second domain, between 710 and 790°C, the diagram provides a value for the activation energy equal to 9.01 KJ/mol.

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