Arrhenius Parameters of the Bimolecular Reaction of SiH4with O(3P) Atom over a Temperature Range of 294.7-378.5 K

2015 ◽  
Vol 36 (10) ◽  
pp. 2577-2579
Author(s):  
Hee-Soo Yoo
Keyword(s):  
Bimolecular Reaction ◽  
Arrhenius Parameters ◽  
Temperature Range

The reactivity of p-nitrophenyl esters with surfactants in nonaqueous solvents. I. p-Nitrophenyl acetate in benzene solutions of dodecylammonium propionate

1980 ◽  
Vol 33 (4) ◽  
pp. 757 ◽  
Author(s):  
CJ O'Conner ◽  
RE Ramage
Keyword(s):  
Rate Equation ◽  
Bimolecular Reaction ◽  
Micellar Catalysis ◽  
Nonaqueous Solvents ◽  
Arrhenius Parameters

The rate of decomposition of p-nitrophenyl acetate, pnpa, in benzene in the presence of dodecyl-ammonium propionate, dap, has been measured at temperatures between 288 and 308 K. The proposed rate equation consists of a term arising from micellar catalysis and a term arising from a bimolecular reaction between the ester and the components of dap. Arrhenius parameters have been estimated for the two reaction modes. Literature data related to similar reactions have been reviewed.

Reactions of methyl radicals. V. Hydrogen abstraction from hydrogen sulfide

1983 ◽  
Vol 36 (11) ◽  
pp. 2195 ◽  
Author(s):  
H Arican ◽  
NL Arthur
Keyword(s):  
Hydrogen Sulfide ◽  
Rate Constant ◽  
Hydrogen Abstraction ◽  
Methyl Radicals ◽  
Arrhenius Parameters ◽  
Temperature Range

Hydrogen abstraction from H2S by CH3 radicals, produced by the photolysis of azomethane, has been studied in the temperature range 334-432 K. The rate constant, based on the value 1013.34 cm3 mol-1 s-1 for the recombination of CH3 radicals, is given by log k4 = (11.00 � 0.01) - (8760 � 80)/19.145T where k4 is in cm3 mol-1 s-1 and E is in J mol-1. The previous data reported for this reaction are discussed and best values for its Arrhenius parameters are recommended. The results indicate that CH3 radicals react faster than CF3 radicals with H2S; this confirms the importance of polar effects in the hydrogen abstraction reactions of CF3 radicals.

The reactivity of p-nitrophenyl esters with surfactants in apolar solvents. V. p-Nitrophenyl acetate in benzene solutions of butane-1,4-diamine bis(dodecanoate)

1983 ◽  
Vol 36 (5) ◽  
pp. 895 ◽  
Author(s):  
CJ O'Conner ◽  
TD Lomax
Keyword(s):  
Rate Equation ◽  
Reaction Rate ◽  
Water Environment ◽  
Water Concentration ◽  
Bimolecular Reaction ◽  
Micellar Catalysis ◽  
Similar Reaction ◽  
Arrhenius Parameters

The rate of decomposition of p-nitrophenyl acetate in benzene in the presence of butane-1,4-diamine bis(dodecanoate) (budb) has been measured at temperatures between 333 and 353 K. The data fit a rate equation which consists of a term arising from micellar catalysis and a term arising from a bimolecular reaction between the ester and the components of budb. Arrhenius parameters have been estimated for the two reaction modes and compared with newly extended data for the similar reaction with dodecylammonium propionate (dap). 13C n.m.r. analysis of the products from there action of p-nitrophenyl propionate in the presence of dap has revealed that the amide is formed by an aminolysis reaction. The decrease in reaction rate observed with increasing water concentration is interpreted in terms of a biphasic water environment.

scholarly journals The thermal decomposition of hydrogen peroxide vapour

1946 ◽  
Vol 185 (1001) ◽  
pp. 207-224 ◽  
Keyword(s):  
Hydrogen Peroxide ◽  
Thermal Decomposition ◽  
Water Vapour ◽  
Surface Reaction ◽  
High Pressures ◽  
Reaction Rates ◽  
Bimolecular Reaction ◽  
Temperature Range ◽  
Low Pressures ◽  
Absolute Reaction

The decomposition of hydrogen peroxide vapour at pressures less than 1 mm. in silica vessels has been investigated, mainly at 80° C, but also over the temperature range 15-140° C. Oxygen at low pressures was found to have no appreciable influence on the rate of decomposition; water vapour retarded the rate slightly. The reaction was predominantly a surface one. In one vessel, the decomposition was bimolecular with respect to the peroxide pressure, the rate being given by k [H 2 O 2 ] 2 /(1+ b [H 2 O]) 2 in another, the bimolecular reaction of the final stages at low peroxide pressures was preceded by one of order approximately 0.7 at the high pressures. Higher pressures of oxygen and nitrogen retarded the decomposition appreciably. At higher pressures of water vapour, a pronounced periodicity in rate was evident. The apparent heat of activation over the temperature range investigated was not constant, being calculated as 4200 cal. from rates at 15 and 70° C and 8400 cal. from rates at 80 and 140° C. On the assumption that the lower value more nearly represents the surface reaction, the velocity of decomposition, calculated for 1 mm. pressure of peroxide at 50° C by the theory of absolute reaction rates, was 0.70 x 10 13 mol.cm. -2 sec. -1 , in agreement with the experimental value of 0.76 x 10 13 mol.cm. -2 sec. -1 .

The thermal isomerization of 1. 2-dimethyl cyclo propane II. Structural isomerization

1961 ◽  
Vol 260 (1302) ◽  
pp. 424-432 ◽  
Keyword(s):  
Transition State ◽  
Thermal Isomerization ◽  
Reaction Vessel ◽  
Rate Equations ◽  
Arrhenius Parameters ◽  
Temperature Range ◽  
Structural Isomerization ◽  
Electronic Integration ◽  
Ring Transition State

This isomerization has been investigated between 434 and 475 °C. In this temperature range, in an ‘aged’ reaction vessel, the structural isomerization from either cis or trans 1. 2-dimethyl cyclo propane occurs as a unimolecular transformation which is slower than the reversible cis-trans isomerization. The products of the reaction are 2-methylbut-1-ene, 2-methylbut-2-ene and cis and trans pent-2-ene. The rates of formation of these compounds have been measured and the Arrhenius parameters evaluated. The rate equations for the formation of 2-methylbut-1-ene and 2-methylbut-2-ene are k ∞ = 10 13.93 exp(-61900/ RT ) S -1 and 10 14.08 exp (-62300/ RT ) S -1 respectively and are the same for their production from either the cis or the trans dimethyl cyclo propane. The pent-2-enes are formed more rapidly from cis 1. 2-dimethy cyclo propane than from the trans compound. From cis 1.2-dimethyl cyclo propane cis and trans pent-2-ene are formed at rates given by the equations k ∞ = 10 13.92 exp (-61400/ RT )s -1 and 10 13.96 exp (-61200/ RT )s -1 , respectively. From trans 1.2-dimethyl cyclo propane the rate equations are k ∞ = 10 14.40 exp (-63600/ RT )s -1 and 10 14.30 exp (-62900/ RT )s -1 . The possible mechanisms for both the geometrical and structural isomerizations have been discussed and it has been concluded than an ‘expanded ring’ transition state gives a satis­factory explanation of the results obtained. It is also suggested that this strengthens the case for a similar mechanism in the case of the isomerization of cyclo propane. Gas chromato­graphy, by means of a katharometer detector with electronic integration, has been used throughout and has been developed to give a precision of ±0.5% in the analysis of the reaction mixtures.

The radical stabilization energy due to an a-chlorine atom from the kinetics of the thermal isomerization of 1-Chlorobicyclo[2,2,0]hexane in the gas and liquid phase

1975 ◽  
Vol 28 (9) ◽  
pp. 2079 ◽  
Author(s):  
RK Solly ◽  
EN Cain
Keyword(s):  
Liquid Phase ◽  
Least Squares ◽  
Gas Phase ◽  
Chlorine Atom ◽  
Excellent Agreement ◽  
Thermal Isomerization ◽  
Stabilization Energy ◽  
Arrhenius Parameters ◽  
Temperature Range ◽  
Kinetics Of

The rate of isomerization of 1-chlorobicyclo[2,2,0]hexane to 2- chlorohexa-1,5-diene, both in the gas phage and in solution, has been measured over the temperature range 409-497 K. The Arrhenius parameters derived from these rates are represented by the equations ����������������������������� log(kg/s-1)=(13.49�0.08)-(148.2�0.6/θ ����������������������������� log(ka/s-1)=(13.21�0.12)-(144.44�0.50)/θ� and����������������������������� log(kb/s-1)=(13.25�0.44)-(144.8�1.6)/θ where the subscripts g, a and b refer to the gas phase, tetrachloroethylene as solvent and o-dichloro-benzene as solvent respectively, θ = 19.15 kJ mol-1 and the errors are least-squares deviations. A radical stabilization energy of 5�2 kJ mol-1 for the α- chlorine atom derived from these Arrhenius parameters is in excellent agreement with the value derived from kinetics of the isomerization of 1,4-dichlorobicyclo[2,2,0]hexane and from the thermochemistry of chloroethyl radicals.

Kinetic study of the thermal isomerization of fulvene

1981 ◽  
Vol 34 (2) ◽  
pp. 449 ◽  
Author(s):  
BJ Gaynor ◽  
RG Gilbert ◽  
KD King ◽  
PJ Harman
Keyword(s):  
High Pressure ◽  
Reaction Mechanism ◽  
Kinetic Study ◽  
Low Pressure ◽  
Thermal Isomerization ◽  
Marcus Theory ◽  
Rate Coefficients ◽  
Arrhenius Parameters ◽  
Temperature Range ◽  
Concerted Reaction

The thermal unimolecular isomerization of fulvene to benzene was studied by the technique of very low-pressure pyrolysis. The observed fall-off regime rate coefficients (obtained over the temperature range of c. 1050-1150 K) were fitted by using RRKM (Rice-Ramsperger-Kassel-Marcus) theory (assuming a concerted reaction mechanism) to give high-pressure Arrhenius parameters in the range E∞ = 268-285 kJ mol-1, log(A/s-1) = 13-14.

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