The thermal decomposition of 2-chloroethanol

1976 ◽  
Vol 29 (3) ◽  
pp. 609 ◽  
Author(s):  
DC Skingle ◽  
VR Stimson
Keyword(s):  
Thermal Decomposition ◽  
Hydrogen Chloride ◽  
Ethyl Chloride ◽  
First Order ◽  
Order Rate ◽  
Polar Transition

2-Chloroethanol decomposes at 430-496� into acetaldehyde and hydrogen chloride with first-order rate given by: k1 = 1012.8�1 exp(-229700 � 4000/8.314T) s-l The rate is slightly less than that for ethyl chloride. That acetaldehyde is the product shows that a 1-2 shift of hydrogen has taken place and this is indicative of a polar transition state.The acetaldehyde subsequently decomposes to methane and this decomposition is catalysed by the hydrogen chloride produced.

The thermal decomposition of 1-ethoxyethyl chloride and the reverse combination

1967 ◽  
Vol 20 (8) ◽  
pp. 1553 ◽  
Author(s):  
RL Failes ◽  
VR Stimson
Keyword(s):  
Thermal Decomposition ◽  
Transition State ◽  
Hydrogen Chloride ◽  
Ethyl Ether ◽  
Reverse Reaction ◽  
Kcal Mole ◽  
First Order ◽  
Polar Transition

1-Ethoxyethyl chloride decomposes cleanly at 164-221� into vinyl ethyl ether and hydrogen chloride in a first-order manner with k1 = 1010.52exp(-30300/RT) sec-1 (1) The equilibrium of the system at 128-221� approached from either direction at various pressures is well represented by (Kp in atmospheres) 1.987 In Kp = 31.1 � 0.9-(16500�500)/T (2) and this leads to ΔH�f,298(g) = -71.9 kcal mole-1 for 1-ethoxyethyl chloride. Combination of (1) and (2) gives k2 = 108.7exp(-14700/RT) sec-1 ml mole-1 for the reverse reaction and rate measurements verify this. The reactions are molecular, and relative rates indicate a polar transition state.

The thermal decomposition of trimethylacetyl bromide

1970 ◽  
Vol 23 (3) ◽  
pp. 525 ◽  
Author(s):  
BS Lennon ◽  
VR Stimson
Keyword(s):  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Hydrogen Bromide ◽  
Transition States ◽  
Volume Ratio ◽  
Reaction Vessel ◽  
Chain Mechanism ◽  
Radical Chain ◽  
First Order ◽  
Polar Transition

Trimethylacetyl bromide decomposes at 298-364� into isobutene, carbon monoxide, and hydrogen bromide in a first-order manner with rate given by k1 = 138 x 1014exp(-48920/RT) sec-1 The rate is unaffected by addition of the products or of inhibitors, or by increase of the surface/volume ratio of the reaction vessel. The likely radical chain mechanism is considered and rejected. The reaction is believed to be a molecular one, and possible cyclic and polar transition states are discussed.

THE THERMAL DECOMPOSITION OF ETHANE: PART I. INITIATION AND TERMINATION STEPS

1966 ◽  
Vol 44 (4) ◽  
pp. 505-514 ◽  
Author(s):  
M C. Lin ◽  
M. H. Back
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Rate Coefficients ◽  
First Order ◽  
Temperature Range ◽  
Order Rate ◽  
Ethyl Radical ◽  
Initiation Reaction ◽  
Ethyl Radicals

The rates of production of methane and butane in the pyrolysis of ethane have been measured over the temperature range 550–620 °C and at pressures of 40–600 mm. At high pressure the rates of formation of both products were first order in ethane, but below 200 mm the first-order rate coefficients decreased. The ratio of methane to butane was consistent with the interpretation that methane is a measure of the initiation reaction and that the combination and disproportionation of ethyl radicals is the main termination step. The order of the decomposition of the ethyl radical with respect to ethane varied between 0.38 and 0.59. The results are discussed in terms of the mechanism of the overall process.

Thermal decomposition of methyl azide

1970 ◽  
Vol 48 (7) ◽  
pp. 1140-1147 ◽  
Author(s):  
M. S. O'Dell Jr. ◽  
B. deB. Darwent
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Order Rate Constant ◽  
First Order ◽  
Hexamethylene Tetramine ◽  
Order Rate

The thermal decomposition of gaseous methyl azide has been investigated at conversions of less than 1% at 155, 170, and 200 °C. The reaction has been shown to be homogeneous and unimolecular, the first-order rate constant being kun1 = 2.85 × 1014 exp − (40 500/RT). The decomposition results in the formation of CH3N(X3∑−) and N2(X1∑g+). The CH3N(X3∑−) do not react with CH3N3 to produce N2, but do form a polymer of composition similar to hexamethylene tetramine and also react with olefins. The major products are N2 and polymer; small amounts of H2 and CH4, but no C2H6, are formed.

THE KINETICS OF THE THERMAL DECOMPOSITION OF ETHYL BROMIDE AND ETHYL BROMIDE-d5

1958 ◽  
Vol 36 (7) ◽  
pp. 1043-1048 ◽  
Author(s):  
Arthur T. Blades
Keyword(s):  
Thermal Decomposition ◽  
Rate Constants ◽  
Pressure Effect ◽  
Ethyl Bromide ◽  
Carrier Gas ◽  
First Order ◽  
Order Rate ◽  
Kinetics Of

The kinetics of the pyrolysis of ethyl bromide and ethyl bromide-d5 have been studied using the toluene carrier gas technique. Variation of the pressure in the range 0.6 to 4.4 cm. Hg reveals what is believed to be a legitimate pressure effect on the first-order rate constants. The Arrhenius rate expressions determined at 4 cm. Hg pressure are: k(ethyl bromide) = 8.5 ± 1.6 × 1012e−52,200±300/RTsec−1 (T = 523°–633 °C);k(ethyl bromide-d5) = 2.1 ± 0.4 × 1013e−54,840±300/RT sec−1 (T = 531°–635 °C).The differences in the two rate expressions are discussed.

Thermal decomposition of propylene oxide

1968 ◽  
Vol 46 (14) ◽  
pp. 2454-2456 ◽  
Author(s):  
T. J. Hardwick
Keyword(s):  
Thermal Decomposition ◽  
Free Radicals ◽  
Propylene Oxide ◽  
First Order ◽  
Temperature Range ◽  
Rate Expression ◽  
Order Rate ◽  
Common Precursor

In the temperature range 402–425 °C, propylene oxide in a toluene medium decomposes to form propionaldehyde (60–70%), acetone (14%), and free radicals (25%). The ratio of products is invarient with temperature, suggesting a common precursor to all three products. Propionaldehyde further decomposes into free radicals. The first order rate expression for propylene oxide disappearance is3.7 × 1012 e−51900/RT s−1.

THE KINETICS OF THE DECOMPOSITION REACTIONS OF THE LOWER PARAFFINS: III. PROPANE

1938 ◽  
Vol 16b (11) ◽  
pp. 411-419 ◽  
Author(s):  
E. W. R. Steacie ◽  
I. E. Puddington
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Excellent Agreement ◽  
Rate Constants ◽  
Initial Pressure ◽  
First Order ◽  
Decomposition Reactions ◽  
Order Rate ◽  
Products Of Reaction ◽  
Kinetics Of

The kinetics of the thermal decomposition of propane has been investigated over a temperature range from 551° to 602 °C. The limiting high pressure first order rate constants are given by[Formula: see text]The first order rate constants fall off strongly with increasing percentage decomposition, and the rate decreases with decreasing pressure in a manner similar to the rate decrease in the decomposition of the butanes.Analyses of the products of reaction at various stages show them to be independent of temperature over the range examined, but to be affected by the initial pressure. This effect is undoubtedly due to the secondary hydrogenation of some of the initial products. The analytical results are in excellent agreement with those of Frey and Hepp.

scholarly journals Studies on Metal Hydroxy Compounds. XIV. Thermal Analyses, Calorimetry, and Decomposition Kinetics of Heterocationic Hydroxy Chloride Compounds

1973 ◽  
Vol 51 (23) ◽  
pp. 3882-3888 ◽  
Author(s):  
Ah-Dong Leu ◽  
Palepu Ramamurthy ◽  
Etalo A. Secco
Keyword(s):  
Thermal Decomposition ◽  
Rate Equation ◽  
Thermal Analyses ◽  
General Pattern ◽  
Type Equation ◽  
First Order ◽  
Order Rate ◽  
Kinetics Of ◽  
Order Rate Equation ◽  
Initial Mode

Studies were carried out on two series of mixed metal hydroxy chloride compounds of the type xMe(OH)2•yMCl2 where Me = Cd, Cu and M = Mn, Co, Ni, Cu, Zn, Cd, Mg, or Ca.Thermal analyses for the Cd–M series reveal that the initial mode of decomposition involves a dehydroxylation step with a concomitant metathetical reaction between MCl2 and CdO. The compound CdCl2•2CdO is formed and decomposes at higher temperature leading to the eventual volatilization of CdCl2. The kinetics of thermal decomposition follow a simple first-order rate equation. The sole exception to this general pattern of behavior is the Cd–Zn compound.The initial mode of thermal decomposition of the Cu–M series compounds follows a parallel pattern described for the Cd–M series. The kinetic data for the Cu–M series are fitted into three groups: (i) phase boundary control embracing the contracting sphere and contracting plate model equations, (ii) A-E type equation with n = 2, and (iii) first-order rate equation.

Thermal decomposition of alcohols. I. 2-Methylbutan-2-ol (t-Pentyl alcohol)

1974 ◽  
Vol 27 (5) ◽  
pp. 1047 ◽  
Author(s):  
WD Johnson
Keyword(s):  
Thermal Decomposition ◽  
Rate Constants ◽  
Arrhenius Equation ◽  
Consecutive Reaction ◽  
First Order ◽  
Order Rate

The thermal decomposition of 2-methylbutan-2-ol has been investigated from 432 to 570�C, over initial pressures ranging from 26 to 288 mmHg, and in the presence of toluene from 519 to 570�C. The decomposition is first order and homogeneous, involving the unimolecular elimination of water from the alcohol. 2-Methylbut-1-ene and 2-methylbut-2-ene decompose through a consecutive reaction under these conditions. The Arrhenius equation giving the variation of the first-order rate constants with temperature was found to be (R = 8.31 J mol-1 K-1) k = 1011.8 exp(- 23OOOO/RT) s-l

A kinetic standard for precise calibration of spectrophotometer cell temperature.

1981 ◽  
Vol 27 (5) ◽  
pp. 753-755 ◽  
Author(s):  
P A Adams ◽  
M C Berman
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Cell Temperature ◽  
First Order ◽  
Order Rate ◽  
Acid Catalyzed ◽  
Pseudo First Order ◽  
Hydrolysis Of

Abstract We describe a simple, highly reproducible kinetic technique for precisely measuring temperature in spectrophotometric systems having reaction cells that are inaccessible to conventional temperature probes. The method is based on the temperature dependence of pseudo-first-order rate constants for the acid-catalyzed hydrolysis of N-o-tolyl-D-glucosylamine. Temperatures of reaction cuvette contents are measured with a precision of +/- 0.05 degrees C (1 SD).

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