Relative-rate study of thermal decomposition of the 2-butoxyl radical in the temperature range 280–313 KElectronic supplementary information (ESI) available: See http://www.rsc.org/suppdata/cp/b1/b111474c/

2002 ◽  
Vol 4 (12) ◽  
pp. 2579-2586 ◽  
Author(s):  
H. G. Libuda ◽  
O. Shestakov ◽  
J. Theloke ◽  
F. Zabel
Keyword(s):  
Thermal Decomposition ◽  
Relative Rate ◽  
Supplementary Information ◽  
Temperature Range ◽  
Rate Study

KINETICS AND MECHANISMS OF THE THERMAL DECOMPOSITION OF PROPIONALDEHYDE: PART II. THE REACTION IN THE PRESENCE OF NITRIC OXIDE

1965 ◽  
Vol 43 (1) ◽  
pp. 278-289 ◽  
Author(s):  
K. J. Laidler ◽  
M. Eusuf
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Relative Rate ◽  
Temperature Range ◽  
Presence And Absence

The decomposition of propionaldehyde in the presence of various amounts of nitric oxide has been studied in the temperature range 520–560 °C and at propionaldehyde pressures from 30 to 300 mm Hg. The reaction is inhibited by small amounts of nitric oxide, and larger amounts give rise to strong catalysis. The order of the maximally inhibited reaction is 1.5 and the degree of inhibition decreases with an increase of propionaldehyde pressure. In the catalytic region the order of the overall reaction is 1.25 with respect to propionaldehyde, and the relative rate (the ratio of rates in the presence and absence of nitric oxide) is independent of propionaldehyde pressure. The overall rate in the catalytic region can be expressed as[Formula: see text]the unit of concentration being mole per cc. A mechanism in which nitric oxide initiates chains by the reaction C2H5CHO + NO → C2H5CO + HNO, propagates them by C2H5NO + C2H5CHO → C2H6 + C2H5CO + NO, and terminates them by C2H5 + C2H5NO → C4H10 + NO and C2H6 + C2H4 + NO and C2H5NO + C2H5NO → C4H10 + 2NO or C2H6 + C2H4 + 2NO is proposed and is shown to be consistent with the results.

Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

1977 ◽  
Vol 55 (20) ◽  
pp. 3596-3601 ◽  
Author(s):  
Michael T. H. Liu ◽  
Barry M. Jennings
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Diazo Compounds ◽  
First Order ◽  
Temperature Range ◽  
Decomposition Reactions ◽  
Consecutive Reactions ◽  
Rate Processes ◽  
Subsequent Decomposition

The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80–130 °C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes.

scholarly journals Uptake of NO<sub>3</sub> and N<sub>2</sub>O<sub>5</sub> to Saharan dust, ambient urban aerosol and soot: a relative rate study

2010 ◽  
Vol 10 (6) ◽  
pp. 2965-2974 ◽  
Author(s):  
M. J. Tang ◽  
J. Thieser ◽  
G. Schuster ◽  
J. N. Crowley
Keyword(s):  
Mineral Dust ◽  
Relative Rate ◽  
Simultaneous Detection ◽  
Saharan Dust ◽  
Uptake Coefficient ◽  
Ambient Aerosols ◽  
Mixing Ratios ◽  
A Value ◽  
Rate Study ◽  
Absolute Basis

Abstract. The uptake of NO3 and N2O5 to Saharan dust, ambient aerosols and soot was investigated using a novel and simple relative rate method with simultaneous detection of both NO3 and N2O5. The use of cavity ring down spectroscopy to detect both trace gases enabled the measurements to be carried out at low mixing ratios (<500 pptv or 1×1010 molecule cm−3). The uptake coefficient ratio, γ(NO3)/γ(N2O5), was determined to be 0.9±0.4 for Saharan dust, independent of relative humidity, NO3 or N2O5 mixing ratio and exposure time. Ambient (urban) aerosols showed a very limited capacity to take up N2O5 but were reactive towards NO3 with γ(NO3)/γ(N2O5)>15. A value of γ(NO3)/γ(N2O5)~1.5–3 was obtained when using candle generated soot. The relative rate obtained for Saharan dust can be placed on an absolute basis using our recently determined value of γ(N2O5)=1×10−2 to give γ(NO3)=9×10−3, which is significantly smaller than the single previous value. With the present uptake coefficient, reaction of NO3 with mineral dust will generally not contribute significantly to its NO3 loss in the boundary atmosphere or to the nitration of mineral dust.

THE THERMAL DECOMPOSITION OF PERACETIC ACID IN AROMATIC SOLVENTS

1963 ◽  
Vol 41 (7) ◽  
pp. 1826-1831 ◽  
Author(s):  
F. W. Evans ◽  
A. H. Sehon
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Peracetic Acid ◽  
First Order ◽  
Aromatic Solvents ◽  
Temperature Range ◽  
Polymeric Compounds

The thermal decomposition of peracetic acid in toluene, benzene, and p-xylene was studied over the temperature range 75–95°C. The main products of decomposition were found to be CH4, CO2, CH3COOH; small amounts of methanol, phenols, and polymeric compounds were also detected.The rate of the overall decomposition was first order with respect to peracetic acid, and the results could be explained by postulating the participation of the two simultaneous reactions:[Formula: see text] [Formula: see text]The rate constant of reaction (1) was independent of the solvent, whereas k2 was dependent on the solvent. The ratio k2/k1 was about 10.

THE KINETICS OF THE THERMAL DECOMPOSITIONS OF THE LOWER PARAFFINS: V. THE NITRIC OXIDE INHIBITED DECOMPOSITION OF n-BUTANE

1940 ◽  
Vol 18b (1) ◽  
pp. 1-11 ◽  
Author(s):  
E. W. R. Steacie ◽  
H. O. Folkins
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Free Radical ◽  
High Pressures ◽  
Free Radical Processes ◽  
Temperature Range ◽  
Radical Recombination ◽  
Radical Processes ◽  
Kinetics Of ◽  
Good Agreement

A detailed investigation of the inhibition by nitric oxide of the thermal decomposition of n-butane has been carried out over the temperature range 500° to 550 °C.In all cases it was found that inhibition decreased with increasing butane concentration. This suggests that radical recombination occurs in the normal decomposition by ternary collisions with butane molecules acting as third bodies.The activation energies of the normal and inhibited reactions have been determined. For high pressures the two values are in good agreement, viz., 58,200 and 57,200 cal. per mole respectively. The products of the inhibited reaction were also found to be the same as those of the normal reaction.It is concluded that free radical processes predominate, involving comparatively short chains.

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