Free radicals by mass spectrometry. XL. Primary processes and transient intermediates in the mercury (3P1) photosensitization of hydrazine

1969 ◽  
Vol 47 (8) ◽  
pp. 1391-1393 ◽  
Author(s):  
A. Jones ◽  
F. P. Lossing
Keyword(s):  
Mass Spectrometry ◽  
Free Radicals ◽  
Mass Spectrometer ◽  
Direct Evidence ◽  
Flow Reactor ◽  
Low Pressure ◽  
Primary Decomposition ◽  
Fast Flow ◽  
Transient Intermediates ◽  
Fast Flow Reactor

The low pressure mercury (3P1) photosensitized decomposition of hydrazine has been studied at 55 °C in a fast flow reactor coupled to a mass spectrometer. Direct evidence was obtained for the participation of N2H2, N2H3, NH2, and NH in the decomposition, and two primary decomposition modes were established[Formula: see text]

Reaction Kinetics of Ground State Fluorine, F(2P), Atoms. I. Measurement of Fluorine Atom Concentrations and the Rates of Reactions F + CHF3 and F + Cl2 using Mass Spectrometry

1973 ◽  
Vol 51 (21) ◽  
pp. 3596-3604 ◽  
Author(s):  
Michael A. A. Clyne ◽  
Donald J. McKenney ◽  
Ronald. F. Walker
Keyword(s):  
Mass Spectrometry ◽  
Reaction Kinetics ◽  
Ground State ◽  
Fluorine Atom ◽  
Flow Reactor ◽  
Bimolecular Reaction ◽  
Inlet System ◽  
Fast Flow ◽  
Kinetics Of ◽  
Fast Flow Reactor

Reactions of F(2P) atoms generated by a 2.45 GHz discharge in dilute F2 + He mixtures have been studied mass spectrometrically with a beam inlet system from a fast flow reactor. F atom concentrations have been measured from the consumption of Cl2 in the simple and extremely rapid bimolecular reaction 1[Formula: see text]k1 was determined to be (1.1 ± 0.3) × 10−10 cm3 molecule−1 s−1 at 300 °K.Rate measurements for the reaction 2, which forms CF3 radicals, are reported, over the range 301 to 667 °K,[Formula: see text][Formula: see text]A less detailed survey of the rates at 298 °K of a series of reactions of F with H2, CH4, CH3Cl, CH2Cl2, and CHCl3, is also given; in these cases, the source of F was a discharge in CF4 + Ar, and [F] was measured by titration with ClNO.

Tubular Fast Flow Reactor for High Temperature Gas Kinetic Studies

1972 ◽  
Vol 43 (5) ◽  
pp. 726-730 ◽  
Author(s):  
Arthur Fontijn ◽  
Shelby C. Kurzius ◽  
James J. Houghton ◽  
John A. Emerson
Keyword(s):  
High Temperature ◽  
Flow Reactor ◽  
Kinetic Studies ◽  
Fast Flow ◽  
Fast Flow Reactor ◽  
High Temperature Gas

FREE RADICALS BY MASS SPECTROMETRY: XXII. PRIMARY DECOMPOSITION STEPS IN THE MERCURY-PHOTOSENSITIZED DECOMPOSITION OF METHANOL AND DIMETHYL ETHER

1961 ◽  
Vol 39 (1) ◽  
pp. 102-109 ◽  
Author(s):  
R. F. Pottie ◽  
A. G. Harrison, ◽  
F. P. Lossing
Keyword(s):  
Mass Spectrometry ◽  
Free Radicals ◽  
Dimethyl Ether ◽  
Excited Molecule ◽  
Primary Decomposition ◽  
Oh Radicals ◽  
No Formation ◽  
Abstraction Reaction ◽  
Reaction Proceeds ◽  
Low Pressures

The Hg 3P1 photosensitized decomposition of methanol at low pressures proceeds mainly by a dissociation into CH3O radicals and H atoms. No formation of CH2OH radicals is observed. A subsidiary reaction to form CH3 and OH may also be a primary step. Formation of CH2OH radicals at higher pressures is attributed to an abstraction reaction of CH3O with CH3OH.Two primary modes of dissociation are found to occur for dimethyl ether:[Formula: see text]The relative probabilities of occurrence at low pressures are ∼45% and ∼50%, respectively. The possibility that the second reaction proceeds by formation of an excited molecule is discussed.

Gas-phase chemical kinetics of small metal clusters: developmen and characterization of a fast-flow reactor for neutral clusters

1993 ◽  
Vol 26 (S1) ◽  
pp. 168-170 ◽  
Author(s):  
L. Lian ◽  
F. Akhtar ◽  
J. M. Parsons ◽  
P. A. Hackett ◽  
D. M. Rayner
Keyword(s):  
Gas Phase ◽  
Chemical Kinetics ◽  
Metal Clusters ◽  
Flow Reactor ◽  
Fast Flow ◽  
Kinetics Of ◽  
Fast Flow Reactor ◽  
Phase Chemical

FREE RADICALS BY MASS SPECTROMETRY: XI. THE MERCURY PHOTOSENSITIZED DECOMPOSITION OF C2–C4 OLEFINS

1956 ◽  
Vol 34 (6) ◽  
pp. 701-715 ◽  
Author(s):  
F. P. Lossing ◽  
D. G. H. Marsden ◽  
J. B. Farmer
Keyword(s):  
Mass Spectrometry ◽  
Free Radicals ◽  
Hydrogen Atom ◽  
Mass Spectrometer ◽  
Cross Sections ◽  
Methyl Radicals ◽  
Allyl Radical

The mercury photosensitized (Hg3P1) decomposition of olefins has been examined using a reactor coupled directly to a mass spectrometer. The primary split of ethylene has been shown to be predominantly molecular, and that of propylene mainly into an allyl radical and a hydrogen atom. With 1-butene the split is predominantly at a C–C bond giving allyl and methyl radicals, although a rupture of a C–H bond occurs as well. With 2-butene and isobutene a C–H bond is broken. It is concluded that the allyl and methallyl radicals produced have large cross sections for reaction with excited mercury atoms.

High-temperature fast-flow reactor study of Sn/N2O chemiluminescence

1975 ◽  
Vol 34 (2) ◽  
pp. 398-402 ◽  
Author(s):  
William Felder ◽  
Arthur Fontijn
Keyword(s):  
High Temperature ◽  
Flow Reactor ◽  
Fast Flow ◽  
Fast Flow Reactor

Tubular fast-flow reactor studies at high temperatures. Kinetics of the reaction

1974 ◽  
Vol 27 (3) ◽  
pp. 365-368 ◽  
Author(s):  
A. Fontijn ◽  
W. Felder ◽  
J.J. Houghton
Keyword(s):  
High Temperatures ◽  
Flow Reactor ◽  
Fast Flow ◽  
Kinetics Of ◽  
Fast Flow Reactor
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