Charge-transfer complexes of bromine atoms with haloalkanes and alkanes

Journal Article · Thu Sep 09 04:00:00 EDT 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100138a009· OSTI ID:5651542

Alfassi, Z B; Huie, R E; Neta, P ^[1]; Mittal, J P; Shoute, L C.T. ^[2]

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1. National Inst. of Standards and Technology, Gaithersburg, MD (United States)
2. Bhabha Atomic Research Centre, Bombay (India)

Charge-transfer complexes of bromine atoms with haloalkanes and alkanes were produced by pulse radiolysis and by laser-flash photolysis in various organic solvents. Br atoms were produced by photolysis of Br[sub 2] (at 351 or 248 nm), by photolysis of bromoalkanes (at 248 nm), or by radiolysis of bromoalkanes (either in liquid form or in cyclohexane solutions). The transient spectra, monitored within microseconds after the pulse, had absorption maxima that varied between 300 and 500 nm and are ascribed to complexes of Br atoms with the various solvents or other solutes present. The absorption maxima for Br atom complexes with alkanes and chloroalkanes correlate with the ionization potential of these molecules, suggesting the existence of charge-transfer complexes. The correlation for the bromoalkanes was more complex. CBr[sub 4]Br and CHBr[sub 3][center dot]Br were observed to react rapidly (k = 10[sup 8]-10[sup 9] L mol[sup [minus]1] s[sup [minus]1]) with Br[sub 2] and with HBr to transfer their Br atom to these latter molecules. 16 refs., 5 figs., 2 tabs.

• OSTI ID: 5651542
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:36; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
ALKANES
BROMINE
CHARGE TRANSPORT
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
COMPLEXES
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELEMENTS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
HYDROCARBONS
LASER RADIATION
NONMETALS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATION EFFECTS
RADIATIONS
RADIOLYSIS