chemical physics of discharges - Argonne National Laboratory

significant reaction int-ermedia te.
Additional experiments were conducted in which toluene and iodine vapors were
passe6 through the R.F. discharge together. Figure 10 shows the composition of the
products Eormed in this experiment. In .:iew of the known affinity of iodine €or free
radicals, (7) the formation of benzyl iodide, iodobenzene and methyl iodide together
with greatly reduced amounts of the previously observed products argues for the
presence of benzyl, phenyl and methyl radicals i'n the discharge. ;
It should also be noted that the visible emission spectrum which is shown in
figure 11 was observed vith the toluene discharge: This spectrum is similar to that 4
vhich Schuler had previously observed from electrode toluene discharges and assigned
to the benzyl radical.
In sumrary, the diCferent products and intermediates formed in this work as
contrasted to Streitwieser and Ward's study indicates that significant differences
are to be anticipated betveen R;F. and microwave powered discharges, and
unequivocal ly establish the importance of radical intermediates in the toluene R.F.
discharge. Addit!onally, the hazards involved in the Tenera1 ization of data
obtained in a specific type of discharge are readily apparent from these observations.
Literature Cited
1. H. Schuler and A. Michel, A. Naturforch., li)a. 495 (1955)
2. H.J. Kraaijveld and H.I. Waterman, Brenstoff-Chem., 43, 33 (1962),
C.A. x, 10627f
3. A. Strcftuicser and H.P.Ward, J. 4m. Cliem. Soc., 2, 539.. (1963).
,I
\
4.
5.
6.
I.V. Herezin, N.F. Kazankava and K. Martinek, Zhur. Obschei
Khim.. 2. 4093 (1960). C.A., 2, 27153b.
R.F. Pottie and F.F. Lossing, J. Am. Chem. SOC., 2. 2634 (1361)
P.N. Rylander, s. Meyerson and H.E. Grubb, J. Am. Chem. SOC. 2.
842 (1957).
' '
4
7. J.F. Carst and R.F. Cole, Tetrahedron Letters. w, 679 (1963).