Co MMUN~CATIONS TO THE EDITOR 2809

whelmed. Reaction 6 is well known from studies of

the hydrogen-oxygen reaction; it inhibits so that hy-
drogen and oxygen will not combine at atmospheric
pressure and temperatures much below 500, except
in the presence of a suitable catalyst. Although the
H02 radical is sufficiently stable that it inhibits hydro-
gen-oxygen below -500, at higher temperatures
chains may be continued through the slow reaction
EO2 + H2- H2Oz + H
Since the hydrogen-fluorine reaction continues, albeit
at a reduced rate, it seems reasonable that HO2 must
react with fluorine, as in reaction 7. Reaction 8 is a
reasonable bimolecular chain-termination step, while
reactions 2, 3, and 1 are familiar links from the
hydrogen-oxygen branched chain. (Reactions 1 , 2,
and 3 must be included to account for the fact that in
the presence of a large amount of oxygen the reaction
rate is independent of oxygen concentration.) Water
is not detected as a reaction product since it further
reacts to yield HF and ~xygen.~
By applying the steady-state approximation to the
concentrations of hydrogen, fluorine, and oxygen atoms
and also the OH and H02 radicals and remembering
that k6[M@)] >>k2, the following rate expression is ob-
tained
Actually the various third-body efficiencies in reaction
6 should be considered
h[M@)] =k6,~,([H2] + 0.43[N21 + 0.35[02] f
fFz[F2l + fHF[HFI)
Here fF, and fHF are the third-body efficiencies of F2
and HF relative to hydrogen (the efficiencies for nitrogen
and oxygen are from Lewis and Von Elbe4). We might
guess that fF* - 0.3 (by analogy with nitrogen and
oxygen) ; based on this assumption an analysis of the
data of Levy and Copelands2 Figure 3 indicates that
fHF - 1. Thus, the mechanism predicts a rate pro-
portional to about the first power of the fluorine con-
centration and a somewhat lower order with respect to
hydrogen. An over-all rate constant can be obtained
by equating the theoretical rate expression with the
empirical formula of Levy and Copeland
klk2k,
ksks
[&I + 0.43[N21 + 0.35[02]
[Hzll
Values so calculated are shown in Table I. The over-
all rate constants show slightly less variation, per-
centagewise, than the empirical 1.5-order rate constants.
kover-all =- - - kV%
Table I: Rate Constants for the Hydrogen-Fluorine
Reaction at 132O
-Rate constants-
Fa HZ Oz Nz m h - 1 (ref. 2) kover-all, mh - 1
-Initial mole fraotions- ka/,, a.u.-/Z
0.032 0.032 0.794 0.142 0.14 0.38
0.066 0.066 0.659 0.209 0.14 0.28
0.129 0.129 0.659 0.084 0.14 0.22
0.066 0.132 0.659 0.143 0.16 0.25
0.132 0.066 0.659 0.143 0.15 0.29
0.066 0.264 0.659 0.011 0.18 0.23
0.066 0.396 0.527 0.011 0.20 0.24
0.066 0.527 0.396 0.011 0.26 0.31
Av. 0.17 i =0.03 0.27 & 0.04
Total pressure 695 torr; from Table I11 of ref. 2.
I n summary, the mechanism proposed here seems to
provide an adequate description of the oxygen-in-
hibited reaction between hydrogen and fluorine. The
experimental data for smaller oxygen additions can
perhaps help to elucidate further the combination of
the mechanisms set forth here and in the preceding
communication.
(5) V. A. Slabey and E. A. Fletcher, N.A.C.A. Technical Note 4374,
Sept. 1958.
LEWIS RESEARCH CENTER RICHARD S. BROKAW
NATIONAL AERONAUTICS AND SPACE
CLEVELAND, OHIO 44135
ADMINISTRATION
RECEIVED JUNE 22, 1965
Parachor and Surface Tension of
Amorphous Polymers
Si r: Knowledge of the surface tension of polymers is
of interest, on the one hand, as a means of elucidating
the nature of the bulk and surface structure of polymeric
liquids and, on the other hand, because of its control-
ling influence on such practical applications of poly-
mers as spinning, adhesion, and stability of dispersions.
The critical surface tension yc of wetting of solid poly-
mers, obtainable from contact angle data by a proce-
dure proposed by Zisman12 has often been employed as
an estimate of the surface free energy of polymers, but
there always remained the question of the precise rela-
tion between yc and the true surface free energy. For
this reason, there has recently been a growing interest
(1) H. W. Starkweather, Jr., SPE Trans., 5, 5 (1965).
(2) W. A. Zisman, Advances inChemistry Series, No. 43, American
Chemical Society, Washington, D. C., 1964, p. 1.
Volume 69, Number 8 August 1966