chemical physics of discharges - Argonne National Laboratory

chemical physics of discharges - Argonne National Laboratory chemical physics of discharges - Argonne National Laboratory

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I 26 in the anode region. Some of these ionized molecules present in that region and the ions were repelled by the potential on the anode and drifted back into the ionization chamber. These primary ions could not be themselves collected, but new second- ary ions could be unequivocally identified. Further, by varying the potential on the anode, it was possible to obtain an appearance potential for the secondary ions and from this to deduce the identity of its precursor. A large number of reactions of ions with neutrals have now been identified and typical examples of the various classes of such bimolecular reactibns are given in tables 1 through 7. Table 1 Atom Transfer Reactions + + Kr + D2 + Xe + CH4 + N+ + D2 + -+ KrD+ + D (9) + + XeH + Cis3 (10) + -+ N2D + D (9,11) + C3H5 (12) 5+ + 0 + N2 + 0 + C02 2+ -+ NO + N (14,15) -+ 0 + CO (16) + CH3 (17)' CH4 + C3H6 + CH + D20 + nC4HI0 --f HD 0 + C4H9 (13) + 2+ I + cH31 -+ I2 (9) Schissler, D. 0. and Stevenson, D. P., J. Chem. Phys.,24, 926 (1956) (Ip' u>ld, F. H., Franklin, 3. L., 2. &. *m. E. 83, 4509 (1961) (11)-Stevenson, D. P., J. a. %m.,6l, 1453 (1957) (12) Frankevich, E. L. and Tal'roze, V. L., Dokl. Akad. Nauk SSSRZ, 1174 (1958) (13) Lampe, F. W., Field, F. H. and Franklin, J. L., J. 3. Km. E., 79, 6132 - (1957) (14) Potter, R. F., J. E m . Phys., 23, 2462 (1955) s= (15) Fehsenfeld, F. C., SchmeltekopfTA. L. and Ferguson, E. E., Planet. Space Science 13, 219 (1965) (16) zhsenfeld, F. C., Ferguaon, E. E. and Schmeltekopf, A. L., 2. Chem. Phys. 2, 3022 (1966) (17) Pottie, R. F., Barker, R. and Hamill, W. H., Radiation Research 2, 664 (1940) (18) (19) (20) Table 2 Positive Atomic Ion Transfer Reactions 0 ++ H2 + H O++ 0 (18) H2 2+ + O2 +€SO> + H (9,11) . HI++ CH31 + CH I + + H (19) 33 C2H: + D20 +€ID 0 + C2H5 + 3 O2 + N +NO + 0 (21) 0; + C2H2 --t C2H20+ + 0 Hutchinson, D. A., Paper presented at American Chemical Society Meeting, Minneapolis, Minnesota, September, 1955 Pottie, R. F., Barker, R. and Hamill, W. H., Radiation Research 10, 664 (1959) Lampe, F. W., Field, F. H. and Franklin, J. L., J. Amer. Chem. s., 2, 6132 (1957) (21) Golden, P. D., Schmeltekopf, A. L., Fehsenfeld, F. C., Schiff, H. I., and 1 - Ferguson, E. E., 2. Chem. Phys. 44, 4095 (1966) (22) (20) c 1 \ !I 4 I\ \ ,

27 (22) Franklin, J. L., Munson, M.S.B., Tenth Symposium (International) on Combustion, The Combustion Institute, 1965, p. 561 (23) (24) (25) (26) (27) Table 3 Symmetrical Transfer Reactions + H; + H2 i H, + H (23,24,11) CH + CH4 i CH' + CH3 (2,3,4,5) i 4+ 5+ H 0 + H20 +H30 + OH (1) 2 HC1+ + + HC1 + H2C1 + H (9) + CH202+ + CH202 4 CH 0 + HC02 (22) NH;+ NH3 +NH4 3+2 + NH2 (25,26,27) I2 + I2 +I + I (28) 3 Eyring, H., Hirschfelder, J. 0. and Taylor, H. S., 2. Chem. Phys. 3, 479 (1936) Stevenson, D. P. and Schissler, D. O., J. %m. Phys.23, 1353 (1953) Lampe, F. W. and Field, F. H., Tetrahedron 1, 189 (l"3) Dorfman, L. M. and Noble, P. C., J. Phys. CEem. 63, 980 (1959) Derwish, G. A. W., Galli, A., Giardini-G-idoni, A., and Volpi, G. G., J. - Chem. Phys. 3, 1599 (1963) and Harkness, R. W., Phys. Rev. 2, 784 (1928) (28) Hogness, T. Table 4 ~ - H- and H,- Transfer Reactions + L + C2H5+ C H + C3H8 + C3H8 + C2H6 + C H 7+ + C H + C3H7 (29) (29) 4+ 5+ CH3 + C2H6 + C2H5 + CH4 (34) + C3H5 + neo-C 5 H 12 + tC5H:1 + '3f6 (34) + C H + C3H8 + C H + C3H6 (29) 2 6 24 C H + iC4H10 -+ C H + + iC4H8 (29) 3 6 3 8 +" (29) M.S.B.Munson, J. L. Franklin and F. H. Field, J. Phys. Chem. 68, 3098 (1964) Table 5 Some+$eactions of Excited Ions + C2H6 + C2Hl+ + C2H5 (29) C2H6 H2+* + He + HeH + H (30) N + N2 O2 2+* + O2 + N -I- + N (21,23,33) + 0: + 0 (22,31) (30) H. von Koch and L. Friedman, J. Chern. Phys. 38, 115 (1963) (31) R. K. Curran, 2. Chem. Phys. 38, 2974 (1963)- (32) M.S.B.Munson, F. H. Field and?. L. Franklin, 2. Chem. Phys. 37, 1790 (1962) - (33) M. Saporoschenko, Phys. Rev. 111, 1550 (1958) (34) Field, F. H. and Lampe, F. W., J. Amer. Chem. z., 2, 5587 (1958)

27<br />

(22) Franklin, J. L., Munson, M.S.B., Tenth Symposium (International) on Combustion,<br />

The Combustion Institute, 1965, p. 561<br />

(23)<br />

(24)<br />

(25)<br />

(26)<br />

(27)<br />

Table 3<br />

Symmetrical Transfer Reactions<br />

+<br />

H; + H2 i H, + H (23,24,11)<br />

CH + CH4 i CH' + CH3 (2,3,4,5) i<br />

4+ 5+<br />

H 0 + H20 +H30 + OH (1)<br />

2<br />

HC1+ + +<br />

HC1 + H2C1 + H (9)<br />

+<br />

CH202+ + CH202 4 CH 0 + HC02 (22)<br />

NH;+ NH3 +NH4 3+2 + NH2 (25,26,27)<br />

I2 + I2 +I + I (28)<br />

3<br />

Eyring, H., Hirschfelder, J. 0. and Taylor, H. S., 2. Chem. Phys. 3, 479 (1936)<br />

Stevenson, D. P. and Schissler, D. O., J. %m. Phys.23, 1353 (1953)<br />

Lampe, F. W. and Field, F. H., Tetrahedron 1, 189 (l"3)<br />

Dorfman, L. M. and Noble, P. C., J. Phys. CEem. 63, 980 (1959)<br />

Derwish, G. A. W., Galli, A., Giardini-G-idoni, A., and Volpi, G. G., J.<br />

- Chem. Phys. 3, 1599 (1963)<br />

and Harkness, R. W., Phys. Rev. 2, 784 (1928)<br />

(28) Hogness, T.<br />

Table 4<br />

~<br />

-<br />

H- and H,- Transfer Reactions<br />

+ L +<br />

C2H5+<br />

C H<br />

+ C3H8<br />

+ C3H8<br />

+ C2H6 + C H<br />

7+<br />

+ C H + C3H7<br />

(29)<br />

(29)<br />

4+ 5+<br />

CH3 + C2H6 + C2H5 + CH4 (34)<br />

+ C3H5 + neo-C 5 H 12 + tC5H:1 + '3f6 (34)<br />

+ C H + C3H8 + C H + C3H6 (29)<br />

2 6<br />

24 C H + iC4H10 -+ C H + + iC4H8 (29)<br />

3 6 3 8<br />

+"<br />

(29) M.S.B.Munson, J. L. Franklin and F. H. Field, J. Phys. Chem. 68, 3098 (1964)<br />

Table 5<br />

Some+$eactions <strong>of</strong> Excited Ions<br />

+ C2H6 + C2Hl+ + C2H5 (29)<br />

C2H6<br />

H2+* + He + HeH + H (30)<br />

N + N2<br />

O2 2+* + O2<br />

+ N -I- + N (21,23,33)<br />

+ 0: + 0 (22,31)<br />

(30) H. von Koch and L. Friedman, J. Chern. Phys. 38, 115 (1963)<br />

(31) R. K. Curran, 2. Chem. Phys. 38, 2974 (1963)-<br />

(32) M.S.B.Munson, F. H. Field and?. L. Franklin, 2. Chem. Phys. 37, 1790 (1962) -<br />

(33) M. Saporoschenko, Phys. Rev. 111, 1550 (1958)<br />

(34) Field, F. H. and Lampe, F. W., J. Amer. Chem. z., 2, 5587 (1958)

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