1056 are well defined and that p is independent of ion energy as previously reported.21 The only major sources of error are in the time interval measurement, which should and in the determinabe accurate to better than tion of the concentration of reactant gas in the reaction region, which is probably accomplished within the same uncertainty. The absolute rate constant of 1.00 f 0.08 X 10-9 cc sec-' derived from these measurements
+5z,
(21) For a recent summary, see R. P. Clow and J. H. Futrell, Int. J . Mass Spectrom. Ion Phys., 4, 165 (1970).
is in good agreement with the value 1.09 f 0.09 X le9cc sec-l reported by other investigators.21 Acknowledgments. This investigation was supported in part by the National Science Foundation and in part by the Robert A. Welch Foundation of Houston, Texas. We are sincerely grateful for this support. One of the authors also wishes to express his gratitude to Professor E. W. McDaniel for a very stimulating and extremely helpful discussion and permission to visit his laboratory.
Rate Constants for Reaction of Hydrogen Atoms with Aromatic and Heterocyclic Compounds. The Electrophilic Nature of Hydrogen Atoms' P. Neta and Robert H. Schuler" Contribution f r o m the Radiation Research Laboratories and Department of Chemistry, Mellon Institute of Science, Carnegie-Mellon University, Pittsburgh, Pennsylvania 15213. Received April 30, 1971 Abstract: Rate constants for the reaction of H atoms with aromatic and nitrogen heterocyclic compounds in aqueous solutions have been measured by a steady-state in situ radiolysis-esr method. The rate constants for the aromatic compounds investigated vary between 2.4 and 26 x I08 M-' sec-1 and those for the heterocyclic compounds between 0.6 and 3.3 X 108 M-l sec-l. Electron-donating substituents enhance the rate and electron-withdrawing groups retard the rate, qualitatively indicating an electrophilic character for the reaction. Correlation of the rate constants for a series of monosubstituted benzenes with Hammett's substituent constants shows a reasonably linear behavior (log k = 9.04 - 0.45~). Additivity ofthe u constants was tested for the case ofthe acid form of the phenylenediamines and for the dicyanobenzenes. In the first instance the rate constants for all three isomers were found to be about one-half that for the anilinium ion, as expected from the Hammett plot. Additivity fails, however, in the case of the dicyanobenzenes where the rate constants for the three derivatives differ by a factor of two and those for the ortho and meta isomers are only slightly less than for cyanobenzeneitself. In the case of pyridine the introduction of a nitrogen atom into the aromatic ring causes a considerable decrease in the rate constant. The effect of a second nitrogen atom is dependent on the position. The rate for pyrimidine is lower while the rates for pyridazine and pyrazine are higher than that for pyridine. These findings appear to reflect a reinforcement of the electron-withdrawingeffect of the nitrogen atoms when they are in the 1 and 3 positions but a partial cancellation in the 1 and 2 or 1 and 4 positions.
I
t is known that, in general, aromatic compounds react with hydrogen atoms with rate constants of the order of IO9 M-' sec-I and that the predominant pathway of this reaction is the addition to the aromatic Studies have been carried out by pulse radiolysis methods in which the formation of the cyclohexadienyl type radical was directly observed, 2-5 by competitive methods"' and by a steady state esr method recently developed in these l a b o r a t o r i e ~ . ~The , ~ former type of study specifically examines the addition reaction while the latter measures the total rate, but for most aromatic systems abstraction contributes little and the two types (1) Supported in part by the U.S . Atomic Energy Commission. (2) P. Neta and L. M. Dorfman, J. Phys. Chem., 73, 413 (1969). (3) E. J. Land and M. Ebert, Trans. Faraday Soc., 63, 1181 (1967). (4) M. C. Sauer, Jr., and B. Ward, J . Phys. Chem., 71, 3971 (1967). (5) II9and in organic solventsz0 so that comparison of the two sets of results is extremely tenuous. The constant 1.1 X IO9 in eq I represents the rate for the unsubstituted system, i.e., benzene. Sauer and Ward4 have reported a rate constant for benzene of 1.1 X IO9 M-I sec-' from direct observations on the production of cyclohexadienyl radical in pulse experiments. Michael and Hart7 report a somewhat lower value of 0.53 X IO9 M-' sec-1 obtained from more indirect experiments. The rate constant for benzene-sulfonic acid which would be predicted from eq I is 1.05 X IO9 M-I sec-l in good agreement with the absolute value of 0.82 X lo9 M-I sec-' previously determined.2 A discrepancy exists, however, in the case of nitrobenzene where values of 1.04 and 5.6 X lo9 M-I sec-l have been reported2s5from pulse measurements as compared to a value of 0.5 X lo9 M-' sec-l expected from the strong deactivating effect of the nitro group (umeta= 0.71 and upara= 0.78).14 The relatively high rate for the reaction of H atoms with nitrobenzene has previously been noted2s6and ascribed to a direct reaction with the nitro group. A contribution of the nitro group of about 0.5 X IO9 M-' sec-' to the total reactivity is suggested. It has since been observed, however, that in aliphatic compounds the nitro group is not particularly reactive. For example, a rate constant of only 4.4 X lo7 M-' sec-l is observed for reaction of n i t r ~ m e t h a n e . ~The apparent high reactivity of a nitro group in the aromatic systems, if real, must be a result of its activation by the aromatic nucleus. A similar situation appears to exist for benzaldehyde and acetophenone, both of which lie above the values predicted from eq I by about 0.5 X lo9 M-I sec-l. Since the carbonyl group is relatively unreactive toward H atom addition in aliphatic compounds (rate constants of only 2.8 X lofiand 3.4 X IO7 M-1 sec-' are observed for reaction of H atoms with acetone and acetaldehyde respe~tively),~ an activating effect of the aromatic nucleus on the carbonyl group must exist for this excess reactivity to be attributed to reaction with the substituent. Disubstituted Compounds. Two series of disubstituted compounds were examined, the phenylenedi(16) M. Anbar, D. Meyerstein, and P. Neta, ibid., 70, 2660 (1966). (17) P. Neta and L. M. Dorfman, Adcan. Chem. Ser., No. 81, 222 ( 1968). (18) W. A. Pryor and R. W. Henderson, private communication. (19) J. I
