SHORT

COMJ~LJXIC_=LTIOKS Co~nmzrsr., (1951) Press. Pno, 1oG3_ 7 (1935) 196.

325

?3 4 5 6

J. HEYROVSK* -*ND D. ILKo~I~, CoZlecLion Czech_ Chent. J_ J. LIPGGAXGE, C1rem. Rec., zg (1941) I. D. D. DEFORD AKD D. N_ HUME, J_ Am. Chenz. SOL. 73 H. IRL?xG. AcEvawces izz Polaroguaphs, Vol. I. Pergamon JO-CHUXXG Lru XKD HSIXO-YUAK Fu, Ko Hsueh Tzcng S. S. MESARIC AXD D. N. HUME, IJzovg. Che~x, 2 (1963)

5321~ London. 23 (1957)

1960. 71%

42.

Received

January

25th.

1965
COMPLESES OF ZISC _%XD CXD~IIUlrI IN AQUEOUS MEDIUM

POLAROGRAPIIIC

STUDIES

OF THE PYRIDISE

Complexes of zinc and cadmium with p>sldine have been studied polarographically using the method of DEFORD AXD HUME. Two comples ions,[Zn(py)]T ar,d [Zn(py)?_=+. having over-all formation constants, fll = S-0 2 0.5 and #l- = 34-o & 1.0, were detected in the zinc--p>-ridine s>-stem. In the cast of the cadmium--p>-rldine system, three complex species, [Cd(py)j+, [Cd(py)z]z+ and [Cd(py)s]z-. were found to be present, having constants /31 = 23 f 2.0, & = 72 & 5-o and 83 = So 2 5.0. The percentage composition of the various complcsed and uncomplesed ions for both systems are presented. J_ Ekclroanal. Chem.. g (1965) 321-325

The

mechanism

of charge

transfer

at electrodes
of the charge transfer mechanics of chemical ion bonds to give

From 1935 until the late sos, most treatmentsIprocess have been analogous to those used in the quantum reactions_ Stretching of ion-solvent and substrate-discharged

entities of equal energy have been the essential processes govemmg the rate of charge transfer. Such treatments allow the prediction of the effect of variablesl-7, e.g., dielectric constant of the solvent, on the rate of charge transfer. They allow calculation of the symmetry factor of electrode reactions and its variation with potentialsHowever, such an ion-transfer model leaves implicit the motion of the electron itself, and omits to consider the charge distribution in the activated state. Since x958 several treatments 8-10 of charge transfer have been made in which the basic model is that of redox processes in solution. In these treatments attention has been focused on the electron, tending to rninimise the role played by ion-solvent and substrate-atom interactions_ GERISCHER 11 has introduced a more general treatment based on the work of GURNEYS. The above treatments of charge transfer lead to incorrect interpretations of the symmetry factor 14- The significance of the crossing point of the potential energy surfaces, pertinent to the reaction, has not been fully recognized and the charge distrib-ution in the activated state has either been neglected or given a false significance. The potential energy profile for electron transfer, e.g., in the discharge step, HsO++Me-++MH+HeO of the energy hydrogen evolution of the initial state, reaction (h-e-r.) may be represented12 by Fig. HaOf +- Me-, with the reactants in their ground
I.

(I) The states,

is represented by EL The energy of the neutralized state, M-H + Hz0 atom in the position immediately after neutralization (not necessarily state of the M-H) is represented by En_
J_ EZectrocmaZ. Chena..

with the H the ground

g (1965)

325-327

326

SHORT

COM~IL~SICATIOSS

metal surroce

Dstonce

from

metal

Fig.

I. Potential

energy

profile

for electron

transfer.

The probability of electron tunnelling from the metal to the HsO+ ion for an unactivated electron is zero, if there is no acceptor state for the electron. Thus, for neutralization of the HsO+ ion by an electron from the Fermi level of the metal, the energy to zero. TIzis is brozcght abozct by LIE (Fig. I). equal to (E II - Er). must be decreased activating the H+-OHs bond by an amount of ener,7 ds. Because stretching of the H+-OHs bond activates the initial state, but stabilizes the resultant neutralized state, ds is equal to some fraction, p. of LZE. where /3 is, general, a function of E. When the system is arranged so that dE = o, electron tunnelling from the metal to the proton can occur with some finite probability. The resulting H atom may then either relax into the ground state of the system MH + HsO, or re-form a proton by electron tunnelhng Ha Of + MeHz0 + H-M to the metal. + + HzO-H+ Hz0 + The discharge + step of the h.e.r. Hz0 + H-M may then be written: + MeMH

The activated state is comprised of tie resonant states, with th& same atomic, but different electronic configuration (cf- a similar conclusion by MARCUS~ for redox systems, reached by a different approach). Consideration of the relative electron tunnelhng probabilities, from H to H+ and H to M, leads to the cbnclusion that the resonant states are equally probable, and that the effective charge on the H nucleus in the activated state is 112 (CC_ a similar conclusion due to HUSH~, attained for redox systems by a different approach)_ Apphcation of an electrical potential difference d$, changes the energy gap, &?Z, to dE(d$) _= LIE + AqW (Aq5 being negative for cathodic potentials). The en_ergy required to activate the H+4Hz bond is then#3dE(d#) _ Thus, the activation energy-at a given d$ is #IdE(d$) and the symmetry factor is fl_ Since for the purpos bf -calculating 8, we are interested only in the energy required to stretch the HzO-H -bond at-a- g-i)ren;A#. then /I nzey_&e obtained by the usual method of vertical shtiftl,3.6~15

SHORT

COMMU-\;IC_~TIONS

327 of the c?aarge distribution in the acti_Jated state. dQ is thus the ratio of energy put into the H+-

and the symntetr;v factor is inde@wdertt The symmetry factor at a given OH2

bond to that put into closing the gap dE(d&I). The present theory thus gives a tenable model for the electron movement in charge transfers-13, but it relates this movement to that of the ion-solvent and atomsubstratel-7. gap dE(d#), other than Means other than the above described mechanism, of closing the energy such as electron activation, solvent activation, or activation of modes the H+-OH2 stretching mode, will lead to higher energies of activation

by virtue of the fact that AE = AE(Aq5) for such processes_ This suggests that, for (or adion-solvent) all types of electrode processes the stretchin, u of the ion-solvent bond constitutes the rate-determining aspect of charge transfer at electrodes. TAX Electrochemistry Laboratory, The Uni-Jenit_v of Pemzsyhania. Ph.iZadeZphia, Pa. rgrog (U.S.A J_ OIM. BOCKRIS D. B. MAJTHEWS* .)

I J_ HORIUTI ASD M. PoL_+x~I, dcla PhysicocJzivz_ URSS. 2 (1935) 505~ 2 0. ESSIN AE?D LT. KOZHEUROV, data Pkysi~o~him. URSS, 16 (rg+-_) 16-g. 3 R. P_XRSOXS AND J. O.&I_ BOCKRIS, Tvans. Favaday Sec.. 47 (1951) 914. 4 l3. E. CONWAY -*ND J_ O'&I. BOCK-CRTS. Cax J_ CJtem., 35 (1957) 1124. 5 B. E. CONWAY XND J_ O'M. BOCKRIS, EZeclrocJzim. Acta, 3 (1961) 340. 6 A. R. DESPIC AND J. O'M. BOCKRIS,~. Chem. PJcys., 32 (1960) 389. 7 J_ O'N BOCKRIS. J_ Chim. Plays., 49 (1952) 41. 8 Ti. A. BIARCUS, /_ Chem. Pkys., 3s (rg63) 1558; 39 (1963) 1734; /_ Pkys. CJzem.. 67 (1963) 853; 21; Tuaxs. Sy~np. EZeclrode Can. J_ Chem.. 37 (rg5g) 155; Disczcssio,rs Faraday Sot., 29 (1960) Processes. PhiZadelphia. Pa.. rg59, edited by E. YB_XGER, \Viley, Xew York, 1961. ch. 13, p_ 239_ g N. S. HUSH, J_ CJrem_ Phys.. 28 (1959) 962. Dokl. Akad. Xaitk SSSR. 144 (1962) 1077; 145 IO R. R. DOGON_+DZE AXD Yu. _I. CHIZX~DZHEV, II 12 13 14 15 (1962) 849; 150 (1963) 333. H. GERISCHER, Z. Pkysik. Chem_ Frankfrcrl, 26 (IgGo) 223, 325; 27 (1961) 48. R. GURKEY. Proc_ Roy. Sot. (London). Ser_ A, 134 (1931) 137~ J_ A. V_ BUTLER, Pvoc_ Roy_ Sot_ (Lundox).Ser_ A. 157 (1936) 423_ D. B. &TAITHEWS, Ph.D. Thesis, Univ. of Pennsylvania. 1965. Vol. I, Butterworth, London, J_ O'M. BOCKRIS. Alodern Aspects of EZecirocJtemislry, ch. 4_
J_ EZecZroanai. Chem.. g
(igG5)

1954,

325-327

* NowattheDepartmentof

Matkials

Science, University of Virginia.-Chtilottesville,Va. (U.S.A.)