2017年後期物理化学演習 甲南大学理工学部

1 2017 Wref RTILH2Ag/AgClPtW2H+ + 2e-= H2 Wref RTILH2Ag/AgClPtW AgCl+ e-= Ag +Cl- Wref H2 PtW KCl Ag PtAg KCl Ag AgCl iAg|AgCl AgCl+ e-= Ag + V (vsSHE, 25 C) | Ag|AgCl Cl- ~ Ag | AgCl |3 mol dm-3aq. NaCl Ag | AgCl | mol dm-3aq. KCl vs :versus SHE : standard hydrogen electrode AgCl+ e-= Ag +Cl- 2 Cl- AgCl > 3 mol dm-3 25 C Pauling pm 2015 B KClNaClO4 mol dm-3~ mol dm-3)O.

2 F. Tower, Z. phys. Chem., 18, 17-50 (1895); 20, 198-206 (1896).LeipzigK+Cl-(Based on Kohlrausch s work) O. F. Tower, Z. phys. Chem., 18, 17-50 (1895); 20, 198-206 (1896).N. Bjerrum, Z. phys. Chem., 43, 428-440 (1905).N. Bjerrum, Z. Elektrochem., 17, 389-408 (1911).LeipzigKlaus Beneke(2005); 40 2012 Electrochemistry Laboratory in 20century(A recent scene in Kakiuchi Lab.) T. Ozeki, Y. Tsubosaka, S. Nakayama, N. Ogawa, T. Kimoto, Anal. Sci., 14, 749-0756 (1998).T. Kakiuchi, T. Yoshimatsu, Bull. Chem. Soc. Jpn., 79, 1017-1024 2006).Salts NaCl 804 C KCl 773 C Molten salt Electrochemistry , alkylimidazolium halides BF4- PF6-Room-temperature Ionic Liquids(Room-temperature molten salts)Ionic Liquids?

3 Ox + ne-= Rd Nernst (1) M1M2S2S1M3M1 Nernst Helmholtz Nernst (2)Nernst P p Ag+ W. Nernst, Z. phys. Chem., 4, 129 181 (1889). R. Peters, Z. phys. Chem., 26, 193 236 (1898). Peters G. Bredig R. Luther(W. M. Clark)E - Walther Hermann Nernst 1864 6 25 1941 11 18 ( )Nernst (3) for the single potential difference between an electrode and an electrolyte G. N. Lewis, Proc. Am. Acad. Arts Sci., 43, 259 293 (1907). while equation XXIX is universally true, the equation of Nernst is obviously only true when the activity of the ion in the electrolyte is proportional to its concentration (p.)

4 291). XXIX G. 1875 10 23 -1946 3 23 1926 "photon" ( ) AgClOxRdS KClMCu | Ag AgCl| Satd. KCl || Ox, Rd | M | Cu AgCu Cu OxRdM OxRdMA. M. O Mahony, D. S. Silvester, L. Aldous, C. Hardacre, R. G. Compton, J. Chem. Eng. Data, 53 (2008) 2884-2891[C2mim][NTf2]Y. Katayama, K. Sekiguchi, M. Yamagata, T. Miura, J. Electrochem. Soc., 152 (2005) iE (