山大物化电化学2.pptVIP

* * * * * * * * * * Chapter 7 Electrochemistry §7.7 Thermodynamics of reversible cell 7.7.1. Measurement of Electromotive forces (emfs) Can voltameter be used to measure electromotive force? V E Ri Ro U Discussion What is electromotive forces? High-impedance input 1) Poggendorff’s compensation method i = 0, thermodynamic reversibility. Principle of potentiometer EW: working cell Ex: test cell Es: standard cell A Es Ex G Ew Ex Es K A B C1 C2 2) Weston standard cell Drawing from Edward Westons US Patent 494827 depicting the standard cell The Weston cell, is a wet-chemical cell that produces a highly stable voltage suitable as a laboratory standard for calibration of voltmeters. Invented by Edward Weston in 1893, it was adopted as the International Standard for EMF between 1911 and 1990. Hg Hg2SO4 Saturated CdSO4 solution Cd(Hg)x + -- Cork sealed with paraffin or wax Commercial Weston Standard cell 2) Weston standard cell E(T) /V = 1.01845 – 4.05? 10-5(T/K –293.15) – 9.5? 10-7(T/K –293.15)2 + 1? 10-8 (T/K –293.15)3 Weston standard cell Temperature-dependence of emf The original design was a saturated cadmium cell producing a convenient 1.018638 Volt reference and had the advantage of having a lower temperature coefficient than the previously used Clark cell 2. Nernst equation and standard EMF of cell 1889, Nernst empirical equation cC + dD = gG + hH Walther H. Nernst 1920 Noble Prize Germany 1864/06/25~1941/11/18 Studies on thermodynamics physical meaning of E? For a general electrochemical reaction: cC + dD = gG + hH Van’t Horff equation Theoretical deduction of Nernst Equation: 7.7.3. Standard electromotive forces E? equals E when the activity of any chemical species is unit. For cell: Pb(s)-PbO(s)|OH–(c)|HgO(s)-Hg(l) Write out the cell reaction and Nernst equation. For: Pt(s), H2 (g, p?)|HCl(m) |AgCl(s)-Ag(s) Write out the cell reaction and Nernst equation. E? E / V Experimental determination of standard electromotive force Cf. Levine, p.