无机化学英文版Chapter20.pptVIP

Copyright 1999, PRENTICE HALL Chapter 20 * Spontaneity of Redox Reactions EMF and Free-Energy Change ?G is the change in free-energy, n is the number of moles of electrons transferred, F is Faraday’s constant, and E is the emf of the cell. We define Since n and F are positive, if ?G 0 then E 0. Copyright 1999, PRENTICE HALL Chapter 20 * Effect of Concentration on Cell EMF A voltaic cell is functional until E = 0 at which point equilibrium has been reached. The point at which E = 0 is determined by the concentrations of the species involved in the redox reaction. The Nernst Equation The Nernst equation relates emf to concentration using and noting that Copyright 1999, PRENTICE HALL Chapter 20 * Effect of Concentration on Cell EMF The Nernst Equation This rearranges to give the Nernst equation: The Nernst equation can be simplified by collecting all the constants together using a temperature of 298 K: (Note that change from natural logarithm to base-10 log.) Remember that n is number of moles of electrons. Copyright 1999, PRENTICE HALL Chapter 20 * Effect of Concentration on Cell EMF Concentration Cells We can use the Nernst equation to generate a cell that has an emf based solely on difference in concentration. One compartment will consist of a concentrated solution, while the other has a dilute solution. Example: 1.00 M Ni2+(aq) and 1.00 ?10-3 M Ni2+(aq). The cell tends to equalize the concentrations of Ni2+(aq) in each compartment. The concentrated solution has to reduce the amount of Ni2+(aq) (to Ni(s)), so must be the cathode. Copyright 1999, PRENTICE HALL Chapter 20 * Effect of Concentration on Cell EMF Concentration Cells Since the two half-reactions are the same, Eo will be zero. Copyright 1999, PRENTICE HALL Chapter 20 * Effect of Concentration on Cell EMF Cell EMF and Chemical Equilibrium A system is at equilibrium when ?G = 0. From the Nernst equation, at equilibrium: Copyright 1999, PRENTICE HALL Chapter 20 * Batteries Lead-Acid Battery A 12 V car