Lecture 15 The Nernst Equation讲座15能斯特方程.pptVIP

Lecture 13: The Nernst Equation Reading: Zumdahl 11.4 Outline: Why would concentration matter in electrochemistry? The Nernst equation Applications E°cell and DG (cont.) E°cell and DG An Example Balance, determine E°cell and K for the following: An Example (cont.) Determining E°cell An Example (cont.) Determining K Concentration and Ecell Consider the following redox reaction: Concentration and Ecell (cont.) Recall, in general: Concentration and Ecell (cont.) With the Nernst Eq., we can determine the effect of concentration on cell potentials. Concentration and Ecell (cont.) Concentration and Ecell (cont.) Concentration and Ecell (cont.) Concentration and Ecell (cont.) Concentration Cells Consider the cell presented on the left. The 1/2 cell reactions are the same, it is just the concentrations that differ. Will there be electron flow? Concentration Cells (cont.) Concentration Cells (cont.) Concentration Cells (cont.) Concentration Cells (cont.) Measurement of pH pH meters use electrochemical reactions. Measurement of pH (cont.) Measurement of pH (cont.) * ? The above relationship states that by measuring E°cell, we can determine K. E°cell = (0.0257 V) ln(K) = (0.0591) log(K) n n E°cell = (0.0591 V) log(K) n DG° = -RTln(K) DG° = -nFE°cell S4O62- (aq) + Cr2+(aq) Cr3+(aq) + S2O32-(aq) S4O62- S2O32- Cr2+ Cr3+ + e- 2 2e- + x 2 S4O62- + 2Cr2+ 2Cr3+ + 2S2O32- S4O62- S2O32- 2Cr2+ 2Cr3+ + 2e- 2 2e- + S4O62- + 2Cr2+ 2Cr3+ + 2S2O32- E°1/2 = 0.17 V E°1/2 = 0.50 V E°cell = 0.67 V S4O62- + 2Cr2+ 2Cr3+ + 2S2O32- E°cell = 0.67 V E°cell = (0.0257 V) ln(K) n = (0.059 V) log K n n(E°cell) (0.059 V) 2 (0.67 V) (0.059 V) = = 22.7 = log K K = 1022.7 = 5 x 1022 Zn(s) + 2H+ (aq) Zn2+(aq) + H2(g) E°cell = 0.76 V DG°= -nFE°cell 0 (spontaneous) What if [H+] = 2 M? Expect shift of equilibrium to products. Therefore DG decreases, and Ecell increases How does Ecell dependend on concentration? DG = DG° + RTln(Q) However: DG = -nFEcell -nFEcell = -nFE°cell + RTln(