Single electrode potentials. Standard reduction potentials (E 0 )
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1 25 Single electrode potentils Stndrd reduction potentils ( )
2 26 Single electrode potentils Which is the strongest reducing gent mong the following metls: Cu, N, Au, Zn? Stndrd reduction potentils ( )
3 27 Stndrd reduction potentils ( ) Stndrd reduction potentils ( ) Cu ++ (q) + 2e - Cu.342 Zn ++ (q) + 2e - Zn -.762
4 28 Stndrd reduction potentils ( ) 1.13 V e - Stndrd reduction potentils ( ) Cu ++ (q) + 2e - Cu.342 Zn ++ (q) + 2e - Zn Cu ++ (q) + 2e - Cu Zn Zn ++ (q) + 2e V.762 V Cu ++ (q) +Zn Zn ++ (q) +Cu 1.13V =.341V - (-.762V) = 1.13 V Zn Zn ++ (q) + 2e - 1M Cu ++ (q) + 2e - Cu 1M
5 29 Stndrd reduction potentils ( ) Stndrd reduction potentils ( ) Cu ++ (q) + 2e - Cu.342 Zn ++ (q) + 2e - Zn Cu ++ (q) + 2e - Cu.342 V Zn Zn ++ (q) + 2e V Cu ++ (q) +Zn Zn ++ (q) +Cu 1.13V red of the cthode + ox of the node =.341V - (-.762V) = 1.13 V red of the cthode - red of the node
6 3 Stndrd reduction potentils ( ) CH 3 CH 2 OH (q) + ½ O 2 (g) CH 3 CHO (q) + H 2 O tnol cetldehyde Clculte for this rection t 25 C (V) (V)
7 31 Stndrd reduction potentils ( ) CH 3 CH 2 OH (q) + ½ O 2 (g) CH 3 CHO (q) + H 2 O tnol cetldehyde Clculte for this rection t 25 C (V) (V) Note tht this is the stndrd electrode potentil, i.e. the potentil of the electrochemicl cell when ll ctivities re 1 nd ll pressures 1br. As the rection progresses, the concentrtions will chnge nd the emf of the cell will chnge ccordingly
8 Thermodynmics of lectrochemicl cells r G = -.F. Chnge in Gibbs free energy (J mol -1 ) Number of electrons exchnged mf of the cell (volts) Frdy constnt (C mol -1 ) F ~ 965 C mol -1 Chrge of mole of electrons This is the most direct wy of mesuring r G (but it works only for electrochemicl rections). Since r G is relted to the equilibrium constnt, emf mesurements provide wy of mesuring equilibrium constnts of redox rections s well. Note tht > for spontneous rection ( r G < ) Cu ++ (q) + 2e - Cu.342 V Zn Zn ++ (q) + 2e V Cu ++ (q) +Zn Zn ++ (q) +Cu 1.13V r G = - 96,5 C mol V = kj mol -1 Spontneous in stndrd conditions
9 Thermodynmics of lectrochemicl cells r G = -.F. Chnge in Gibbs free energy (J mol -1 ) Number of electrons exchnged mf of the cell (volts) Frdy constnt (C mol -1 ) F ~ 965 C mol -1 Chrge of mole of electrons CH 3 CH 2 OH (q) + ½ O 2 (g) CH 3 CHO (q) + H 2 O tnol cetldehyde ) Clculte for this rection t 25 C b) Clculte r G
10 Thermodynmics of lectrochemicl cells r G = -.F. Chnge in Gibbs free energy (J mol -1 ) Number of electrons exchnged mf of the cell (volts) Frdy constnt (C mol -1 ) F ~ 965 C mol -1 Chrge of mole of electrons CH 3 CH 2 OH (q) + ½ O 2 (g) CH 3 CHO (q) + H 2 O tnol cetldehyde ) Clculte for this rection t 25 C b) Clculte r G c) Clculte the equilibrium constnt
11 Thermodynmics of lectrochemicl cells r G = -.F. Chnge in Gibbs free energy (J mol -1 ) Number of electrons exchnged mf of the cell (volts) Frdy constnt (C mol -1 ) F ~ 965 C mol -1 Chrge of mole of electrons 2 CH 3 CH 2 OH (q) +1 O 2 (g) 2 CH 3 CHO (q) +2 H 2 O tnol cetldehyde Does r G chnge? Does chnge?
12 Thermodynmics of lectrochemicl cells Use the dt in the tble below to clculte the stndrd reduction potentil for the hlf cell Fe e - Fe
13 Thermodynmics of lectrochemicl cells Use the dt in the tble below to clculte the stndrd reduction potentil for the hlf cell Fe e - Fe Most common mistke: Fe e - Fe.33 V
14 Thermodynmics of lectrochemicl cells Use the dt in the tble below to clculte the stndrd reduction potentil for the hlf cell Fe e - Fe r G = -.F. r G = -2 F (-.44) V r G = -1 F.77 V Fe e - Fe 1.21 r G = +.11 F = -3 F -.11/3 = -.4 V
15 The Nernst eqution So fr we hve been working with stndrd conditions (everything 1M or 1 br). Wht is the emf of cell under other conditions? Cu ++ (q) + 2e - Cu.342 2H + (q) + 2e - H 2 (g) Zn ++ (q) + 2e - Zn Cu ++ (q) + 2e - Cu.342 V Zn Zn ++ (q) + 2e V Cu ++ (q) +Zn Zn ++ (q) +Cu 1.13V [Zn +2 ] =.7 M [Cu +2 ] =.1 M This is wht we would mesure if [Zn +2 ] = [Cu +2 ] = 1 M
16 The Nernst eqution Q A + bb cc +dd r G r G RT ln c C A d D b B r G = -.F. Stndrd conditions F F RT F ln RT c C A d D b B ln c C A d D b B
17 b B A d D c C F RT ln R = J/K mol T = 298 K F = 96,5 C/mol RT/F =.257 V b B A d D c C ln.257 ln x =2.33 log x b B A d D c C b B A d D c C log.59 log The Nernst eqution
18 The Nernst eqution So fr we hve been working with stndrd conditions (everything 1M or 1 br). Wht is the emf of cell under other conditions? Cu ++ (q) +Zn Zn ++ (q) +Cu.257 ln Zn Cu 2 2 = 1.13V 2 = 1.78 V.7/.1= 7 [Zn +2 ] =.7 M [Cu +2 ] =.1 M The ctivities of the pure metls is 1
19 The Nernst eqution CH 3 CH 2 OH (q) + ½ O 2 (g) CH 3 CHO (q) + H 2 O tnol cetldehyde ) Clculte for this rection t 25 C b) Clculte r G c) Clculte the equilibrium constnt d) Clculte when (ethnol) =.1, P(O 2 ) = 4 tm, (cetldehyde) = 1 nd ( H 2 O) = 1.
20 The Nernst eqution: The Biochemicl (or biologicl) stndrd A + bb cc +dd RT F ln c C A d D b B Stndrd conditions: ctivity =1 for ll species If rection involves [H + ], this mens tht the ph is ~ The stndrd reduction potentil for biologicl hlf-rections is usully bsed on the hydrogen electrode t ph 7 ([H + ] = 1-7 M insted of [H + ] = 1 M s in the SH). The stndrd free Gibbs energy is lso bsed on ph = 7.
21 The Nernst eqution: The Biochemicl (or biologicl) stndrd RT F ln c C A d D b B 2H + (q) + 2e - H 2 (g) Stndrd Hydrogen electrode (SH). (H + ) = 1, p(h 2 ) = 1br. The potentil is rbitrrily set to zero t 298K
22 The Nernst eqution: The Biochemicl (or biologicl) stndrd RT F ln c C A d D b B ' When 1 1 2H + (q) + 2e - H 2 (g) RT F p H 2 ln [ ] H RT 1 ln [1 7 ] 2 F 2 ' = -.414V
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