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Salt Bridge= any medium through w/c ions can slowly pass. (e.g.
a piece of a bent tubing w/c is U-shaped. This could be filled with
hot sat. salt/5% agar solution. The ions can still pass through the
gel).
Functions of a salt bridge:
Allows electrical contact between the two solutions
Prevents mixing of the electrode solutions
Maintains the electrical neutrality in each half-cell as ions flow into and out
of the salt bridge. From Petrucci_2010
1
The Zn-Cu Cell = Daniel Cell The Zinc-Copper Cell
Zn |Zn+2(1M) || Cu+2(1M) | Cu
Experimental Observation: e- are release in the anode and consumed on the cathode.
Therefore, the e- flow through the wire from Anode to Cathode, as
Initial voltage is 1.100 volts.
in all electrochemical cells.
Mass of the Zn electrode decreases. The concentration of
Zn+2 in solution increases as the cell operates.
The mass of the Cu electrode increases. The concentration
From Petrucci_2010
2
20-1 Electrode Potentials and
Their Measurement Anode
3
Activity Series of Elements
Galvanic (or voltaic) cells
Produce electricity as a result of spontaneous reactions. There is an activity series (see tables on Gen Chem Books)
(Li, K, Ca, Na) > Mg, Al, Mn, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, H,
Electrolytic cells Sb, Cu, Hg, Ag, Pt, Au.
Non-spontaneous chemical change driven by electricity.
Couple, M|Mn+ (metals above H would readily displace H+; H2 gas is then
A pair of species related by a change in number of e-. produced and the metal is oxidized.
Mg0 + 2H+ Mg 2+ + H2
However, Cu + 2H+ No spontaneous reaction
From Petrucci_2010
For this cell the components are:
The standard electrode potential of A Zn strip immersed in 1.0 M zinc (II) sulfate.
the other half cell can thus be SHE (Standard The other electrode is the Standard Hydrogen Electrode.
determined in reference to SHE. Hydrogen Electrode
A wire and a salt bridge to complete the circuit.
With E= 0.0000volts
The initial cell voltage is 0.763 volts.
4
Zinc-SHE Cell Copper-SHE Cell
E0
Anode reaction Zn 0 Zn 2 + + 2 e - 0.763 V
Cathode reaction 2 H + + 2 e - H 2 g 0.000 V
Cell reaction Zn 0 + 2H + Zn 2 + + H 2 g E 0cell 0.763 V
Oxidation
Positive E0 values denote that the reaction tends to occur Is favored
to the right.
The larger the positive value, the greater the tendency to
occur to the right. (as written, thus as a reduction
reaction).
5
Uses of Eo values
• Use standard electrode potentials to predict
whether an electrochemical reaction at standard
state conditions will occur spontaneously.
• Question: Will Ag+ ions oxidize metallic Zn to
Zn2+ ions, or will Zn2+ ions oxidize metallic Ag
to Ag+ ions?
You do it!
• Steps for obtaining the equation for the
From Petrucci_2010 spontaneous reaction.
6
Standard Electrode Potentials Standard Electrode Potentials
Calculation of E0Cell Calculation of E0Cell
Example: Will permanganate ions, MnO4-, oxidize Fe Example: Will nitric acid, HNO3, oxidize arsenous
(II) ions to Fe(III) ions, or will Fe(III) ions oxidize acid, H3AsO3, in acidic solution? The reduction product
Mn(II) ions to MnO4- in acidic solution? 0 of HNO3 is NO in this reaction.
E
E0
Reduction 1(MnO -4 8H + 5e - Mn 2 4H 2 O) + 1.51 V Reduction 2(NO-3 4H + 3e - NO 2H 2 O) + 0.96 V
Oxdation 5(Fe 2 Fe 3+ + e - ) - (0.771 V) Oxidation 3(H 3 AsO 3 H 2 O H 3 AsO 4 2H + 2e - ) - ( 0.58 V)
2 2
Cell reaction MnO 5Fe 8H Mn 4H 2 O + 5Fe
-
4
3+
E 0
cell = +0.74 V Cell reaction 2NO -3 3H 3AsO 3 8H 3H 2 O 2NO 4H 2 O + 3H 3 AsO 4 6H
2NO 3- 3H 3 AsO 3 2H 2NO H 2 O + 3H 3 AsO 4 6H E 0cell = +0.38 V
Thus MnO4-, permanganate ions will oxidize Fe(II) ions Eo HNO3/NO= +0.96 V; E0 H3AsO4/H3AsO3= +0.58V
to Fe(III) and are reduced to Mn(II) ions in acidic Eocell = Eocathode – Eoanode = [Eo HNO3/NO] − [Eo H3AsO4/H3AsO3] =
= 0.96− 0.58 = 0.38 V
solution.
7
The Nernst Equation: Non- The Nernst Equation: Non-
Standard Conditions Standard Conditions
Nernst Equation Nernst Equation
The value of the cell potentials change if conditions are
non-standard (for concentrations or partial pressures).
The Nernst equation describes the electrode potentials at Ecell = Eocell – {(2.303/zF)*RT log Q}
nonstandard conditions. (Ecell)
Ecell = Eocell – {(2.303/zF)*RT log Q}
Or
Where z= no. of mol e- involved in the overall balanced redox
reaction.
F = Faraday’s constant = 96485 J /Volt mol e-
Ecell = Eocell – {(RT ln Q)/zF)}
R = 8.314 J/mol K; T is temperature in K;
Q = reaction quotient
E = E0 -
0.0592 Cu + consisting of a Cd electrode immersed in a
solution that is 0.0150M in Cd+2?
log
1 Cu2 Cd2+ + 2e- Cd E0 Cd+2/Cd(0) = -0.403V
E= E0 – (0.0592/n) log 1/[Cd+2]
If [Cu2+] and [Cu+] are both 1.0 M, i.e. at E= -0.403 – {(0.0592/2) log (1/0.0150) = -0.457V
standard conditions, then E = E0 because the
concentration term equals zero. Negative sign indicates that when this half-cell is coupled with SHE,
the reverse reaction would occur.
Cd|Cd2+(0.0150M) || H+ (1M),H2 (1atm)|Pt Ecell=+0.457V
anode cathode
8
Nernst Equation is useful to calculate the potential for
Nernst Equation a cell that consists of two nonstandard electrodes
. 102 010.
2
What is the E for this non-standard conditions? 2 10
Practice Exercise
E cell = 0.62 V -
0.0592
log
0.10 1.0 2
2 2
1.0 10 2 0.10 How do we relate the constant
E cell 0.62 V -
0.0592
3.00 of equilibrium, K with the Eocell ?
2
E cell 0.62 0.09 V
E cell = 0.53 V
9
Relationship of E0cell to G0 and K Relationship of E0cell to G0 and K
ΔG0 = -z F E0cell
Where
F= 96485 J/V mol e- Lesson: We can solve for the equilibrium constant given the
z= no.of e- involved (in balanced rexn) standard cell potential and the number of e- involved in the redox.
10
1st Step: Calculate E0cell 2nd Step: Calculate Ecell
Calculate the Gibbs Free Energy change, G and the equilibrium constant
at 25C for the following reaction with the indicated concentration
Zn 2 Ag 0.30 M 2Ag Zn 2 0.50 M
Use the Nernst equation to calculate E cell for the given
Zn 2 Ag 0.30 M 2Ag Zn 2 0.50 M concentrations.
Ag 0 .30
0
E Q=
+ 2 2
2Ag e Ag
- 0
0.799 V
log 5.6 = 0.748
Zn 0
Zn 2e
2 -
- - 0.763 V
0 . 0592
E cell E 0cell log Q
2 Ag Zn0 2 Ag0 Zn2 E0cell 1.562 V 2
Ag 0.30
Q=
+ 2 2
ΔG = - n F Ecell
log 5.6 = 0.748 ΔG = - {(2 mol e-)(96485 J/V mol e-)(1.540V)
0.0592 ΔG = - 2.97x105 Joules
Ecell E0cell log Q
2 ΔG = -297 kJ (per mol rxn)
0.0592
Ecell 1.562V - log5.6V The negative ΔG tells us that the reaction
2
Ecell = 1.540V is spontaneous.
- nFE0cell = - RT ln K
ln K = (nFE0cell)/RT
ln K = (2mol e-)(96485 J/V-mol e)(1.562 V)
(8.314 J/mol K) (298.15K)
K = 6.44x105 = [Zn+2]/[Ag+]
11
Ecell as a Function of Concentration
Galvanic Cells RT
Ecell = Ecell° - ln Q
Concentration Cells zF
FIGURE 20-9
Batteries Convert to log10 and calculate constants.
Variation of Ecell with ion concentrations
Corrosion
0.0592 V
Ecell = E°cell - log Q The Nernst Equation
z
Concentration Cells
Two half cells with identical electrodes but different ion concentrations.
2 H+(1 M) → 2 H+(x M) 0.0592 V
Ecell = Ecell° - log Q
Pt|H2 (1 atm)|H+(x M)||H+(1.0 M)|H2(1 atm)|Pt(s) z
E°cell = E°H+/H2 - E°H+/H2 = 0
0.0592 V x2
Ecell = Ecell° - log
2 H+(1 M) + 2 e- → H2(g, 1 atm) z 12
but we can calculate 0.0592 V x2
H2(g, 1 atm) → 2 H+(x M) + 2 e- Ecell = 0 - log
using the Nernst Equation 2 1
Measurement of Ksp
Ag|Ag+(sat’d AgI)||Ag+(0.10 M)|Ag(s)
Ag+(0.100 M) + e- → Ag(s)
Ag(s) → Ag+(sat’d) + e-
12
The Glass Electrode and the Electrochemical Measurement of
pH
20-5 Batteries: Producing Electricity
Ag|AgCl(s)|Cl-(1.0M),H+(1.0M)|glass membrane|H+(unknown)|| Cl-(1.0 M)|AgCl(s)|Ag(s)
Through Chemical Reactions
Ag(s) + Cl- AgCl(s) + e- Primary Cells (or batteries).
H+(1.0 M) H+(unknown) Cell reaction is not reversible.
AgCl(s) + e- Ag(s) + Cl-(aq) Secondary Cells (e.g. Rechargeable batteries)
ΔG = G(unknown) – G(1.0M) Cell reaction can be reversed by passing electricity
= G° + RTln[unknown] – G° - RTln(1.0) through the cell (charging).
=RTln[unknown] Flow Batteries and Fuel Cells.
E°cell = -RTln[unknown]/zF Materials pass through the battery which converts
chemical energy to electric energy.
pH = -log[unknown]=zFE°cell/RT
The Leclanché
The alkaline cell
Dry Cell
Reduction: 2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH-
Oxidation: Zn(s) → Zn2+(aq) + 2 e-
Oxidation reaction can be thought of in two steps:
Reduction: 2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH-
Zn(s) → Zn2+(aq) + 2 e-
Acid-base reaction: NH4+ + OH- → NH3(g) + H2O(l)
Zn2+(aq) + 2 OH- → Zn (OH)2(s)
Precipitation reaction: NH3 + Zn2+(aq) + Cl- → [Zn(NH3)2]Cl2(s)
Zn (s) + 2 OH- → Zn (OH)2(s) + 2 e-
Oxidation:
Pb (s) + HSO4-(aq) → PbSO4(s) + H+(aq) + 2 e-
FIGURE 20
The lead-acid (storage) cell
Slide 77 of 53
13
The Silver-Zinc Cell: A Button The Nickel-Cadmium Cell: A
Battery Rechargeable Battery
Zn(s) + Ag2O(s) → ZnO(s) + 2 Ag(s) Ecell = 1.8 V Cd(s) + 2 NiO(OH)(s) + 2 H2O(L) → 2 Ni(OH)2(s) + Cd(OH)2(s)
Air Batteries
4 Al(s) + 3 O2(g) + 6 H2O(l) + 4 OH- → 4 [Al(OH)4](aq)
Special Topic: Corrosion
How to prevent corrosion: the
unwanted oxidation oxidation of metals?
14
Petrucci FIGURE 20-20
20-6 Corrosion: Unwanted
In neutral solution:
Voltaic Cells Anode Basic Media
Zn is preferentially
oxidized before Fe
Defects allow
penetration of
oxygen and water
15