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Intro Electrochem 824 7 8 2015
Intro Electrochem 824 7 8 2015
Analysis
A.) Introduction:
electrons
Cl- K+
Zn2+ Cu2+
SO42- SO42-
At Cu electrode: Cu2+ + 2e- ↔ Cu(s) reduction – gain of e- net decrease in charge of species
At Zn electrode: Zn(s) ↔ Zn2+ + 2e- oxidation – loss of e- net increase in charge of species
3.) Net Reaction in Cell – sum of reactions occurring in the two ½ cells
Galvanic Cell
4.) Types of Cells:
Electrolytic Cells – reaction does not occur naturally, requires external
stimulus (energy) to occur
- negative potential (Ecell = -)
- endothermic requires energy
Electrolytic Cell
Liquid Junction
d.) Liquid junctions – interface between two solutions with different
components or concentrations
Phase boundary
Electrode/solution interface
Pt,H2(p atm)|H+(aH+ = x)
2H+ + 2e- ↔ H2(g)
stream of H2 keeps surface at electrode saturated w/H 2(g)
note: potential affected by pH, [H+], used as an early pH indicator, also dependent on P H2
By convention, ESHE = 0V at [H+] = 1M, PH2 = 1 atm and at all temperatures
By definition:
Ecell = Ecathode – 0
Ecell = Ecathode
Standard Electrode Potential (Eo) – measured Ecell when all species in solution or gas has
an activity of 1.00
ax = x[X]
where:
x is the activity coefficient of solute X
[X] is the molar concentration of solute X
is favored or spontaneous.
If Eo is “-”, it indicates that the reaction is not favored or spontaneous and requires energy
to proceed
For ½ reaction:
nF (aP)p(aQ)q …
reactants
where:
R = ideal gas law constant (8.316 J mol -1 K-1) y-intercept = E0
T = absolute temperature (K)
- TK= 273.15 + ToC
slope = -(RT/nF)
n = number of electrons in process
F = Faraday’s constant (96487 C mol -1)
a = activities of each species ([X])
- in solution at time of measurement
- not necessarily at equilibrium (aR)r (aP)p
At room Temperature:
RT 2.5693x10-2
nF = V
n
Once have Ecathode & -Eanode by above procedure, can also get Ecell:
**may need to also include junction potential, etc., but good first approximation
Activity Coefficients
- experimental determination of individual activity coefficients appears to be impossible
- can determine mean activity coefficient ():
Debye-Huckel Equation
0.509 Z A2 1
log A (cA Z A2 cB Z B2 cC Z C2 ...)
1 3.28 A 2
where:
ZA = charge on the species A
cA = concentration of species A
= ionic strength of solution
A = the effective diameter of the hydrated ion
½ cell reactions:
AgCl(s) + e- ↔ Ag(s) + Cl- Eo = 0.222 V (cathode)
H+ + e- ↔ ½ H2(g) Eo = 0.00 V (anode)
0.0592 (a )r(a )s …
Eelectrode = E0 - log R p S q
n (aP) (aQ) …
Actual Potentials:
Cathode
Ecathode = E0AgCl – (0.0592/1) log acl- since satd. solids, activity of
AgCl and Ag = 1.
Actual Potentials:
Anode
Eanode = E0H+/H – (0.0592/1) log (aH+)/(P1/2H )
2 2
Eanode = 0.149 V
Ecell = Ecathode – Eanode = 0.371 V – 0.149 V = 0.222 V
6.) Limitations in the Use of Standard Electrode Potentials (E o):
- example:
Fe3+ + e- ↔ Fe2+ E = +0.73 V in 1M HClO4
Fe3+ + e- ↔ Fe2+ E = +0.70 V in 1M HCl
Fe3+ + e- ↔ Fe2+ E = +0.60 V in 1M H3PO4
- reason: Fe2+ & Fe3+ form different complexes with Cl- & PO4- that affects
net activity of Fe2+ and Fe3+ in solution
7.) Formal Potential (Ef or Eo’):
- used to compensate for problems with E o in using activity and with side-
reactions
- based on conditions of 1M concentration with all species being specified
e.g. HCl vs. HClO4 as acid
- gives better agreement than Eo with experimental data and Nernst
Equation
‚conditions need to be similar to conditions where E o’ was
measured
a) Ohm’s Law
E = IR
where:
E = potential (V, voltage)
I = current (amps)
R = resistance (ohms)
E = IR
- need to subtract from Ecell calculation to get “true” potential of
the cell
Note: at high or low cell potential, get less “+” or “-” current than expected.
– due to polarization
‚ solution or reaction can not keep up with changes in
potential of system
‚ limits the rate of the overall reaction
Types of Polarization
1) Slow Mass Transfer = Concentration Polarization
‚ mass transfer due to:
diffusion concentration gradient
migration ions move in potential
convection mechanical stirring
2) Slow Intermediate Reactions = Reaction Polarization
3) Slow Transfer of Electron Between Electrode and Species = Charge-
Transfer Polarization
= E – Eeq
where
E < Eeq
Learning Objectives: