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VII Electrochemistry PDF
VII Electrochemistry PDF
Basic Concepts:
The quantity of charge per second is called the current I (in ampere A = Cs-1)
The difference in electric potential E between two points is the work needed
(or that can be done) to move an electric charge from one point to the other,
per unit charge. It is measured in Volts (V).
Work = E q (in Joule, J)
The maximal possible electrical work that can be done by a chemical reaction
on its surroundings (at ct. T and p) is the free-energy change (G):
-G = work done on surroundings
G = - E q = - nFE
Relates the free-energy change of a reaction to
the voltage that can be generated by that reaction
Standard reduction potentials (E) for half cells are determined experimentally.
(Standard means at 25 C and all activities 1)
Idealized exp. to determine E for: Ag+ + e- Ag:
LHS cell: Standard Hydrogen Electrode
(S.H.E.): Pt surface in contact with an
acidic solution (A(H+) = 1) through which
H2 gas is bubbled (A(H2) = 1)
H+ + e- H2 (g)
By convention: E (S.H.E.) = 0 V
RHS cell: Ag+ + e- Ag
Here, Ecell = EAg+ = +0.799 V, which means that e- flow into the neg.
terminal; the LH cell is the anode; the RH cell is the cathode.
With the cell: S.H.E. Cd2+ Cd(s) we find Ecell = ECd2+ = -0.402 V and e-
flow in the other direction the LH half cell is now the cathode; the RH cell is
the anode.
ABb
Reaction quotient Q = ; when all activities are unity, E = E
AAa
(Note: pure solids, pure liquids, and solvents have activity = 1)
At 25 C, we can simplify this equation to:
0.05916 PPH3
E = -0.046 - log
3 [H+]3
Note that if we multiply the half-reaction by any factor, this does not
change E
P(s) + 12 H+ + 12 e- 4 PH3(g)
0.05916 P4PH3
E = -0.046 - log
12 [H+]12
4
0.05916 PPH3
= -0.046 - log
12 [H+]3
0.05916 PPH3
= -0.046 - 4 log
12 3 [H+]3
7
A galvanic cell produces electricity because The potentiometer that measures the
the cell reaction is not at equilibrium. voltage of the cell has a very high
resistance (1013 ), and thus allows
Replacing the potentiometer with a wire,
only a very small current (e.g. if Ecell =
there would be an appreciable current flowing 1 V, then I = 10-13 A). This does not
through it, and the concentrations of the noticeably change the concentrations
reactants would change until equilibrium is of the reactants in the cell.
reached (Ecell = 0)
10
aA + ne- cC E+
dD + ne- bB E-
11
Note: the procedure can also be used to find K for reactions that are not redox
reactions! (e.g. FeCO3(s) Fe2+ + CO32- K = Ksp).
It is just a matter of finding half-reactions with known E values that, when
combined, add up to that particular reaction. A redox potential is simply another
way of expressing the free-energy change of a reaction. See Box 13-3 on
Latimer diagrams in Harris 8th Ed.
12
0.05916 [B]b[H+]m
E = E - log Conversion from [A] to FA : see
n [A]a fractional composition equations.
IV. Acid/Base Chemistry, slides
35-39
13
Reference Electrodes:
Consider a galvanic cell with Fe2+/Fe3+ and a Pt wire as one half-cell, and a
constant potential half-cell:
RH cell: Fe3+ + e- Fe2+ E+ = 0.771 V
LH cell: AgCl(s) + e- Ag(s) + Cl- E- = 0.222 V
[Fe2+]
E = 0.771 0.05916 log - 0.222 - 0.05916 log[Cl-]
[Fe3+]
Cell voltage only depends
on [Fe2+] / [Fe3+] ! = ct 14
Reference electrode
connected to reference
terminal (-) of potentiomenter
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16
17
18
Since K+ and Cl- have similar mobilities, KCl is often used in salt bridges
because this minimizes the junction potential. Where Cl- cannot be used (e.g.
with half-cells containing Ag+), NO3- is a good substitute.
19
0.05916 [H2C2O4]
E = E - log
2 (pCO2)2 [H+]2
The rate at which CO2 reacts to produce oxalic acid is extremely
slow. Changes in partial pressure of CO2 therefore have little effect
on E; the Nernst equation does not apply.
Indicator Electrodes:
Metal electrodes: electric potential develops in response to a redox reaction at
the metal surface
Ion-selective electrodes: selective binding of analyte generates electric potential
no oxidation-reduction takes place!
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Metal electrodes can be made from the same metal as the cation to be
analyzed (Ag/Ag+, Cu/Cu2+,) or from an inert metal (Pt, Au), or from C.
1
E = 0.799 0.05916 log - 0.241 V = (0.558 + 0.05916 log [Ag+]) V
[Ag+]
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22
The two reference electrodes measure the electric potential difference across
the glass membrane. Except for Eb, which depends on [H+] on either side of
the membrane, all other potentials are constant. Since [H+]intside is fixed, Eb in
fact only depends on [H+]outside (i.e. pH of analyte solution).
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24
Or: E = k - 0.05916 pH
In practice: E = k - (0.05916) pH
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28
Before EP:
With the addition of each aliquot of Ce4+, Fe2+ is consumed and converted
into Fe3+. We can easily calculate [Fe2+], [Fe3+] and [Ce3+]; [Ce4+] is more
difficult to calculate. Therefore, we use:
29
[Fe2+]
E = E+ - E- = 0.767 0.05916 log - 0.241
[Fe3+] ES.C.E.
[Fe2+]
E = 0.526 0.05916 log
[Fe3+]
Note: 1. When V = VEP, E+ = E+ for the Fe3+/Fe2+ couple
2. The voltage at V = 0 cannot be calculated (E = -?)
At EP:
All Fe2+ and Ce4+ are converted to Fe3+ and Ce3+; which exist in equilibrium
with Fe2+ and Ce4+ as:
Fe3+ + Ce3+ Ce4+ + Fe2+ Since [Fe3+] = [Ce3+], [Fe2+] = [Ce4+]
[Fe2+] [Ce3+]
E+ = 0.767 0.05916 log E+ = 1.70 0.05916 log
[Fe3+] [Ce4+]
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[Fe2+] [Ce3+]
2 E+ = 0.767 0.05916 log + 1.70 0.05916 log
[Fe3+] [Ce4+]
[Fe2+] [Ce3+]
2 E+= 2.467 log
[Fe3+] [Ce4+]
[Fe3+] = [Ce3+] and [Fe2+] = [Ce4+] at EP
2 E+ = 2.467 V E+ = 1.23 V
Independent of
The cell voltage E = E+ - Ecalomel = 1.23 0.241 = 0.99 V conc., for this
particular titration
After EP:
The # moles of Ce3+ = the # moles of Fe3+, and there is a known excess of
(unreacted) Ce4+. We now use:
[Ce3+]
E = E+ - Ecalomel = 1.70 0.05916 log - 0.241
[Ce4+]
The titration curve is symmetrical around the EP only because the reaction
stoichiometry is 1:1. For a 2:1 ratio, the curve is not symmetrical. However,
with a steep rise in E near the EP, the error in VEP is minimal.
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EXAMPLE: potentiometric titration of Fe2+ (400.0 mL; 3.75 mM) with MnO4-
(20.0 mM); calomel electrode as reference (Ecalomel = 0.241 V) in 1.00 M H2SO4
Fe3+ + e- Fe2+ E = 0. 68 V (in 1 M H2SO4)
MnO4 + 8H + 5e-
- + Mn2+ + 4H2O E = 1.507 V
MnO4 + - 8H+ + 5Fe2+ Mn2+ + + 5Fe3+ + 4H2O
1 mol MnO4-
VEP? # moles MnO4- = # moles Fe2+
5 mol Fe2+
VEP x 20 mM = 1/5 x 400 mL x 3.75 mM VEP = 15.0 mL
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1 400
6 E+ = 8.215 0.05916 log With [H+] = 1.00 M = 0.964 M
[H+]8 415
After EP: e.g. 17.0 mL MnO4- added: excess of 17.0 15.0 = 2.0 mL MnO4-
We now use the other half-reaction:
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[Mn2+]? All the Mn2+comes from oxidation of Fe2+ by MnO4-, and only as much
Mn2+ can be formed as the amount of MnO4- added at VEP:
[Mn2+] = 15.0 mL x 20.0 mM = 0.719 mM
(400.0 mL + 17.0 mL) Or using [Fe2+]:
400.0 mL x 3.75 mM x 1/5
[Mn2+] =
[MnO4-]? All MnO4- that is added after the 400.0 mL + 17.0 mL
EP is in excess: = 0.719 mM
[H+]? The original [H+] is simply diluted by the addition of the titrant:
400.0 mL The small amount of H+
[H+] = 1.00 M = 0.959 M consumed during the
400.0 mL + 17.0 mL reaction can be ignored.
0.05916 [Mn2+]
E+ = 1.507 log
5 [MnO4-] [H+]8
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37
0.05916
The color change thus occurs over the range: E = E V
n
Ferroin (E = 1.147 V) will change color in the range of 1.088 1.206 V with
respect to the S.H.E.; this is the range of 0.847 0.965 V vs. S.C.E. This
would be a good indicator for the titration on slide 29.
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Preoxidation:
Peroxydisulfate (or persulfate): S2O82- (requires Ag+ as a catalyst)
S2O82- + Ag+ SO42- + SO4- + Ag2+
2 powerful oxidants (E(Ag2+) 2.0 V)
Prereduction:
Stannous chloride (SnCl2): reduces Fe3+ to Fe2+ in hot HCl
Excess SnCl2 is destroyed by adding HgCl2:
SnCl2 + 2 HgCl2 Sn4+ + Hg2Cl2 + 4 Cl-
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Zn(Hg)(s)
Non-selective (E0 = -0.80 V); reduces many ions e.g. Fe3+, Cr3+, UO22+
Most reduced analytes are oxidized again by air, so the eluent has to be
titrated immediately.
The eluent can also be collected in an acidic Fe3+ solution (except when Fe
is analyzed), which is reduced by the analyte(s) to Fe2+ (stable) and can then
be titrated with an oxidant such as MnO4- (indirect determination)
42
This reaction is slow at room temperature; when most of the titrant (90-95%)
is added, the reaction mixture is heated up to ~60 C to drive off CO2 and
shift the equilibrium to the right. A blank is performed to account for the
amount of titrant necessary to impart a pink color to the solution.
A pure iron wire can be dissolved in warm 1.5 M H2SO4 (under N2); the cooled
solution can be titrated directly 5 mL of H3PO4 / 100 mL solution can be
added to mask the yellow color of Fe3+ to make the endpoint more distinct.
If great accuracy is not needed, Fe(NH4)2(SO4)2.6H2O can also be used
(sufficiently pure for most purposes).
An indirect application of KMnO4 as a titrant is in the analysis of non-oxidizable
or difficult to oxidize cations such as Ca2+, Mg2+, Ce3+, Cu2+. They can be
precipitated with Na2C2O4, filtered, redissolved in acid and the H2C2O4 can then
be titrated as above.
43
Primary standard, cheap, its solutions (orange) are stable. Cr3+ complexes
can be green to violet, so indicator necessary (or potentiometric).
Not as strong an oxidant as MnO4- and Ce4+; mainly used for determination
of Fe2+ and for indirect determination of species that can oxidize Fe2+ to
Fe3+ (e.g. NO3-, MnO4-): a measured excess of Fe2+ is added to the
unknown, and excess Fe2+ is titrated with K2Cr2O7.
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Prepared solutions are stable at neutral pH (in the absence of heat, light),
but not at acidic (6 I- + O2 + 4 H+ 2 I3- + 2 H2O - slow) and basic pH
(disproportionation of I3- to HOI, IO3-, I-).
Alternatively, KIO3 can be added to a small excess of KI, then strong acid is
added to bring the solution to pH 1, and I3- is produced by quantitative
reverse disproportionation:
IO3- + 8 I- + 6 H+ 3 I3- + 3 H2O
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Electrogravimetric Analysis:
Analyte is quantitatively deposited on an electrode
(cathode) by electrolysis. The electrode is weighed
before and after deposition.
e.g.: Cu2+ + 2e- Cu(s)
Check for completion of the reaction by
disappearance of color, or by exposing fresh
surface of the cathode to the solution and
checking if deposit forms with continuing
electrolysis.
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Amperometry:
Electric current I between pair of electrodes that drive an electrolysis reaction
is measured analyte is one of the reactants and I ~ [analyte].
There are numerous variations on this technique.
Example: blood glucose monitor:
Voltammetry:
Number of techniques where the relationship between current and voltage is
observed during electrochemical processes. These techniques include:
52
Polarography
Uses a dropping-Hg electrode
(fresh Hg surface = reproducible I V behaviour)
Qualitative (identify analyte by half-wave potential) and quantitative
(diffusion current ~ [analyte])
Stripping Analysis
Analytes are first reduced from a solution onto an electrode (Hg)
Analytes are then oxidized by applying a positive potential I ~ [analyte]
Most sensitive voltammetric technique.
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