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Introduction to

Analytical Chemistry
Redox Titrimetry and Potentiometry
Electrochemistry
Oxidation/Reduction Reactions
Redox reactions involve electron transfer
from one species to another
Ox1 + Red2 Red1 + Ox2
Ox1 + ne- Red1 (Reduction
reaction)
Red2 Ox2 + ne- (Oxidation
reaction)
Reducing agent donates electrons (is
oxidized)
Oxidizing agent accepts electrons (is
reduced)
Electrochemistry
Oxidation/Reduction Reactions
Typical oxidizing agents: Standard
Potentials,V
O2 + 4H+ + 4e- 2H2O
+1.229
Ce4+ + e- Ce3+ +1.6
(acid)
MnO4- + 8H+ + 5e- Mn2+ + 4H2O +1.51
Typical reducing agents:
Zn2+ + 2e- Zno -0.763
Cr3+ + e- Cr2+
-0.408
Na+ + e- Nao -2.714
The salt bridge allows charge transfer through the solution and prevents mixing.
The spontaneous cell reaction (Fe2+ + Ce4+ = Fe3+ + Ce3+) generates the cell potential.
The cell potential depends on the half-reaction potentials at each electrode.
The Nernst equation describes the concentration dependence.
A battery is a voltaic cell. It goes dead when the reaction is complete (Ecell = 0).

Fig. Voltaic cell.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Electrochemistry
Standard Reduction Potentials
Half-Reaction Potentials:
They are measured relative to each other
Reference reduction half-reaction:
standard hydrogen electrode (SHE)
normal hydrogen electrode (NHE)
2H+(a=1.0) + 2e- H2(g 1atm)
0.0000 volts
The more positive the Eo, the better oxidizing agent is the oxidized form (e.g., MnO4-).
The more negative the Eo, the better reducing agent is the reduced form (e.g., Zn).

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


Electrochemistry
Reduction Potentials
General Conclusions:
1. The more positive the electrode
potential, the stronger an oxidizing agent
[the oxidized form] is and the weaker a
reducing agent [the reduced form] is
2. The more negative the reduction
potential, the weaker the oxidizing agent
is [the oxidized form]is and the stronger
the reducing agent [the reduced form] is.
Electrochemistry
Oxidation/Reduction Reactions
Typical oxidizing agents: Standard
Potentials,V
O2 + 4H+ + 4e- 2H2O
+1.229
Ce4+ + e- Ce3+ +1.6
(acid)
MnO4- + 8H+ + 5e- Mn2+ + 4H2O +1.51
Typical reducing agents:
Zn2+ + 2e- Zno -0.763
Cr3+ + e- Cr2+
-0.408
Na+ + e- Nao -2.714
Electrochemistry
Voltaic Cell
The spontaneous (Voltaic) cell reaction is the one
that gives a positive cell voltage when subtracting one
half-reaction from the other.
Eocell = Eoright Eoleft = Eocathode Eoanode
=Eo+ - Eo-
Which is the Anode? The Cathode?
Convention:
The anode is the electrode where oxidation occurs
the more negative half-reaction potential
The cathode is the electrode where reduction occurs
the more positive half-reaction potential
anode solution cathode
Electrochemistry
Oxidation/Reduction Reactions
Net Redox Reactions: Standard Potentials,V
MnO4- + 8H+ + 5e- Mn2+ + 4H2O +1.51
Sn4+ + 2e- Sn2+
+0.154
Balanced Net Ionic Reaction:
2MnO4- + 16H+ + 5Sn2+ 2Mn2+ + 5Sn4+ +
8H2O
Eocell = Eocat Eoan = (+1.51 (+0.154)) = +1.36 V
Electrochemistry
Nernst Equation
Effects of Concentrations on Potentials:
aOx + ne- bRed
E = Eo (2.3026RT/nF) log([Red]b/[Ox]a
Where E is the reduction at specific conc.,
Eo is standard reduction potential, n is number of
electrons involved in the half reaction,
R is the gas constant (8.3143 V coul deg-1mol-1),
T is absolute temperature,
and F is the Faraday constant (96487 coul eq-1).
At 25oC(298.16K) the value of 2.3026RT/F is
0.05916
Note: Concentrations should be activities
Electrochemistry
Calculations:
MnO4- + 8H+ + 5e- Mn2+ + 4H2O Eo
= +1.51 V
For [H+] = 1.0M, [MnO4-] = 0.10M, [Mn2+]
= 0.010M
E = Eo 0.05916/5 (log ([Mn2+]/[MnO4-
][H+]8)
E = +1.51 0.1183(-1) = +1.63 V vs NHE
Note: This is more positive than Eo
Greater tendency to be reduced compared
to standard conditions.
Electrochemistry
Calculations:
Silver electrode/silver chloride deposit/0.010M NaCl
AgCl + 1e- Ago + Cl- E=?
Ag+ + 1e- Ago Eo = +0.799 V
AgCl Ag+ + Cl- Ksp= 1.8 x
10-10
AgCl + e- Ago + Cl-
E = Eo - (0.05916/1) Log (1/[Ag+])
[Ag+] = Ksp/[Cl-] = 1.8 x 10-10/(0.010) = 1.8 x 10-8
E = +0.799 (0.05916)(7.74) = +0.341 V
Potentiometric Electrodes
Potentiometric electrodes measure:
Activity not concentration
Concepts to review:
Activity and affect factors
Potentiometric Electrodes
Electrode of the First Kind:
Metal in contact with Cation: M/Mn+
Example: Ag/Ag+
Ag+ + 1 e- Ag(s)
Nernst Equation:
E = EoAg+/Ag 2.303RT/nF(log1/aAg+)
Where aAg+ = activity of silver ion
Emeasured = Ecell = Eind vs NHE = Eind
ENHE
Eref solution Eind
Potentiometric Electrodes
Electrode of the Second Kind:
General Form: MMXXn-
Example: AgAgCl(S)Cl-
AgCl + 1 e- Ag(s) + Cl-
Nernst Equation:
E = EoAgCl/Ag 2.303RT/nF(log aCl-)
Potentiometric Electrodes
Electrode of the Second Kind:
General Form: MMXXn-
Example: Calomel Electrode
Hg , Hg2Cl2(S)Cl-
Hg22+ + 2 e- Hg(s)
E = EoHg22+/Hg 2.303RT/nF(log
1/aHg22+
Hg2Cl2(s) + 2e- 2 Hg + 2 Cl-
E = EoHg2Cl2/Hg 2.303RT/nF(log aCl-)2
Kosp = aHg (aCl-)2
Potentiometric Electrodes
REDOX ELECTRODES:
Inert Metal Electrode: Platinum, Pt
Ma+ + n e- M(a-n)+
E = EoMa+/M(a-n)+ - 2.303RT/nF (log aM(a-
n)+/ aMa+
Example:
MnO-4 + 8 H+ + 5e- Mn2+ + 4 H2O
Can you write the potential for this half cell?
Potentiometric Electrodes
Normal Hydrogen Electrode:
H+ + e- H2(g)
Can you write the Nernst Equation for
this half cell?
H+ + e- = H2
E = Eo 2.303RT/F log (PH2)1/2/aH+
Eo = 0.000 V. If PH2 = 1 atm., E = -2.303RT/F pH

Gary Christian,

Fig. Hydrogen electrode. Analytical Chemistry,


6th Ed. (Wiley)
Potentiometric Electrodes
Cells Without Liquid Junction:
Two Half Cells Required
Indicator Electrode
Reference Electrode
Example: PtH2(g), HCl
(solution)AgCl(s)Ag
Can you write the cell potential Ecell for
this electrode system?
Potentiometric Electrodes
Cells With Liquid Junction:
Two Half Cells Required
Indicator Electrode
Reference Electrode
Example:
HgHg2Cl2(s)KCl(saturated)HCl(soluti
on), H2(g)Pt
Can you write the cell potential Ecell for this
electrode system?
Ecell = (Eright Eleft) + Ej
Ej is due to unequal migration of cations and anions at the boundary of a liquid
junction, e.g., at a salt bridge interface.
This charge separation results in a potential at steady state.
Ej is minimized by a high concentration of a salt with nearly equal mobilities of
cation and anion in the salt bridge, e.g., saturated KCl.
The flux of the migration of this electrolyte is much greater than more dilute ones,
and largely determines Ej.

Fig. Representation of liquid-junction potential.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
H+ and OH- have high mobilities and so pH markedly affects Ej.
Therefore, pH electrode calibration should be done near the sample pH.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


The S.C.E. is a common reference electrode.
The cell half-reaction is: Hg2Cl2 + e- = Hg + Cl-.
E = Eo 0.0592 log 1/aCl- = 0.242 V for saturated KCl.

Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Fig. Commercial saturated calomel electrode.


Reference electrode potentials are all relative.
The measured cell potential depends on the one used.

Fig. Schematic representation of electrode potential


relative to different reference electrodes.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


A complete cell consists of an indicating electrode that responds to the analyte
and a reference electrode of fixed potential.
The potential difference between the two is measured.

Fig. Cell for potentiometric measurements.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Eglass = constant 2.303RT/F log (aH+ int/ aH+ ext)
The hydrated glass responds to aH+.
The asymmetry potential of the glass membrane is unknown,
so the electrode must be calibrated with a standard buffer.

Makes electrical
contact with glass,
and sets potential of
ref. electrode.

Fig. Glass pH electrode.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
This is two electrodes in one.
The porous plug salt bridge must be immersed in the solution.

Fig. Combination pH-reference electrode.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
When aH+ is very small, the glass electrode senses other cations.
The solution appears more acidic than it really is.

Fig. Error of Corning 015 glass electrode in


Gary Christian,
strongly alkaline solutions containing various cations. Analytical Chemistry,
6th Ed. (Wiley)
In very acid solutions, the activity of water is less than unity (it solvates the proton).
The aH+ is decreased, and the pH reading is increased.
High concentrations of dissolved salts or adding a nonaqueous solvent does the same.

Fig. Error of glass electrode in hydrochloric acid solutions.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
These are really accurate to 0.01 pH, due to Debye-Huckel limitations in calculating activity of the
chloride ion in the Ag/AgCl reference electrode used in measurements.
But they are reproducible to 0.001 pH unit.
Only the phosphate mixtures are really buffers.
Ka values change with temperature, and so the pH changes.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


The potential scale is calibrated in pH units (59.16 mV/pH at 25o C).
A temperature adjustment feature changes the slope by 2.303RT/F.

Fig. Typical pH meter.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The isopotential point (usually at pH 7) of a glass electrode is temperature insensitive.
The potential is set at zero here (if different than zero, this is the offset).

Fig. Isopotential point.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The most common ion-selective electrode of this type is the fluoride electrode:
LaF3 crystal doped with Eu(II) to increase conductivity.
Plastic membrane-ionophore electrodes have a similar design, with a soft plastic PVC
membrane containing a neutral lipophilic ionophore that selectively complexes with the
test ion.

Fig. Crystal membrane electrode.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
The potential determining membrane is a layer of water-immiscible
liquid ion exchanger at the porous membrane face.

Fig. Liquid-membrane electrode.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
There are numerous plastic membrane-ionophore electrodes also,
e.g., for Na+, K+, Li+, and Ca2+.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


The crown ether cavity size is just right for complexing lithium ion.
It is placed in a PVC plastic membrane.

Fig. 14-Crown-4 ether that selectively binds lithium ion.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Amide-based ionophores in PVC membranes are good complexers of these ions.

Fig. Ionophores for H+, Na+, and Ca2+.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


The larger the potential difference, the more selective the electrode.

The separate solution method of determining


selectivity coefficient for ion A with respect to ion B.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)


The calibration curve for A is prepared in the presence of fixed activity of interfering ion.
zA and zB are the charges of the ions.
The intersection is where the electrode responds equally to both ions.

Fig. Fixed interference calibration curve.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
These are ion-selective field-effect transistor electrodes.
A semiconductor transistor serves as the base for electrical contact.
It is coated with insulating layers of SiO2 and Si3N4, and then an ion-sensitive membrane.
This one is a non-glass ISFET pH electrode.

Fig. Solid-state ISFET electrode.


Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Redox Titrations
Titrate 50.0mL of 0.050 M Fe2+ vs
0.100M Ce4+
How do we observe the end point?
Is the equilibrium constant large enough?
To Observe End Point:
Redox Titrations
Titrate 50.0 mL 0.050 M Fe2+ vs
0.100 M Ce4+
Use Pt Indicator Electrode:
Ept = EFe3+/Fe2+ = ECe4+/Ce3+ at
Equilibrium
a) Add 10.0 mL Ce4+:
Redox Titrations
Titrate 50.0 mL 0.050 M Fe2+ vs
0.100 M Ce4+
b) At 50% of Titration (12.50 mL Ce4+)
Redox Titrations
Titrate 50.0 mL 0.050 M Fe2+ vs
0.100 M Ce4+
c) Just Before Equivalence Point (24.90
mL Ce4+)
Redox Titrations
Titrate 50.0 mL 0.050 M Fe2+ vs
0.100 M Ce4+
d) Just Beyond Equivalence Point (25.10
mL Ce4+)
Redox Titrations
Titrate 50.0 mL 0.050 M Fe2+ vs
0.100 M Ce4+
e) Equivalence Point Potential (25.00 mL
Ce4+)
Redox Titrations
Titrate 50.0 mL 0.050 M Fe2+ vs
0.100 M Ce4+
e) Equivalence Point Potential (25.00 mL
Ce4+)
Redox Titrations
Titrate 50.0 mL 0.050 M Fe2+ vs
mL Titrant 0.100
E(V. vs NHE) M Ce4+
Redox Titration
0.00 ----
10.00 0.761 1.500
12.50 0.771 1.400
24.90 0.912 1.300
25.00 1.106 E, volts 1.200
25.10 1.300
1.100
50.00 1.440
1.000
0.900
0.800
0.700
0.00 20.00 40.00 60.00
mL Titrant