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Unit 3

Ch.12 Christian Text
• Two kinds of electrochemical cells: voltaic and electrolytic
• In voltaic cell – chemical reaction spontaneously occurs to produce electrical
energy ( i.e. battery)
• In electrolytic cell- electrical energy is used to force a nonspontaneous chemical
reaction to occur (i.e. elctrolysis of water)
• Anode- oxidation occurs (loss of e-)
• Cathode-reduction occurs (gain of e-)
• Salt Bridge-allows change transfer through the solution but prevents mixing of
the solutions
• Two inert platinum wires are placed in each solution which creates a voltaic cell,
current is flowing , platinum wires can be considered electrodes
• Each wire will adopt electric potential, that is determined by the tendency of the
ions to give off or take on electrons, that is called electrode potential

• Electron donor-a reducing agent
• Electron acceptor-an oxidizing agent
• If the potential of all half-reactions could be measured, then we could determine
which oxidizing and reducing agents will react. The difference between two
electrode potentials can be measured. The electrode potential of the half-reaction
2H+ +2 e-  H2 this has Arbitrary been assigned a value of 0.000V and is called
normal hydrogen electrode(NHE) OR standard hydrogen electrode (SHE)
• Arbitrary define the potential of this half-reaction as zero (as standard conditions)
all others are measured relative to this.
• Nernst Equation:

• aOx + ne-  bRed Where E is the reduction potential at the specific
concentrations , n is the number of electrons involved in the half-reaction , R is
the gas constant . Note that in the cell potential of a spontaneous reaction the log
term contains the product [] over the reactants [] , that is right side of the equation
over the left side.
• Formal Potential –since the complexes are of unknown composition we usually
define formal potential as E0’ = this is the standard potential of a redox couple
with the oxidized and reduced forms at 1 M [] and with the solution conditions
• Liquid junction potential- Ecell= (Eright-Eleft) + E j where Ej is the liquid
potential , it can be positive or negative, it results from the unequal diffusion of
the ions on each side of the boundary. A careful choice of the salt bridge ( or
refernce electrode ) can minimize the liquid-junction potential and make it
reasonably constant. Example : the simplest type of liq. Junction occurs between
two solutions containing the same sample at different concentrations such as
HCl (0.1M) II HCl (0.01M) where both hydrogen and chloride ions will migrate
to either side, but hydrogen ions will move faster thus creating an excessive
charge on the right side (smaller concentration) that is the separation of charge.
• How to minimize Liquid junction:
1. Similar liquid junction potential of the two ions (i.e. KCl)
2. It is apparent that the liquid junction can be minimized by keeping on one
side of the boundary a high concentration of a salt whose ions have nearly
the same mobility, such as KCl.
3. As the concentration of the electrolyte on the other side of the boundary
increases, or as the ions are made different, the liquid-junction potential
will get larger.
4. The liquid junction potential will vary with the pH of the solution

1. Indicator Electrode
1. Metal Electrodes for Measuring the Metal’s Cations (13.1): an electrode
of this type is a metal in contact with a solution containing its cation. An
example is a silver metal electrode inserted in a solution of silver nitrate.
The potential becomes increasingly positive with increasing Ag+. (the
case for any electrode measuring a cation). Emeas.= Ecell=Eind.
2. Metal-Metal Salt Electrodes for Measuring the Salts Anion: the general
form of this type of electrode is M/MX/Xn- where MX is slightly soluble
salt, example Ag/AgCl(g)/ Cl- . The electrode can be used to measure the
activity of chloride ion in solution. AS the activity of chloride increases
the potential decreases. This is true for any electrode measuring an anion-
the opposite for a cation electrode. Another widely used electrode of this
type is the calomel electrode (reference electrode).
3. Redox Electrodes- Inert Metals: an inert metal is in contact with a
solution containing the soluble oxidized and reduced forms of the redox
helf-reaction. The inert metal used is usually platinum. The potential of
such an inert electrode is determined by the ratio at the electrode surface
of the reduced and oxidized species in the half-reaction. Example : MnO 4-
+ 8H+ + 5 e-  Mn2+ + 4 H2O , the pH is usually held constant. A very
important example of this type of electrode is the hydrogen electrode
Pt/H2, H+.
1. Sources of Error in Potentiometry:
1. Ionic Strength – is a measure of total electrolyte concentration and is
defined by µ=1/2∑CiZi2 where µ is the ionic strength, if more than one
salt is present , then the ionic strength is calculated from the total
concentration and charges of all the different ions. Very weak acids can
usually be considered to be nonionized and do not contribute to the ionic
strength . Nernst Equation strictly uses activities. Solutions: calibration
and ion strength adjustment buffer (ISA).
2. Poising Capacity- accuracyh required can be determined from the percent
error caused by a 1-mV error in the reading at 25 degrees. +/- 1 mV error
results in error in the activity such as +/- 4%, the same error will result for
all the measurements of silver ion which then can lead to a higher error \
(as n is doubled the error is doubled). Poising capacity is analogous to the
buffering capacity in pH measurements. If the solution Is very dilute, the
solution is very poorly poised and the potential readings will be sluggish.
Solution has a low ion [] that it takes longer for the solution to around the
electrode to rearrange its ions and reach a steady state . |To help correct
this problem and to maintain a constant ionic strength, a relatively high []
of an inert salt (ionic strength buffer) can be added. Stirring helps as well.
3. Temperature-samples and standards should be at the same temperature,
adjust pontentiometer for actual temperature.
4. Voltage Reading-
• Ion Selective Electrode:
1. Glass Memebrane Electrodes: reference electrode(external)|| H+
(unknown) | glass membrane | H+ (internal) | reference electrode
(internal). This electrode has to be calibrtated from day-to-day (cant dry
out- changes asymmetric potential). The internal filling solution will
usually be the chloride salt of the cation to which the electrode is most
responsive . The response to ions other than the desired one is called
‘alkaline error’.
2. Solid –State Electrodes : -conductivity of the crystal, I don’t get this one
at all…..13.7 pH range is 4-9, a useful solution to minimize interference
with the fluoride electrode is to add 1:1 ratio of CDTA(chelating agent)
also available as TISAB total ionic strength adjustment buffer.
3. Liquid-Liquid Electrode: the filling for ISE usually contains a chloride
salt of the primary ion, for example CaCl2 for a Ca+ electrode or KCl for
K+ electrode. The chloride establishes the potential of the internal
Ag/AgCl electrode. Here the potential-determining membrane is a layer
of a water-immiscible liquid ion exchanger held in place by an inert,
porous membrane. Example calcium selective.

• Nikolsky Equation:

• it can be written for mixtures of two ions of different charges.