DQ 4.

2
If we follow the potentiometric titration with a voltmeter, what is the source of the
emf?
Answer
As with all electrochemical cells, the emf represents the separation
between two half-cell potentials (see equation (3.3)). In accepting this statement,
we are implying that the cell has neither a junction potential nor any IR drop. The
latter assumption is valid since the solution in our example is acidified and hence
its ionic strength is high. Solution with high ionic strengths can be assumed to
have a a minimal solution resistance R.
The assumption that junction potential are absent is also valid. Since our
usual practice during a potentiometric titration is to stir the solution vigorously.
Such stirring causes rapid mixing, hus obviating any worriers about poor mass
transport. In addition, note that junction potentials are caused by differing rates of
ionic movement across a membrane. No such membrane is incorporated any
where in our cell here.
The cell emf comprises two half-cell potentials. One of these half cells will
be a standard reference, such as a saturated calomel elecyrode (SCE). While the
other will be an inert electrode such as platinum or gold.
There is no redox couple in solution at the start of the ferrous-ceric
titration because the solution contains only Fe2+. The oxidation of ferrous to ferric
occuts as soon as an aliquot of ceric ions enter the solution to effect the redox
reaction shown in equation (4.1). The bulk of the initially present ferrous ions
remain. With the ferric products of the redox reaction residing in the same
solution, i.e.a Fe3+, Fe2+ redox couple is formed. This couple has the electrode
potential E Fe3+-Fe2+.
Note that all of the ceric ions in the aliquot are converted (in this case,
reduced) to form cerous ions, i.e. there is only one redox form of the cerium in
solution.
Therefore , there is no Ce4+, Ce3+ couple present during the first part of the
titration. Accordingly, the emf can be represented by the following:
Emf= E Fe3+-Fe2+- Erefence electrode (4.2)
As the volume of ceric ion solution increases, so the ratio of ferrous ion o
ferric ion will decrease, and hence the electrode potential E Fe3+-Fe2+ changes during

the course of the titration. This is why a potentiometric titration can be followed
by using the emf as the reaction variable.
SAQ 4.2
The cell SCE An, Am+ Pt is constructed to use in a potentiometric titration. At the
equivalence point, the end emf is 0,308 V. Taking ESCE= 0,242 V, Calculate the
electrode potential E An, Am+.
DQ 4.3
So how is the end point determined?
Answer
As we have just seen, there are no redox couples either Ce 4+, Ce3+ or
Fe3+, Fe2+ - in solution before the itration is started. As soon as ceric ions are added
to the solution, the Fe3+, Fe2+ couple forms. At no point before the and point will
any ceric ions remain in solution, i.e. within a reasonable time scale because
they react- and so there is no Ce4+, Ce3+ couple in solution.
After the end point, all of the ferrous ions will have been consumed and
converted to ferric ions, i.e. There is no longer a Fe 3+, Fe2+ couple in solution.
However, after the end point, the ceric ions added to the solution will not react
because there is nothing left to oxidize, so Ce 4+ and Ce3+ reside together as a new,
different redox couple with its own electrode potential E Ce4+, Ce3+.
The end point of the titration it seen as the transition from one electrode
potential to the other, as shown below in figure 4.2.
An S- shaped curve is produced (this shapes arises from ogarithmic
dependence of emf on activity, as discussed below). The curve is symmetrical if
the reaction is 1:1, 2:2, etc., i.e. both redox couples involve the same number of
electron. The equivalence point is obtained as he point of inflection of such
symmetrical curves. If the reaction has a different stoichiometry, then the trace is
not symmetrical, and ascertaining the equivalence point can be considerably more
difficult. For the reason, it is advantageous to know the stoichiometry beforehand
and thus choose the couples o be employed accordingly.