Quintus Fernando calculation of Titration Error

and John Butcher

of Arizona
University in Precipitation Titrations
Tucson, 85721
A graphical method

O n e of the first instances in which a
student encounters simultaneous equilibria is either in
a discussion of fractional or selective precipitation or
in the familiar laboratory exercise for the determination
of chloride by the Mohr method. Frequently, however,
the student gains only a superficial knowledge of the
simple concepts involved and is thus unprepared to deal
with the more complicated situations which are pre-
sented later. We have found that it is well worth the
time to emphasize the early study of simultaneous
equilibria. A productive topic in this respect is the
calculation of theoretical titration errors in precipitation
titration errors, it is convenient to define the end point
as the point at which the solution becomes saturated
with AgzCrOh.
Consider the tit,ration of an anion, Z-, with silver
nitrate to form an insoluble salt, AgZ. Before and a t
the end point, the titration solution is described by two
equations: the solubility product:
and the electroneutrality equation:
[Ag+l + Cz- = [Z-] + Ck+ (2)

titrations. The Mohr titration is ideal for this purpose
and is preserved as a laboratory exercise in our under-
graduate chemistry curriculum since, if for no other
reason, it does offer a great deal of insight into calcula-
tions involving simultaneous equilibria.
The calculation of titration errors in precipitation
titrations has been described previou~ly.~-~ In this
article, a graphical method is introduced which greatly
clarifies the nature of the calculation and illustrates the
significance of the various equilibria.
The Mohr Titration
The Mohr method is a precipitation titration in
which silver ion is the titrant. The indicator is chro-
mate ion, and the end point is the point a t which the red
oranCre of Ag,Cr04 is observed. For the calculation of
' SMITH,T. B., "Analytical Processes,'' Edward Arnold, Lon-
don, 1940, p. 148.
COETZEE, J. F., in KOLTHOFF, I. M., AND ELVING,P. J.,
''Treat,ise on Andytical Chemistry," Part 1, Vol. I, Interscience
(division of John Wiley & Sons, Inc.), New York, 1959, p.,?92.
BUTLER, J. N., J. CHEM.EDUC. 40, 66 (1963); also Ionic
Equilibrium," Addison-Wesley Publishing Ca., Reading, Mass.,
1964, p. 187.
Here, C s and CA.+ are the formal concentrations of
Z- and Ag+, respectively, in the titration solution;
these quantities include the Ag+ and Z- present as the
solid AgZ.
The stoichiometric fraction of the anion titrated, X,
is given by:
and the fractional titration error is:
When defined in this manner, the titration error is
negative before the equivalence point is reached and
positive after the equivalence point.
Substitution of eqn. (2) into the numerator of eqn.
(4) gives:
where [Z-] is, of course, calculated from eqn. (1).
Note that neither the silver nor the anion concentration
at the equivalence pnint appears in either eqn. (5) or in its
derivation.

166 / Journal of Chemical Edvcotion

 Given, then, the chromate concentration a t the end end point pAg (and thus the titration error) is less sen-
point,, the silver ion concentration at that point and, sitive to the concentration of the indicator ion than it
hence, the t.itrat,ion error are readily calculated. The would be if that ion were univalent.
same derivation applies, and the same method of cal- Another conclusion which can be drawn from eqn.
culation is used, whether the end point occurs before, (5) arises from the following considerations: The
at, or after the equivalence point. pAg at the end point is determined solely by [CrOa=].
The variation of both terms in eqn. (5) as well as of Further, the largest possible error is obtained when the
[CrOs] are readily shown graphically as functions4 of
pAg when dilution by the titrant is negligible. For
example, consider Figure 1,which represents the solution
second term in the error equation is negligibly small
(i.e., K., is small). I n that case, and when [Ag+],.d
is the usual M, the titration error is:
.*
conditions during a titration of 0.050 F chloride with
silver, the indicat,or being 0.005 M c h r ~ m a t e . ~The
signs shown on the graph are those of the corresponding
terms in eqn. (5). Whether one plots -log [Ag+] and is independent of K.,. This is the maximum
and - log [Cl-1, as in the figure, or the negative possible overtitration when [CrOa=] = 5 X M.
logarithms of [Ag+]/Ccr and [Cl-]/Car is a matter of On the other hand, when K., is large, the first term is
personal preference. Both graphs are equally in- negligible and the error becomes large and negative:
formative, although, in the first case, it is necessary to - 10"' X K,,
E = X 100
remember to divide by Ccr to obtain the titration error. Cz -
The [Cl-] curve in Figure 1 is horizontal until the
K., of AgCl is satisfied (i.e., pC1 +
pAg = 10.00);
thereafter, the [Cl-] curve is a straight line plot of the
solubilit,yproduct equation:
-log [Cl-I = 10.00 - pAg
with a slope of -1. The [Cr04=]curve is likewise
horizontal nnt,il the K,, of silver chromate is reached;
t,hen, chromat,e obeys the solubility product equation:
-lag [CrO&-I = 11.70 - 2pAg
The end point occurs a t the break in this curve, i.e., at
the point a t which Ag,CrO, just begins to precipitate.
Thus for the example considered in the figure, pAg at
the end point is 4.70; pC1 is 5.30; and the titration
error is:

PA9
The graph ran also be used to illustrate several other Figure I. Grophicol calcvlafion of the titrotion error-the Mohr titrotion:
points regarding the RiIohr titration. For example, the Ccr = O.05OF; CE,O,- = O.OOSOF.
equivalence point obviously falls a t the intersection of
the silver arid chloride curves, i.e., at the point of zero
error. Changing [CrO&-] results in an upward or The Volhard Titrotion
downward shift of the horizontal segment of the The classical procedure of Volhard involves the
[CrOa=]rurve. Thus, to obtain E = 0, the break in addition of an excess of silver to a solution of halide,
t.he chromate curve must occur at pAg = 5 and [CrO4-1 followed by the back titration of the excess silver ion
must be 10-'.'A/T. At higher values of [Cr04=],the ti- with thiocyanate. The indicator is Fe3+ and the end
trat~ionerror is negative since point is taken a t the first permanent red coloration due
IC1-lend 0, > lAgt1en, nt to the formation of FeSCN++. I n order to describe the
I n Figure 1, changes in Cor likewise affect only the Volhard titration of, e.g., chloride, the following
horizontal portion of the [CI-] curve; an effect on the equilibria are considered:
titration error arises, however, from the Ccr term in the Few + SCN- e FeSCN++ 01= 1 0 P m
denominator of eqn. (5). AgCI<., = Ag+ + CI- K =D -
- 10-10.m
The -2 slope of the chromate curve reveals that the AgSCNcs, e Ag+ + SCN- K SP -
- 10-'P.W

At the low pH employed for this method and at the low

[SCN-] encountered during the course of the titration,
' firr.rsN, L. G., in KOLTHOFF,I. M., AND ELVING,P. J., the extent of formation of iron(II1) hydroxo complexes
"Treatise "on Analytical Chemistry," Part 1, Val. I, Interscience, and of Fe(SCN),+, etc., is negligibly small.
(division of John Wiley & Sons, Inc.), New Yark, 1959, p. 302. From the electroneutrality equation for the solution,
The scales on the axesin Figure 1are inverted so t h a t thefrac-
tion t,it,rated increases toward the right side and concentrations of +
[Ag+l + CCI- C m - + +
3[FeP+I 2[FeSCNt++I =
the various ions increase toward t,he top of the graph. Through-
out this discussion cert,ain liberties have been taken with the CA,+ + ICI-I + [SCN-I + BCFP (6)
values of the equilibrium const,ants in order to simplify the and from the material balance equation for iron:
mrmerical ealcr~lations.
' SWIFT,E. H., ef al., .4nal. Chem., 22, 306 (1950).

Volume 44, Number 3, March 1967 / 167

 the solubility product expressions for AgCl and AgSCN:

Thus
pCl = pSCN - 2.00

An equation for [FeSCN++]as a function of [SCN-I is

obtained from eqn. (7) and from the expression for 0, for
the monothiocyanatoiron(111) complex:

Thus, when [SCN-] << 10-2.20,the equation of thc

[FeSCN++]curve is:

Figure 2. Graphical colculotion of the titrotion ermr-the Volhord

titration: C d + = 0.010F. Dashed Curve; CFP = 0.20F and, when [SCN-I >> 10-2.2" the equation is:

it is readily shown that:
Alternatively, eqn. (8) can be derived from the material
balance equations for thiocyanate, chloride, silver, and
iron.
Although silver ion is the titrand and thiocyanate is
the titrant in the actual titration, i t is chloride that is
being determined so that it is appropriate to define the
fraction titrated by:
I n the region where [SCN-] is near 10-2.20,the plot
curves as shown in Figure 2.
Taking the end point at [FeSCN++] = 10-5.20,the
titration error is:
This represents an undertitration of chloride; is., a11
excess of thiocyanate has been added. If, as recom-
mended by S ~ i f tthe
, ~ iron concentration is raised to
0.20 F, the dashed curve in Figure 2 applies, and thc
titration error is:

ThusX = 1 when CncN-= CAp+- CC,-and X = 0 when

CBON-= CA.+. The titration error is given by:

This corresuonds to an error of -0.5%. - when Ccr =

0.010 F.
Substitution of eqn. (8) into the numerator of eqn. (10) When the solid AgCl is not allowed to equilibratc
gives : with SCN-, either by filtering the solution or by the use
of nitrobenzene, onlv the titration of the excess An+
with SCN- need bk considered. I n that case, the
-
titration error is given by:
Experiments have shown that the red color of Fe- IAg+] - [SCN-I - [FeSCNr']
E =
SCN++ is just perceptible when its concentration is Ccr
about 6 X Thus it can he assumed that the
end point of the Volhard titration is reached when Figure 2 still applies if the [Cl-] curve is rcmovcd, aud
[FeSCN++] reaches that value. If CFez+and Ccr the titration error for the case represented in that figurc
are known, the concentrations of the other species a t (CF,a+ = 0.010) is then
the end point and, hence, the titration error can be 10b.M - 10-6.40 - 10-5SC
E = 10-1.00 100
calculated.
Alternatively, the graphical method can be used to
emphasize the significance of the various equilibria. while, when Gea+
= 0.20;
Figure 2 shows a graph for this calculation when
Cor = 0.10 F and CFsa+ = 0.010 F. Either pAg,
pC1, or pSCN could be chosen as the master variable;
pSCN has been used in this case since it allows the most
direct calculation of the other variables. The [Ag+] Another method of interest is the Liebig titration of
line in the figure is the plot of the AgSCN solubility cyanide. Although the description of this method
product expression: requires the consideration of acid-base and complex
equilibria in addition to precipitation, the titration error
calculation can be handled in the same manner as has
The expression for [Cl-] is obtained from the ratio of been described.