James N.

Butler
University of British Columbia
Vancouver, British Columbia
Calculating Titration Errors

CV
Calculating titration errors is one of the $ =
(4)
C0V0
most important applications of equilibrium principles
to analytical chemistry. Unfortunately, most treat- Note that at the equivalence point, $ 1. =

ments of this problem have been unsatisfactory from Eliminating P between (I) and (2), using (3) to ex-
one of two points of view. Either approximations were press [Cl-] in terms of [Ag+], and using (4) to eliminate
used which were not valid at the equivalence point, or CV, we obtain the equation of the titration curve (4):
else the equations obtained rigorously were cumbersome
CuFq A so
to evaluate. In this paper some explicit expressions for (4> l) V + =
[Ag+] (5)
F0 [Ag+]
the titration error in acid-base and precipitation
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titrations will be presented and also a simple method for For the purposes of calculating titration error, we can
deciding qualitatively whether or not a given titration use an approximate relation for the volume factor
Downloaded via UNIV DE ALICANTE on December 23, 2022 at 21:32:24 (UTC).

is feasible.1 which applies in the region near the equivalence point.

The theoretical point in a titration where an amount Setting $ 1 in (4), we have:
=

of titrant exactly equivalent to the amount of substance

Fo C
being titrated has been added is called the equivalence V + F0
=

C0 + C
K 1

point. The experimental approximation to this, ob-

tained by using a colored indicator or a potentiometric When (6) is used to evaluate the volume factor in (5)
measurement, is called the end point. The difference in weobtain the equation for the titration error:
volume added between the equivalence point and the
end point, divided by the volume added at the Titration error = $ -
1 =
lA-g(7)
equivalence point, is the titration error. The titration
error results from the failure to know the exact For the reverse titration of' silver ion with chloride,
equivalence point, and is in addition to any errors re- the signs of the terms on the right hand side of (7) are
sulting from volume measurements and weighing. reversed.
At the equivalence point, $ =
1, and (7) gives
Symmetrical Precipitation Titration [Ag+]! =
Kan (8)
As an example of a precipitation titration where an which is the equation for [Ag+] in a solution of AgCl
insoluble 1-1 salt is formed consider the titration of in pure water.
chloride with silver ion. The same formalism applies If the concentration of free silver ion at the end point
to any 1-1 salt such as ITg2S04, PbS04, AgBr, Agl, is known, it can be substituted in (7) to obtain the
AgSCN, etc. titration error.
If V0 ml of chloride ion of molar concentration C0 is
titrated with V ml of silver ion of molar concentration Example. In the Mohr method for chloride determination, 50
ml of 0.1 M NaCl is titrated with 0.1 M AgNO:;. As an indi-
C, the mass balances (1,2) are cator, 1.0 ml of 0.1 M K2Cr04 is added. If the end point is taken
when the first red precipitate of Ag2Cr04 forms, calculate the ti-
CoVo tration error.
[CI-] + P =

V + F„ (1)
The red precipitate will form when the solubility product of
CV AgsCr04 is exceeded, that is when
[Ag+] + P =

V + Vo (2) > 1.1 X 10-12

[Ag+HCrOr]
where P is the number of moles of AgCl that precipitate Since [Cr04~] = 1.0 X 10-3, when roughly 50 ml of silver nitrate
has been added, the end point will occur when
per liter of solution. The only equilibrium that need be
considered in most of the usual analytical methods (3) [Ag+] = 3.3 X 10 3

is the solubility product:

When this value is substituted in (7), together with Co C 0.1 = =

[Ag+] [Cl-I =
K'0 (3) and Ksa = 1.8 X 10-!0 we get # 1 5.5 X 10-J. This titra-
— -

tion error (0.06%) is half the usual buret reading error (0.1%).
The fraction titrated is defined to be the ratio of the In practice, the solubility product at a finite ionic strength, will be
number of equivalents of titrant added to the number larger than the value given, and an appreciable amount of the red
added at the equivalence point: precipitate must form before it is visible. Thus the value calcu-
lated represents the minimum possible titration error.

A popular method for determining the end point

1
This treatment of titration errors wilt be included in the au- in a potentiometric precipitation titration is to choose
thor’s forthcoming book, “Ionic Equilibrium,” which will be pub-
lished early in 1963 by Addison-Wesley Publishing Co., Reading, the point where the slope of the titration curve is a
Mass. maximum. For a symmetrical titration this is the best

66 / Journal of Chemical Education

way of determining the end point, since the point of [M]s =
8Ato (15)
maximum slope theoretically coincides with the equiva- The equivalence point, on the other hand, is obtained by
lence point. This can be seen by differentiating (7)
setting# 1 in (13), and is at
=

with respect to pAg (—log [Ag+]), which gives for the

[M]3 2 Km (16)
slope near the equivalence point
=

dpAg -0.434 CoC [Ag+] +

Abo \ An explicit expression for the titration error from this
Slope =

Co A C [Ag+] / source is obtained by substituting (15) in (13):

The point of maximum slope occurs where the deriva-
tive of the slope is zero. By differentiating the above Titration error = * -

1 =
A,0*/s (17)
expression, we find that at the point of maximum slope
The positive sign applies for the titration of a divalent
[Ag+]» =
A'.o
ion with a monovalent ion, and the negative sign
This is the same as (8), which gave the value of [Ag+] applies for the titration of a monovalent ion with a
at the equivalence point. divalent ion.
This expression should prove useful in practical
Unsymmetrical Precipitation Titrations potentiometric analysis because the error introduced by
For titrations forming unsymmetrical salts, M3X, taking the end point at the point of maximum slope
can be corrected for.
such as silver oxalate or mercurous chloride, the titra-
tion curve equations are of slightly different form.
Example. In the titration of 0.005 M Pb ion with 0.01 .1/
+ +
For the titration of V0 ml of the divalent ion X of IO3- ion, since Astl 2.6 X 10~13, the titration error calculated
—

normality Ce (molar concentration 1/2 Co), with V ml from (17) is + 1-9%. If the correct end point volume is desired,
of the monovalent ion M of molar concentration C, the 1.9% must be subtracted from the volume at which the maximum
slope occurs.
mass balances are
In applying (17) in practice, it must be remembered
[X]+P =

iy^V0 (9)
that K,0 is the concentration equilibrium constant,
which holds at the ionic strength of the solution at the
[M] + 2F =
(10)
equivalence point.
The equilibrium is governed by the solubility product Acid-Base Titrations
[M]>[X] -
A8„ (11)
The titration of a strong acid with
strong or weak a
Eliminating P between (9) and (10), and using (11) base and the titration of a strong a strong or base with
and (4), we have the equation for the titration curve weak acid, can all be considered as special cases of the
CqVq
titration of a weak acid with a weak base. We shall
V A Vo
(*-D= 1M] -

[XIV.
2[X] (12) derive an expression for the titration error in a weak
acid-weak base titration, and then simplify to give the
Near the equivalence point, the volume factor can be other eases (5,6).
approximated by (6), and the titration error is given by If Va ml of an acid HA of molar concentration C<,
is titrated with V ml of a base B of molar concentration
Titration error =
4> —
1
Co
CoC
A C

C0
(IM]
AC
-

If) =

C, the mass balances are

(,3)
CoCr (bps ~21X1) [HA] + [A-] =
(18)

For the reverse titration of a monovalent ion with a

divalent ion, the signs on the right hand side of (13) are [BH+] + [B] =
(19)
reversed.
It is well known that the point of maximum slope in There are three equilibria involved in this system:
an unsymmetrical titration does not coincide with the [H+][A ] A„[HA] =
(20)
equivalence point, but explicit expressions for the
titration error from this source arc not usually given.2 [TT+][OII-I A„ =
(21)
Such an expression is very simple to derive from (13). Ab[H+]IB] AW[BH+] =
(22)
Differentiating (13) with respect to pM gives for the The final relation required is the charge balance, or
slope
electroneutrality condition (1,2):
’

Sl»p» - -

-»«<m(iMJ + 4
[§f.) (14) [H+l + [BH+] [OH-] + [A% (23) =

The point of maximum slope is found by differentiating Eliminating [HA] between (20) and (18) gives
this expression and setting the result equal to zero,
which gives the condition [A—1J
1
=

V A Vo
(_—_'l
\A0 + [H+] /
(24)J

Eliminating [B] between (22) and (19) gives

2
Hibbits. J. Chem. Educ., 35, 201 (1958) gives an expres-
J. O.
sion for this titration error which differs from our result by about a CV ( Ab[H+]
[BH+I V A Vo \KV A Ab[H+D (25)
factor of two, because he defines titration error in an unconven-
tional way. See H. L. Christopheeson, J. Chem Enuc., 40, 63
(1063) for an alternative derivation which gives the same result as Substituting (21), (24), (25), and (4) in (23) gives the
ours. equation for the titration curve:
Volume 40, Number 2, February 1963 / 67
 '
Ai,[H ~] activity coefficients can be assumed to be unity, but for
A* + Ah[H+] ) (a„+[H+[) more accurate calculations (if these should become de-
I + sirable for some reason) an empirical activity coefficient
(m
1 o

|H'0
-

CoF„
expression such as the Davies equation (7) is useful.
This may be rearranged to give: In aqueous solution at 25°C the activity coefficient of
an ion of charge z is given by
4> -
1
V + To / Aw ,, \ ( Aw
r i ,
+ +
CoF ([H+] [H+I) (a„[H 1) -

log T =
0.509 22 -
0.2
A' [H+] Q
\Ab[HH N)(\K* + [H-* ) \K. + [H+]/ (20)
where 7 is ionic strength.
This equation represents exact solution of the six an In converting from pH to [H+] remember that
equations in six unknowns, but is cumbersome to use pH -log [H+] 7w+ =

in this form.
For calculating titration error in practical acid-base The Sharpness Index
titrations certain simplifying assumptions can be A convenient quantity to deal with in considering
made. If we arc close to the equivalence point, the titration errors qualitatively in acid-base titrations is
volume factor can be approximated by (6). If [H+] the sharpness index, defined to be the magnitude of the
is small compared to 77a yet large compared to K„/Kb,
slope of the titration curve at the equivalence point
we can reduce (26) to the simpler form
(6):
Co + C
Titration error <S>
-
1
CoC (m ~[H ]) +
v =
IdpH
d‘t>
(31)
Aw [H +
_

(27) By differentiating the expressions derived above for the

Ab[H+] K,
titration curve in the region near the equivalence point,
which will give the titration error for the titration it is a straightforward matter to obtain explicit expres-
of a weak acid with a weak base under any conditions sions for the sharpness index.
where a practical end point could be observed.3 For For the titration of a strong acid with a strong base,
the titration of a weak base with a weak acid, the oppo- differentiation of (30) and application of the equivalence
site signs are taken for all the terms on the right hand
point condition [H+]2 77„ gives =

side of (27). By differentiation, it can be shown that

the point of maximum slope of the titration curve v 0.217
CoC 1
2.17 X 10®
CoC
(32)
coincides with the equivalence point, so that the maxi- Co + C A,V‘A Co + c
mum slope method can be used for determining the end where the value of 77„. at 25°C has been used.
point under conditions where indicators are inap- For the titration of a weak acid with a strong base,
plicable. differentiation of (28) and application of the equivalence
If Kb is very large, we have the titration of a weak point condition $ = 1 gives
acid with a strong base, and the titration error is given
0.217
CoC [H+]'
In- (33)
Co + C Aw
Co
Titration error = 4> —
1 =

C0C (m -

IH*0
+
where [H+]' is the value of [H+] obtained by setting
$ =
1 in (28). If the equivalence point is more basic
[H
A (28) than pH 8, the sharpness index is given by
=
a

/ CoC A* 'A
If very large, we have the titration of a strong
A';, is v 0.21
VCo + C Aw )
(34)
acid by a weak base. This titration is usually per-
formed the other way around, so we shall give the ex- For the titration of a weak base with a strong acid,
pression (from (27) with opposite signs) for the titration differentiation of (29) and application of the equivalence
of a weak base with a strong acid: point condition $ 1 gives =

Aw \
Titration error = $ —
1 = '
“ 2175TTcnFp <33>
(jH+] [H+l/
Aw
(29)
where [H + ]' is obtained by setting $ 1 in (29). If =

Ab[H+J the equivalence point is more acid than pH 6, the =

If both 77a and 771, are very large, we have the titration sharpness index is given by
of a strong acid with a strong base, whose titration 0.217
CoC
v (36)
error is given by ( Co + c

Titration error = $ —
1 = —~
[H 1

] (30)
For the titration of a weak acid with a weak base,
^ differentiation of (27) under the assumption that both
As in the case of the precipitation titrations, the [H+] and [Oil-] are small at the equivalence point
equilibrium constants to be used are concentration con- gives
stants applying at the ionic strength of the solution at
the equivalence point. For rough calculations, the v = °’21'
Co + C [Bp
(3'}

3
If [H + ] at the equivalence point is of the same order of magni- where [B\ [HA ['is the concentration of free base or
=

tude as either A„ or Aw/Ab, the equivalence point will occur in the acid at the equivalence point. Using the mass and
buffer region of either the acid or the base. charge balances (18) through (23), with CV C0V0, —

68 / Journal of Chemical Education

and neglecting [H + ] and [OH-] compared to [B] and reading errors. An example of such a titration is the
[HA], we can obtain titration of acetic acid with 0.1 molar strong base, for
which the sharpness index is 2 X 10:!. Strong acid-
” “
0-217
jl + (%f-b)V,[
(38) strong base titrations, where C and Co are larger than
10-3 molar, also fall in this class, provided C02 is ex-
For the intermediate equivalence point in the titra- cluded from the solutions.
tion of a diprotic acid with a strong base, it can be shown Using a pH meter to determine the end point by
by similar methods that under the assumption that finding the point of maximum slope in the titration
[H + and [OH-] are small compared to [H2A] and
]
curve, the pH at the equivalence point can be estimated
[A-] at the equivalence point, the sharpness index is to within 0.1 units. From (31), this means that if the
given approximately by sharpness index is smaller than 10, even the most pre-
cise measurements of the end point pH will result in a
v = 0.217 (39)
(§£)'A titration error greater than 1%. An example of such a
where ZCi is the ionization constant of II2A and ZC,2 is
titration is the titration of HCN with 0.1 molar strong
the ionization constant of HA-. Equation (39) breaks base, for which the sharpness index is 10.
down when Kal/ZL2 is smaller than 103, but this is not
It is hoped that the use of the simple equations de-
rived in this paper will clear up some of the mystery
a situation of practical importance for titrations.
Other equivalence points in polyprotic acid-base titra- surrounding the calculation of titration error and will
make it easier for analytical chemists to decide whether
tions can be treated analogously.
or not a given titration is feasible.
These various expressions for the sharpness index
can be easily evaluated when the equilibrium constants
Literature Cited
are known, and the value of the sharpness index can be
used to give a qualitative or rough quantitative estimate (1) Butler, J. N., J. Chem. Educ., 38, 141 (1961).
of the error in a given titration. (2) King, E. J., “Qualitative Analysis and Electrolytic Solu-
tions,” Harcourt-Braee, New York, 1959, chap. 4 ff.
With an indicator, using no special methods such as (3) Butler, J. N., J. Chem. Educ., 38, 460 (1961).
color matching, the pH at the equivalence point can (4) Bolie, V. W., J. Chem. Educ., 35, 449(1958).
usually be estimated to within one unit. From (31), (5) Ricci, J. E., “Hydrogen Ion Concentration,” Princeton
this means that if the sharpness index is larger than University Press, Princeton, N. J., 1952.
(6) Smith, T. B., “Analytical Processes, A Physico-Chemical
103, the titration error will be less than 0.1%, and the Interpretation,” 2nd ed., Edward Arnold and Co., 1940.
accuracy of the titration will be governed by the buret- (7) Davies, C. W., J. Chem. Soc., 1938, 2093.

Volume 40. Number 2, February 1963 / 69