F. J. C.

Rossotti and
Potenliometrit Titrations
Hazel Rossotti
University of Oxford Using Gran Plots
England
A textbook omission

A number of recent textbooks (1-10) of use a similar function defined by

analytical chemistry discuss potentiometric acid-base (F 4- y)lQ-BB/2.10Mr
=
(5)
titrations, but, none of these mentions Gran’s graphical
method (11) of end point determination. Gran's From equations (1), (2), and (5)
method seems to us to be the best yet suggested, and lias =
10-W + _

v)Bya (0)
been successfully used for many years in Stockholm and
elsewhere for the precise analysis of acids and bases. After the equivalence point,
The method is very simple. A volume V of acid of
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m + Km if„{ F + y)
initial concentration H is titrated with a volume v of J
_
~ -
_

(7)
1

[OH-j B(o -

vt)
strong base of concentration B in the galvanic cell (I)
where Kv. is the stoichiometric ionic product of water.
electrode reversible to titration reference,, For use in the alkaline range, functions analogous to
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/_ . I II .
'
hydrogen ions | solution II half-cell ^
and may be defined in terms of the experimental
The potential of cell (I) is given by quantities pH and E respectively, viz.
RT
B =
E0' -

In [H+Hh + Ej (1) <# '- = (F + «)/[H+]th= (F + y)l(F" (8)

and ’ =
(F + yjKF"2·3»3KT (9)
where E0' includes the potential of the reference half-
cell and the standard potential of the probe half-cell, From equations (7) and (8)
and E¡ is the liquid junction potential. A cell of type ' =
(o
—

Ve)B/Kw Ju (10)
(I) is also used in commercial pH meters, which, when
suitably calibrated, give direct readings of pH. and from equations (1), (7), and (9)
1 (y=
vc)B lOm’ + Bi)pBmitT/Kwyn
-

(11)
Titration of Strong Acid with Strong Base
If 7h, Ej, and Kw remain constant throughout the
For any value of v before the equivalence point ve,
titration, then from equations (4) and (10) the quanti-
+1 V1- VMv‘ G ~

B(ve -

v) ties and ' arc linear functions of v, such that ( ),

11 = = =

V + v vt(V + y) V + P
K

'( ) and the abscissa all intersect at the point 0, ve.

If pH is measured directly, we may make use of a func- Similarly, equations (6) and (11) show that, for constant
tion defined as 7n, E¡, and Kw, the functions ( ) and '( ) are also
linear, and both functions again cut the abscissa at the
=
(F + [ +] =
(F + e)10-i>* (3) point 0, ve. Thus the value of ve may be obtained by
From equations (2) and (3) plotting any one of the quantities , ', , or ^'against
v, and extrapolating the line obtained to cut the abscissa
=
(i··,
-

v)B7k (4) at the point v =

ve.
If, instead of pH, the potential E is determined, we may The method may be illustrated by the following

Volume 42, Number 7, July 1965 / 375

Figure 1. Gran plots ( ) and '( ) for the titration of a strong acid
with a strong base. Data for the filled points are given in the table.
example which is suitable for inclusion in an under-
Figure 2. Gran plot ( ) or ( ) for a system in which E/ = (£,—RTF-1 In
7h) varies with [H+], 35.0 ml of 0.210 M HhtOj was titrated with ~2
M LiOH in 50% v/v aqueous dioxarre containing 0.5 1 (Li +, H 4) NOs ~.

graduate course on pH. A mixture of 5 ml 0.1 M HCI

and 50 ml water was titrated with ~0.1 M NaOH,
obtained for [H+] < 8 X 10-3 . A method for cal-
using a cell containing glass, and saturated calomel,
electrodes. The calculations1 *are shown in the table, culating E/ from Gran plots has been described else-
where {12) together with a similar method for obtaining
and the resulting points plotted as full circles in Figure
for HCI from data obtained during titration of HCI
1.
in a Harned type cell without liquid junction, (2) If the
acid solution contains a metal ion which starts to
Titration of o Mixture of 5.00 ml 0.1000 M HCI +
50.0 ml H2O with ~0.1 M NaOH Using a
Commercial pH Meter
V V + V 'pH' -'pH' 10 “'pH'

0 55.0 2.160 3.840 6.918 X "® 0.831

1.00 56.0 2.257 3.743 5.534 X 10-3 0.310
2.00 57.0 2.393 3.607 4,050 X "» 0.231
3.00 58.0 2.575 3.425 2.661 X 10~3 0.154
4.00 59.0 2.897 3.103 1.268 X "·1 0.075
'*11' (5 X 10-‘5)4/
5.00 60,0 9.828 6.73 X 109 0.002
6.00 61.0 11.268 185,2 X 109 0.056
7.00 62.0 11.549 354.0 X 109 0. 109
From Figure 1, *>e =
4,97 ml, whence B =
0.1006 M.

Deviations from linearity may be due to one or more of

the following factors: (1) Curvature of any of the Gran
plots at values of v remote from ve suggests that the
quantity E/ E¡ RTF-1 In yn is not negligible at
= —

the extreme values of [H+] or [OH-] used. If the

plots are linear nearer the equivalence point, the value
of ve must be obtained from this region alone (Fig. 2).
For the junction H20/Sat:KCI, linear functions are

From equations (4), (6), (10), and (11), the point, of inter-
1

section 0, t'e of the plots for acid solution either with those for
alkaline solution or with the abscissa, is unaffected by changes
in the slopes of the lines. The various quantities , , ,' and
' may therefore be multiplied by any constants which make
plotting more convenient. The terms io-B-SV3·303RT and I0-PH
may, if required, be replaced by iO<c-®:F/2-30lOT and Figure 3. Gran plot [ ) or \p[v) for the standardization of a strong acid
where C is any constant. A value of 'pH' pH C may be = —

containing hydrolyzable metal ions. 40.0 ml of ^0.01 M HCIO4 containing

obtained merely by using an unstandardized commercial pH ~50 mM VO(CIO.i)2 was titrated with 0.021 8 M NaHCOs in a 3 M (Na)-
1

meter. CIO4 medium.

376 / Journal of Chemical Education

hydrolyze at a hydrogen ion concentration in the re-
gion > [H+] > 10 ~4 M the functions ( ) and ( )
may become curved as the acidity is decreased. If the
plots are linear at the highest acidities used, the equiv-
alence point of the strong acid may again be deter-
mined by extrapolation to 0 or 0 (Fig. 3). = =

(3) If the strong base is contaminated with carbonate,

the functions '( ) and '( ) are curved in the region
of ve.
The value of ve VH/B (where B ([OH-] +
= =

2[C032-]) is the total concentration of base) may be

found using only measurements in the acid region v <
ve (Fig. 4). If the functions '( ) and '{ ) are linear
over an appreciable range of v, they may be extrapolated
to cut the abscissa at the point v/ VH/B' (where />' =

is the total concentration of hydroxyl ions in the solu-

tion of base). An estimate of the carbonate ion con-
centration may therefore be obtained.
Titration of Weak Acid with Strong Base
If an acid HA is not fully dissociated in solution, the
free hydrogen ion concentration is no longer given by
equation (2) but by the relationship
[H+] K„[HA]/[A-] (12) =

Figure 4. Portions of Gran plots ( ) or \//(v) and '[ ) or '[ ) for the titra-
tion of a strong acid with a solution containing both carbonate and hy-
where Ka is the stoichiometric acid dissociation constant droxide.
of HA. If the titrant is the monacidic base MOH, then
[A-] =
[M+] + [H+] -

[OH-] =

are linear functions of v, such that t(v) intersects '( )

y~-v + [H+] [OH-] (13) and ( ) intersects '( ) at the point 0, ve (Fig. 5).
-

Deviations f rom linearity may be due to one or more of

and the following factors: (1) At the beginning of the titra-
[HA] =
Ca -

[A-] = -

[H+] + [OH-] (14)

tion, condition (15) may not be fulfilled, especially if
V -+- V the acid is only moderately weak. The value of ve
where is the total concentration of HA in the solu- must then be found using only that part of the function
CA
tion. If t(v) or ( ) which is found to be linear (Fig. 5). (2) As v
approaches ve, condition (16) may not be fulfilled if the
i>B
V + v
» [H+] -

[OH-] 05)
and
VH vB -

V + v
» [H+] -

[OH-] (16)

then from equations (12), (13), and (14)

Ka( VH -

vB)
[H+] =

vB (17)

By analogy with equations (3), (4), (5), and (6) we may

define the functions2
T =
y[H+]TH = yio-r" =
Ka(v. -

»)y„ (18)
and
-- «10-^/2.803nr =
Ka{ve -

v)yw\0~t.E«' + e¡)f/2mrt (19)

After the end point, v > ve and equations (7) to (11) are
again valid.
Since, for a weak acid, [H+] is low even at the be-
ginning of a titration, Ej will probably be negligible. If,
moreover, the initial solution of HA is not too con-
centrated, the ionic strength will not vary grossly
throughout the titration, and the terms Ka, Kw, and
7n will remain approximately constant. Then r and

Figure 5. Gran plots t[v) or 0(v) and <¿/(v) or i^'(v) for the standardiza-
2
The remarks in footnote 1 apply to the quantity r, and also tion of a weak acid with a strong base. 20.0 ml of -^0.05 M acetic acid
to , ', and T below. was titrated with 0.106 M NaOH.

Volume 42, Number 7, July 1965 / 377

acid is very weak. The equivalence point may then be
found by extrapolation of the linear region of ( ) or
9(v) to 0 or =0. (3) If the acid is contaminated
with a metal ion which forms complexes with A”,
equations (13) and (14) will no longer be valid. De-
viation of t(v) and 9(v) from linearity will increase as v
approaches ve. (4) Curvature in the alkaline region will
again be observed if the base contains carbonate (see
P- 377).
Titration of Strong Base with Strong Acid
For the titration of a volume Y of strong base with a
volume y of strong acid, the functions analogous to
and ' [equations (4) and (10) ] are
(Y + í/)[H+]7h
=
(Y + (y yt)HyK (20)
dpM/dv against v, Gran plots do not require large
numbers of readings, corresponding to very small
=
changes in v, in the region of the equivalence point.
Simplicity of Calculation. The calculations are
quick and easy. One point may be computed and
plotted in the one or two minutes which elapse between
the addition of base and the taking of a steady potentio-
metric reading (see the table).
Versatility. The method may be used when only
part of the pH range is accessible to measurement,
e.g., when the acid contains metal ions which hydrolyze
in the region pH~2.5 (see Fig. 3). It would be very
difficult to determine the concentration of strong acid in
a solution of this type by conventional methods. Gian’s
method has the further advantage that the presence of
= = -

carbonate in the alkali can readily be detected.

' =
(F + ¥)/[H+]t* (T + y)10f« - =
The application of the method to other types of po-
(v. y)H/Kvy„ (21) -

tentiometric data (e.g., those obtained in titrations of

in the acidic and alkaline regions respectively.2 Here polybasic acids and in redox, complex formation, and
ye is the equivalence point. Similar functions, and precipitation reactions) is discussed in Gran's original
', analogous to (6) and (11) may be obtained from paper (11).
measurements of E. Precision. The end points obtained by a linear Gran
extrapolation are much more precise than those ob-
Titration of Weak Base with Strong Acid tained by the differential method, especially if the
titration curve is not symmetrical.
If the base MOH is incompletely dissociated, equa- The value of ve obtained from a Gran plot may, if
tion (7) must be replaced by required, be refined to give an even more precise value.
_KW_ 1C.IM+] If the plot of ( ) or ( ) is linear, then E/ 0 and =
_ _

(22)
[OH-] At [MOH] 1, whence from equations (1) and (2)
1 1
7h =

where Kb =
[M+] [OH-]/ [MOH]. Now Ed E
2.303177’
+ --
.
B(oe -

v)
=
l0E =

(7
[Ml 2.303/7 VH(vt
/-J- + [OH-] [H+] (23) v)
-

= -

A + —p—
„
,
log (29)
vt(V + v)
and If either H or B is accurately known, values of E0r may
be calculated from (29) using several different values
[MOH] =
Cm -

[M+] = -

[OH-] + [H+] (24)

-y-jTy1 of ve within the small range permitted by the Gran ex-
where Cm is the total concentration of base in the solu- trapolation. The most precise value of vc is obtained
tion. If by trial and error as that which gives the most nearly
constant value of Ef. A value of ye may be refined
yH/{Y + y) » [OH-] -

[H+] (25) similarly.

and
(YB -

yH)/(Y + y) » [OH-] -

[H+] (20) Literature Cited

then from equations (22), (23), and (24)
(1) Lingane, J. J., “Electroanalytical Chemistry,” 2nd ed.,
r II - Am yH A N·,'/_ Interscience Publishers, New York, 1958.
(27)
_ _
_ _

(2) Kolthoff, I. M., and Elving, P. J., Editors, “Treatise

"

J
Kh(YB yH)
1
-

Kb(yc y) -

on Analytical Chemistry, Part I, Vol. I, Interscience

Thus, in the alkaline range, a function2 Publishers, New York, 1959.
(3) Belcher, R., and Nutten, A. J., “Quantitative Inorganic
T =
y/[H+h„ =
ylO-H =
K„(ye -

y)/KwjH (28)
Analysis,” 2nd ed., Butterworths, London, 1960.
can be plotted against y to give a straight line such that (4) Ewing, G. W., “Instrumental Methods of Chemical
T = 0 when y A similar function can be defined Analysis,” McGraw-Hill Bonk Co., New York, 1960.
ye.
—

(5) Laitinen, . A., “Chemical Analysis,” McGraw-Hill Book

for use with measurements of E. In the acid range, Co., New York, 1960.
equation (20) is again valid, and ye can be located (6) Vogel, A. I., “Quantitative Inorganic Analysis,” 3rd ed.,
using plots of ' or ' against y. Even when the plot Longmans, London, 1961.
in the alkaline region is nonlinear owing to the presence (7) Rtrouts, C. R. N., Wilson, . N., and Parry-Jones,
R. T., Editors, “Chemical Analysis,” Vol. II. Oxford
of carbonate in the base, or to the fact that conditions 1962.
University Press,
(25) and (2(5) are not fulfilled, a precise value of yc may (8) Meites, L. Editor, “Handbook of Analytical Chemistry,”
be obtained using only the measurements obtained McGraw-Hill Book Co., New York, 1963.
after the end point. (9) Skoog, D. A., and West, D. M., “Fundamentals of An-
alytical Chemistry,” Holt, Rinehart, and Winston, New'
York, 1963.
Advantages of Gran’s Method (10) Butler, J. N., “Ionic Equilibrium,” Addison-Wesley Pub-
lishing Co., Reading, Mass., 1904.
Simplicity of Measurement. Potcntiometric readings (11) Gran, G., Analyst, 77, 661 (1952).
can betaken after regular increments in v throughout the (12) Rossotti, F. J. C., and Rossotti, H. S., J. Phys. Chem., 68,
whole titration; unlike differential plots of dE/dv or 3773 (1964).

378 / Journal of Chemical Education