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Talanta.1966.Vol. 13.pp. 1431to 1442. PergamonPressLtd.

Printedin NorthernIreland

GRAPHIC

Department

METHOD FOR THE DETERMINATION


OF TITRATION END-POINTS *

FOLKE INGMAN and EBBE STILL


of Analytical and Inorganic Chemistry, Abe Akademi, Abo, Finland

(Received 21 April 1965. Revised 9 April 1966. Accepted 10 May 1966)


Summar-Aa extension of Grans method for the determination of
equivalence points in potentiometric acid-base titrations is presented.
Equations are derived assuming that the stability constants of the
reactions are known. The equations make it possible to locate the
equivalence point with fair accuracy when acids with stability constants
ranging from KEa N 10 to Kz* - lOlo are titrated. The limit of
KL above which Grans equations do not yield satisfactory results is
about 10. Conditional constants and a-coefficients are used to extend
the method to apply to more complex systems, where more than one

speciesreacts with the titrant.


AMONG

the graphical methods for the determination of titration end-points published


by various authors, those of Gran 1*2have attracted considerable attention.
Grans first method1 involves the plotting of either AV/ApH or AV/AE as a
function of V, the volume of added titrant, after values of E or pH have been experimentally determined for several values of V. In the ideal case the resulting plot
consists of two straight lines, which intersect each other and the V-axis at the
equivalence point. One of the drawbacks of this method is that the accuracy of the
TABLE I.-GRANS

Substance
titrated
Strong acid
Weak acid

SECOND METHOD

Functions plotted
on the acid side of the
on the alkaline side of the
equivalence point
equivalence point
(V, + V)lO(k-pa) =f(V)
V.lO-*= =f(V)

(V, + V)lO*H-) = f(V)


(V, + V)lOp=-k =f( V)

The titrant is in each case assumed to be a strong base. V, is the


volume of the solution before the titration is started, Vthe volume of added
titrant, and k, k are arbitrarily chosen constants.

plot is influenced by the accuracy of the experimental data, and another that the
lines for titrations of weak electrolytes are more or less curved and do not yield
reliable results, because the change in pH or E at the equivalence point is too small.
The second method of Gran2 is based on an original idea of Ssrensen,8 who
plotted {H}, the antilogarithm of -pH, as a function of V for titrations of strong
protolytes, disregarding the effect of the changing volume. Sorensen employed an
analogous method when titrating halides with silver nitrate. Gran introduced a
correction for the volume change during the course of the titration. He also extended
his method to titrations of weak protolytes, and to other types of titrations than
those involving neutralisations.
The functions plotted when Grans second method2 is applied to acid-base titrations
are presented in Table I.
+ Presentedin part by E.S. in December 1962 at Finska Kemistsamfundet, Helsingfors.
1431

F.

1431

INGMAN

and E. STILL

Grans second method yields excellent results when a moderately weak acid
such as acetic acid is titrated with a strong base. Two straight lines are obtained
and the point where these lines intersect each other and the V-axis is the equivalence
point.
For weak acids with stability constants of 10 to 10s the lines obtained by this
method are no longer straight but slightly curved. Moreover, the asymptotes do
not intersect at the V-axis, and the point where they intersect only occasionally
coincides with the true equivalence point. These deficiencies originate in the simplifying assumptions made by Gran when deriving his equations.
The aim of the present work is to show how it is possible, when the stability
constant for the reaction is known, to derive an expression which, when plotted
against the titrant volume V, yields a straight line that intersects the V-axis at the
equivalence point. The expression for the titration of a weak acid with a strong
base will first be derived.
It will further be shown how it is possible to generalise this expression by the
introduction of conditional constants and a-coefficients.4 The determination of the
equivalence points of titrations of complex systems is thereby facilitated. As an
example, the titration of a weak acid in the presence of another weak acid or a metal
ion will be considered.
TITRATION

OF A WEAK

ACID

WITH

A STRONG

BASE

A weak acid HA is titrated with a strong base (sodium hydroxide). The initial
concentration of the acid is denoted by C,, and the initial volume by V,. The
concentration of the strong base is denoted by CNaOHand the volume added by V.
The consumption of the base at the equivalence point is denoted by V,,.
The derivation is based upon the following three conditions:
(a) The law of mass action must hold:
HA+

KH _ tHA]
HA- (H)[A] *

H 4-A;

(1)

(For convenience, all signs of charge are omitted in this paper). The constant Kg*
is a mixed constant, valid at a certain ionic strength. Mixed constants, where
the activities of the hydrogen and hydroxide ions (denoted by {H} and {OH)) are
used in conjunction with concentrations of all other species, are very convenient for
equilibrium calculations, since pH-values are nowadays almost solely determined
potentiometrically.
The activity of the hydrogen ion is related to the concentration
by the expression
{H}

=_fiJHl.

(2)

where fHis the activity coefficient of the ion.


(b) The solution must be electrically neutral, meaning that

[Al + [OHI =

Wal

+ [HI.

(3)

(c) The equation


ve&NsOH

must be valid at the equivalence point.

v0cHA

(4)

Determination

The concentration

1433

of titration end-points

of the sodium ions is

2vo+ v cKaOH

(5)

which, when combined with equation (3), gives

[Al = ?-

+ WI -

v, + v C&H

[HA] = +

C,,

- [A] = +$

WI

CNaoH-

[HI + [OHI.

(7)

Substitution of (6) and (7) into (1) and subsequent rearrangement of the terms yields
Veq -

V = V{H}K&

~([Hl-

tOHI)(1+ (H}K,H,I

The values of most of the constants have been determined at an ionic strength
of ,U = 0.1. It is thus practical to adjust the ionic strength to this value, and in our
experiments sodium perchlorate was used for this purpose. It may be noted that in
equation (8), the concentrations [H] and [OH], caused by the electroneutrality
rule, occur in addition to the hydrogen ion activity {H} determined potentiometrically.
For accurate analyses the [H] and [OH] values in equation (8) should be calculated
from the activities. This means that at an ionic strength of 0.1, [H] = {H}/10-~08
and [OH] = {OH}/10-0.12.
A comparison of equation (8) with the Gran equations for the titration of a
weak acid reveals that Gran plotted only the first term V{H}K&, written in the form
VIO(k-*H), on the acid side of the equivalence point, k being a constant arbitrarily
chosen to yield numerical values that could conveniently be handled. On the alkaline
side of the equivalence point Gran plotted the term (V. + v>[OH]/C,,,,
against
V. Gran wrote the term in the form (V, + V)lO(pH-K), k being a constant similar
to k. When plotted against V, equation (8) yields a straight line with a slope of 45.
The titration curves of p-alanine (log K& = 10.2) and ammonium nitrate
(log K& = 9.4) with sodium hydroxide are shown in Fig. 1. The titrations were
performed at an ionic strength of ,u = 0.1. Kiellands values6 were used for the activity
coefficients, and the values of the stability constants were taken from the literature,6
The use of equation (8) is illustrated in Tables II and III and Fig. 2. For comparison,
Fig. 3 shows the curves that result when Grans formulae are used for the titration
of ammonium nitrate.
The method described can be used only if the value of the stability constant
K& is known. This could naturally be considered a serious drawback. The method
is, however, intended for use in cases where no other means are available for the
determination of the equivalence point with satisfactory accuracy. Such cases are
encountered in practice when very weak acids (7 < log K& < 10) are titrated.
The limit beyond which the simple Gran equations do not yield satisfactory results
can be considered as log K& N 7.
For most analytical purposes the value of the stability constant can be estimated
with satisfactory accuracy from the pH value at the point where VN V,,/2, i.e.,
3

F. INGMAN
and E. STILL

1434
12
77
10
9
PH

18
7
6
5
4
0

-1

4 5vs

10

FIG. l.-Titration
of 50 ml of 1.07 x lO-SM p-alanine (log KL = 10.2) and titration
of 77 ml of 1.02 x lo-*M ammonium nitrate (log K& = 9.36) with O*lOOM sodium
hydroxide. At the equivalence point, the consumption is theoretically 535 ml for
&alanine and 7.85 ml for ammonium nitrate.
TABLEII.-/I-ALANNE
log v, + V

V
::;
2.0
2.5
3.0
3.5
40
4.5
5.0
5.5
6.0

pU3

CNaOE

955
9.77
9.95
10.12
10.28
10.43
10.59
10.75
10.91
11.07
11.21

1%

2.71
2.72
2.72
2.73
2.73
2.73
2.74
2.74
2.75
2.75
2.75

-4
-4.1133
-3.93
-3.76
-360
-3.43
-3.29
-3.13
-2.97
-2.81
-2.67

(HI&

1+

(W-II - [HD

1 + l~6
100. =
1 + 100.86 =
1 + 100.08 =
1 + 10-0.08 =
1 + lO-0.as =
1 + lO-0.*0 =
1 + 10-0.65 =
1 + 10-0.1 =
1 + 10-0.81 =
1 + 10-1.0 =

K,
100*4
loo.67
100.U
1OO.U
100.N
lOWI
100.16
100.
100.08
100.06
100.04

4.47
4.03
3.56
300
2.50
2.06
164
1.27
098
0.59
0.06

V, = 50 ml, log K, = 1400, log K& = 10.20 (from Fig. l), log foH = -0.12,
VW -

V = V(H)K:A + E(D-U

0.13
0.15
0.17
0.20
0.25
0.30
040
0.53
0.73
0.98
1.32

=
=
=
=
=
=
=
=
=
=

logf,

4.34
3.88
3.39
2.80
2.25
1.76
1.24
0.74
0.25
-0.39
-1.26
= -0.08

[OHD(1+ U-W&I

TABLE III.-AMMONIUM NITRATE

log
V

3.0
4.0
5.0
6.0
7.0
8.0
9.0
10-o

PUS

8.50
8.89
9.15
9.38
960
9.85
10.18
10.69
11.14
11.37

v, + v

cN,O,

290
2.90
2.91
2.92
2.92
2.93
2.93
2.94
294
294

logWH1

[HI)

-538
-4.99
-4.73
-4.50
-4.28
-4.03
-3.70
-3.19
-2.74
-2.51

1 +

100.86

1 + 100 =
1 + 100.8 =
1 + 10-0.0 =
1 + lO-0.S =
1 + 10-O.&@=
1 + lO-o.s* =
1 + lO-l.88 =
1 + 10-1.18 =
1 + 10-5.0 =

I, = 77 ml, log Km = 1400, log Kg* = 9.36, logfoX

V,, - V = V{H}KL

ZWl

v,, - v

1 -t U-XV&

= -0.12,

1(-y.=

l@*EO
100.
lOo.P@
lOWSO
100.
100.0
100.0
100.0
lOc!.OO

7.24
5.91
4.87
3.82
2.88
1.95
1.06
0.37
0.15
0.10

logfH = -0.08

- PHDU + O-IV&)

0.03
0.03
0.04
0*05
0.07
0.11
0.20
0.59
1.62
2.69

=
=
=
=
=
=
=
=
=
=

7.21
5.88
4.83
3.77
281
1.84
0.86
-@22
-1.47
-2.59

Determktion

2-

of titration end-points

I
p-ALAN/NE

o-

1435

\I

1
7

I\

51

--vu

,\I

f
I

9mllO
I\

-1

FIG. 2.-Straight
lines that result when titration data in Fig. 1 are substituted in
equation (8). The principles of calculation are illustrated in Tables II and III. For
/k&nine the straight line intersects the V-axis at V = 5.22 ml, which corresponds to an
error of -2-4 %. For ammonium nitrate the straight line intersects the V-axis at V =
7.78 ml, which corresponds to an error of -0.9 %.

-1

FIG. 3.-The straight line (a) that results when the titration data for ammonium nitrate
shown in Fig. 1 are used to compute V, - V from equation (8), and the curves
(b, c, c, c) that result when Grans second method is used. The abscissa of the point
of intersection depends on the value of the arbitrarily chosen constants k and k (cJ
Table I). The values of k used for computing c and c differed by &@30 from the
value of k used for computing c.

when approximately
half of the acid has been titrated. If a very high degree of
accuracy is sought, the method developed by Goldman and Meites can be used.
If an incorrect value of the constant has been used, the plot will not have a slope of
45 and will not be linear.
It may be mentioned that the results of the titrations given in Figs. 1 and 2 can
be found without using any graphic procedure by calculating Vea for the various
volumes of titrant (ix., in the last column of Table II, V is added to Feq- v).

F. INGMAN
and E. ST~L

1436

However, this procedure is not always appropriate


Table V).
TITRATION

OF A WEAK

BASE

(cJ the titration presented in

WITH

A STRONG

ACID

An analogous expression can be derived for the determination of the equivalence


point when a weak base is titrated with a strong acid (hydrochloric). The equation is :
Veq -

V = V{OH}K,O& +

owl

- [HI)0 + WW%d

(9)

where

POW
K% = [Bl(OH)
This case will not be treated in this paper.
TITRATION

OF TWO

WEAK

ACIDS

WITH

A STRONG

BASE

The determination of the total amount of acid in a mixture containing two weak
acids HAr and HA,, is usually quite easily accomplished, provided both acids are
strong enough to be titrated in the conventional manner, i.e., provided that both
K&, and K&11 < 10. When, however, the amount of the stronger acid (here
taken to be HA,) in the mixture is to be determined, complications often arise owing
to the fact that the difference between the stability constants of the two acids is too
small to permit a conventional stepwise titration.
When conditional constants and a-coefficients4 are used, it is quite easy to derive
an expression analogous to the one already derived for the titration of one weak
acid, and this will permit the determination of the first equivalence point.
In this case the equation
HA, + OH + A, + H,O

(10)

HA,, + OH =S A,, + H,O

(11)

represents the main reaction.


The reaction

is considered a side-reaction, the effect of which is taken into account by introducing


the appropriate cr-coefficient.8
The electroneutrality rule states that in this case

Dal + WI = (PHI + LW + [AI1= PHI + LW

(12)

Comparison of this equation with equation (3) shows that [OH] should be substituted
for [OH] in equations (6) and (7), and this in turn means that the only change that
need be made in equation (8) is the substitution of [OH] for [OH], which yields

ve,-

J-,= V(H}K& +

(WI - tOHI)(l + (H}K&J.

(13)

As usual, [OH] denotes the concentration of not only the free hydroxide ion but
also of all the hydroxide ion added to the solution that has not reacted with HA,
according to the main reaction. There will be no noticeable error if the activity

Determination of titration end-points

1437

coefficient foaP is considered equal to foH. The concentration


that has reacted with HAzr is given by [A,,]. Hence
WI1 = [OH] +

IM =

of hydroxide ion

%H[OHI

(14)

where
(15)
To test the equation derived several titrations of chloroacetic acid (log K& =
2GQs in the presence of acetic acid (log K& = 4.7) were performed using sodium
hydroxide. As can be seen from Table IV and Figs. 4 and 5 the results were in close
agreement with the theoretical. Figure 4 shows one of the titrations curves and Fig. 5
shows the straight line that results when Yeq - Y computed from equation (13) is
plotted against Y to determine the location of the equivalence point.

3
PH

7
6

3
4
---+v

FIG. 4.-Titration
of 50 mi of a solution 0.72 x 10-W in cbloroacetic acid and
0.50 X lO-#M in acetic acid (A log K& = log Ii& - logKm,,
= 1.9) with O*lOOM
sodium hydroxide. At the equivalence point, the consumption is theoretically 360 ml
for chloroacetic acid.
TABLEIV.-MONO~HLOROACETZCACID(HA*) AND ACETICACID@A~~)
Y
0.0
0.5
1.0
1~5
2.0
2.5
3.0
3.5
4.0
4.5

~0.0
2.59
2.68
2.78
2.91
3.06
3.24
348
3.80
4.14
4.47

log v, + v
ClWOli
2.70
2-71
2.71
2.72
2.72
2.73
2.73
2.73
2.74
2.74

[HI - [OH1

1O-%8 _
] O-9.80_
IO-P.70_
10-1.8 _
IO-P.08_
IO-B.16_
IO-0 _
~0-9.72_
IO-.00_
IO-WJ_

v, = 50 ml, log K&, = 2~35, bg K& = 9.24, [HA,,1 log& = -0.08,

V,, -

VW-- v

I+ W&

~O-l.85=E*(ye.sa
IO-4.8 = ,0-W
*o-*.1, =E*O-8.1
IO-4.0P=i IO-#.86
10-m = 10-8.03
10-a.,* 3 IO-a.ao
IO-Em =E 10-u*
,0-w, 5 _ 10-W
,O-8 1 _,O-8.87
10-861= - ,0-2.6#

V-

V(H}K&

0% +
0.74 +
1.18 +
1.30 +
I.23 +
1.02 +
0.70 +
0.39 0.20 0.11 -

427 = 4.27
3.09 = 3.83
219 = 3.37
1.35 =I 2.65
0.79 = 2.02
0.38 = I.40
0.05 = 0.75
0.30 =i 0.09
0.78 = -0.58
1.70 = --I*59

10-aso, log aoa = 6-94 log fox = --0*12~

+ ~GHI-

WU)(1

+ WK&)

F. INGMANand E. Snu

1438

FIG. 5.--Straight line obtained when titration data plotted in Fig. 4 are used to compute
V,, - V from equation (13). The different steps of the calculations are shown in
Table IV. The straight line intersects the V-axis at V = 3.62 ml, which corresponds
to an error of +0.6x.
TITRATION

OF A WEAK

ACID

IN

THE

PRESENCE

OF A METAL

ION

A very weak acid can be made apparently stronger if its conjugate base A produced
in the reaction
HA+OH+A+H,O

(16)

can be forced to take part in a side-reaction. The equilibrium of the main reaction
will then shift to the right and the numerical value of the conditional constant4 of
reaction (16), Kiu = CC&~, will increase. Many metal ions react readily with the
conjugate base of an acid to form a complex according to the scheme
A+M+MA.

(17)

As has been pointed out by Ringborn, 4 this side-reaction permits the titrating of
many acids that are too weak to be titrated directly.
However, the metal ions are themselves acids, and will consequently react to
some extent with hydroxide ions. This side-reaction is undesirable, but cannot be
avoided. It may be written
M+OH+MOH.

(18)

Frequently matters are further complicated by the fact that the metal hydroxide
starts to precipitate at a pH that is very close to the pH at the equivalence point
of the titration. As a result, the titration curve will be deformed as in Fig. 6.
In order to determine the location of the equivalence point on a titration curve of
this shape, it is necessary to employ a method that utilises points on the titration
curve that lie on the acid side of the equivalence point only.
The value of the conditional constant of the acid may be low enough to permit
the use of one of Grans simple equations. In other cases one may be forced to use
an expression which can be derived similarly to the expressions already presented in
this paper.
The effect of these two side-reactions is taken into account by introducing the
coefficients :
aA

QOH(M) =

1 -I MKMA

(19)

1 +

(20)

WKHOH

Determination of titration end-points

1439

where Knaa and &on denote the stability constants of the complexes MA and MOH
respectively.
Assuming that a bivalent metal is added to the solution in the form of MB, the
condition of electroneutrality now is:
2[B] + [A] + [OH] = [H] + [Nal+

2[Ml+

[MAI + [MOW.

(21)

When [MA] + [MOH] is added to both sides and ([Ml + [MA] + [MOH]) is
substituted for [B], it is found that
([Al + [MA]) + (PHI

+ NOHI)

= [A] + [OH] = WI.

(22)

A comparison of this equation with equation (3) shows that the following changes
should now be made in equation (8): K,Hk = K&/ccAcMI should be substituted for
K&, and [OH] should be substituted for [OH]. The final result is then
V., - V = V{H}Kgf

+ F([H]

- [OH])(l + {H}K,f)

(23)

NaOH
Note. If a univalent metal is added as MrBr, the solution will be electrically
neutral when
WI1 + [Al + COHI = [HI + Ml + Ml.
(24)

As tB,l = [WI + MA1

+ MOHI, substitution will again lead to equation (22).


However, most of the metals that can be used for the purpose discussed are bivalent.

To determine whether equation (23) is valid in practice, an aqueous solution of


acetylacetone (about lO_aM) containing an approximately three-fold excess of copper(II) salt was titrated with sodium hydroxide. In this titration the reaction between
copper ions and the acid proceeds towards completion during the titration; therefore
the conditional constant Kgf will not be constant but will attain the calculated
value at the end of the titration. Nevertheless, an approximately straight line will
be obtained, and the intersection with the V axis will coincide with the equivalence
point.
The stability constant is KHfIA= IV.@, corresponding to KiH = 105.1. When
the appropriate values
= 1 + 10-1.51(j3.2
=
106.7
(25)

uA(Cu)

and
aOB~Cu~ f

1 + 10-1.5105.7= 104.?

(26)

are inserted, the conditional constant of the base formed will be


Ki,u =

ctA(CujKzH_ 10e*71051 lo,_6

-_Z

a0H(Cu)

104.2

(27)

This constant corresponds to an acid constant of 10s.4 which determines the shape
of the titration curve.0 The titration is thus a borderline case and could possibly
be accomplished with visual end point indication, were it not for the fact that copper
hydroxide begins to precipitate at pH very close to that at the equivalence point.
Furthermore, the colour of the copper compounds may affect the colour change of
the indicator.

F. INGMAN and E. STILL

1440

The titration results given in Table V and Figs. 6 and 7 are seen to be in good
agreement with the theoretically calculated values. The ionic strength in this titration
is not 0.1 but O-13. This, however, means a difference in the log fa value of only
O-01, which is neglected.
Figure 6 also illustrates the difficulties encountered when an attempt is made to
locate the equivalence point on a titration curve which is deformed by the precipitation of a metal hydroxide. The pH of the equivalence point is 5.0 andcopper hydroxide
begins to precipitate at pH N 5.2 (if the solubility product of copper hydroxide is
10-18.2,the point where precipitation should occur can be calculated to be pH N 5.6).
72
11

10

8
t
ri7
6

-v

FIG. 6.-Titration of 50 ml of 0.91 x 10-eM acetylacetone

(log K& = 8.9) containing

about a three-fold excess of copper


([C&t,,
= 0.04M) with O.lOOM SOCCU~
hydroxide. At the equivalence point the consumption is theoretically 4.55 ml.
TABLE V.-ACXTYLACETONECOMPLEXEDWITHCOPPER

log v, + V
V

p{W

CNsOH

o-0

2.63
2.76
2.93
3.19
3.38
3.66
4.30

2.70
2.71
2.72
2,73
2.73
274
2.74

1.0
2.0
3.0
3.5
4.0
4.5

log

1 -t- {J$KHA H,Aj

([HI - W-U)
1
1
1
1
1
1
1

-2.55
- 2.68
-2.85
-3.11
-3.30
-3.58
-422

+
+
+
+
+
+
+

lO-0.aa =
10-M =
10-0.88 =
10-0.84 =
10-L =
lO-X.01=
10-8.06 =

V, = 50 ml, log K& = 8.95, log Kcti = 8.2, log KcuOH = 5.7,
tLA(cu)= 6.7, log aOHICu,= 2.25, and log KziA = 2.25
logfn = -0.08, logfen = -0.12
H,A'
V,,

V=

VIWKHA

K, -

100.X
loo.*
100.08
100.06
100.08
1OwJa
100.00

000
0.31
0.42
0.35
0.26
0.16
0.04

+
+
+
+
+
+
+

200
1.41
089
047
029
0.15
0.03

[Cu] = 3 x lo-*

WI - [OHl)(l + {H)@iA)

v
=
=
=
=
=
=
=

200
1.72
1.31
0.82
0.55
0.31
0.07

gives log

Determination

Oo

of titration end-points

3
-v

1441

5 ml

FIG. 7.-Straight
line obtained when titration data plotted in Fig. 6 for a titration of
acetylacetone complexed with copper are used to calculate V,, - Vfrom e uation (231.
The intermediate and final results of the calculations are collected in Taa le V. The
straight line intersects the V axis at F = 4.63 ml, which corresponds to an error of
+1-s %.

EXPERIMENTAL
The experimental work was performed using a Metrohm Potentiograph E 336 recording potentiometer equipped with an EA 107 glass electrode and an EA 404 saturated calomel reference electrode.
All solutions were prepared from reagent-grade chemicals. Special care was taken to ensure that
the O~lOOM sodium hydroxide solution was free from carbonate.
The following procedure was
followed in the titrations:
A lO-ml sample of an approximately 5 x lo-*Macid solution was transferred to a W-ml beaker.
Any additions of other acids or metal salts were made and the solution was diluted to 50 ml after
the addition of sodium perchlorate to adjust the ionic strength to 0.1, The solution was titrated
with @lOOM sodium hydroxide solution with magnetic stirring at the slowest practical speed of
titration.
Esumb-On
propose une extension de la mdthode de Gran pour
determiner les points d%quivalence dam les titrages potentiometriques
acide-base. On dtduit des equations en supposant que les constantes
de stabilite des reactions sont connues. Les equations rendent possible
la localisation du point d&privalence avec une assez grande precision
lorsquon titre des acides dont les constantes de stabilite se situent
entre K$ N 10 et KS N lOlo. La limite de KL au-dessus
de laquelle les equations de Gran ne donnent pas de resultats satisfaisants est denviron 10. On utilise. des constantes conditionnelles et
des coefficients a atin detendre la mtthode pour lappliquer a des
systemes plus complexes, oh plus dune esp&ce reagit avec lagent de
titrage.
Zusammeafassnng-Es
wird eine Erweiterung der Granschen Methode
zur Bestimmung von Aquivalenzpunkten
bei potentiometrischen
+%ure-Basen-Titrationen gezeigt. Unter der Voraussetzung, daB die
Stabilitltskonstanten
der Rcaktionen bekannt sind, werden Gleichungep abgeleitet.
Die Gleichungen ermbglichen die Lokalisierung
des Aquivalenzpunktes mit ziemlicher Genauigkeit, wenn Stiuren mit
Stabilitiitskonstanten
von
K~A - 10 bis K& - lOlo titriert
werden. Die Grenze von K&, tiber welcher die Granschen Gleichungen keine zufriedenstellenden
Ergebnisse liefem, ist ungefahr 10.
Mediumabhangige
Stabilittbskonstanten
und a-KoefIizienten
zur
Erweiterung der Methode gebraucht, urn sie auf kompliziertere
Systeme anzuwenden, wo mehr als eine Spezies mit dem Titranten
reagiert.

1442

F. INGMANand E. SELL
REFERENCES

1.
2.
3.
4.
5.
6.
7.
8.
9.

G. Gran, Acta Chem. &and., 1950,4,559.


G. Gran, Analyst, 1952,77,661.
P. Sprrensen, Kern. Maanedsblad, 1951,32,13.
A. Ringbom, Complexation in Analytical Chemistry, Wiley/Interscience, New York/London, 1963.
I. M. Kolthoff and P. J. Elving, Treatise on Analytical Chemistry, Part I, Vol. 1, p. 242. Interscience,
New York, 1959.
A. E. Martell and L. G. Sillkn, Stability Constants of Metal-ion Complexes, Special Publication
No. 17. The Chemical Society, London, 1964.
J. A. Goldman and E. Meites, Anal. Chim. Acta, 1964,30, 28.
E. W&n&en, Tukzntu, 1963, 10,221.
B. Eklund and A. Ringbom, Finska Kemists. Medd., 1962,71, 53.