Professional Documents
Culture Documents
Determination of The Equivalence Point in
Determination of The Equivalence Point in
SUMMARY
When the potential - volume curve obtained during potentiometric
titrations shows only a small potential change a t the end-point, it has been
customary to plot a AE/AV - volume curve and to take the peak of this curve
as the equivalence point. In 1950 the author proposed a method of trans-
forming these curves by a numerical manipulation into straight lines
intersecting a t the equivalence point. In this paper another way of trans-
forming titration curves into straight lines has now been developed.
A simple theoretical treatment shows that the method can be applied to
titrations involving acids and bases, ionic precipitations formation of com-
plexes, and oxidation - reduction reactions. To facilitate the use of the
method a table has been compiled giving quantities to be calculated and
plotted against volume of titrant added. These quantities can be evaluated
by simple slide rule calculations and, since straight line relationships hold,
end-points can be obtained by simple extrapolation.
The practice of the method is applicable to potentiometers calibrated
either in millivolts or in pH units, even when titrations other than acid - alkali
reactions are in use.
R ~ ~ s u M ~
Quand la courbe potentiel - volume obtenue au cours des titrages potentio-
mktriques ne montre qu’un petit changement de potentiel a u point d’kquiva-
lence on a l’habitude de tracer la courbe AE/AV-volume et d’appeler le
sommet de cette courbe le point d’kquivalence. En 1950 l’auteur a..ait
proposk une mt’thode pour transformer, par une faqon de calcul, ces courbes
en lignes droites s’entrecoupant au point d ’Cquivalence. Dans ce rapport
une autre manizw a k t 6 dheloppee pour transformer ces courbes de titration
en lignes droites.
Un traitement thkorique simple dkmontre que cette mkthoae peut etre
appliquke au titrage d’acides et bases, aux prkcipitations ioniques, B la
formation de complexes et & l’oxydimktrie. On a compilk un tableau, afin de
faciliter l’emploi de la mkthode, donnant les quantitks 2~ calculer et & tracer
contre le volume de solution titrante. Ces quantitks peuvent Btre calculkes
simplepent B l’aide d’une rhgle A calcul, et on peut obtenir les points d’kquiva-
lence simplement par l’extrapolation, puisqu’il existe une proportionnalit6
directe.
On peut se servir d’un potentiomhtre graduk en unitks de pH aussi bien
qu’en millivolts, meme quand les titrages envisagks ne sont pas limitks B la
neutralisation d’acides et bases.
ZUSAMMENFASSUNG
Wenn die bei der potentiometrischen Titration erhaltene Potential -
Volumenkurve nur eine geringe Potentialanderung beim Neutralpunkt
aufweist, so war es ublich eine AE/AV - Volumenkurve aufzutragen und
den Scheitel dieser Kurve als Aquivalenzpunkte anzusprechen. Im Jahre
1950 hatte der Verfasser eine Methode vorgeschlagen, diese Kurven rechnerisch
in Gerade umzuwandeln, die sich im Aquivalenzpunkt schneiden. Im
For details of part I of this series (not in The A m l y s t ) see reference list, p. 670.
View Article Online
NEUTRALISATION
TITRATIONS
STRONG ACID - STRONG BASE-
If V,ml of a strong acid, with original concentration in gram-equivalents per litre of
CA,is titrated with a strong base of concentration CB,the concentration of hydrogen ions,
after the addition of V ml of base, will be-
1,’o -c.i T/
which can be transformed to-
+
(Vo V)l0-PR JIr* x C,(V, - V ) , . .
I= .. .. (6)
or more generally to-
+
(V, T/)1041--DH = k,(V, - V ) , .. .. .. (7)
where k, and k, are constants including the activity factor, which, in most instances, can be
considered constant during a titration.
When the equivalence point has been passed-
- cB
vo+ v (V - V,) .. .. .. ..
and further-
Smensen did not make any correction for the increase in volume of the solution during
the titration and did not obtain linear graphs. This correction is, however, easily made in
the same way as in conductimetric titrations, as can be seen in equations (7) and (11) above.
Volume. rnl
An example of a titration of a strong acid with a strong base is shown in Fig. 1, and it is
evident that the straight lines obtained by applying the correction for the volume increase
make the determination of the equivalence point much more reliable.
View Article Online
V oml of a weak acid, HA, with original concentration CA,is titrated with a strong base
of concentration C,. For weak acids-
a=* = k a - ,
CE.4
c*t
.. .. .. .. .. .. (12)
where-
and c,.yo
=-
cB
+ v v. . , I .. .. .. ** .* (la)
CA"
.. .. .. .. .. ..
(18)
where
In determining the first equivalence point this equation should be used in the form-
(Ve2- V)lOpE-k~ = k, (V -- Vel) . . .. . ..
(23) .
and for the second equivalence point equation (22) is rewritten to give-
(V - Vel) 10kn-PH= kl, (V,,, - V)* .. .. .. (24)
The use of equation (23) presupposes knowlledge of the second equivalence point, Ve2,
but as for this purpose V,, need not necessarily be known exactly, it may be estimated
with sufficient accuracy directly from the titration curve.
The use of equation (24) in the same way requires knowledge of the first equivalence
point, Ve,,which, however, is usually determined before the second equivalence point.
View Article Online
As seen from equations (17) (23) and (24) the correction factors influence the results
much more for weak acids than for strong acids. This is illustrated in Fig. 2, where the
curves obtained by the Sarensen method and by the proposed method are shown. I t is
evident that the former curves are noticeably non-linear, while the latter pair are linear.
Volume. ml
For polymeric weak acids, e g . , polymethacrylic acid, Katchalsky and Spitnik4 have
shown that the titration curve follows the generalised Henderson - Hasselbach equation-
1-u
pH = pk, - n log ~
J * ’ .. .. .. .. (25)
or .. .. .. .. .. (25a)
(v)n
With the same nomenclature as before] the following equations are obtained:
a=. = k, .. .. .. .. .. .. (26)
and
antilog (-pH) = = k, (->”, .. .. .. (27)
ION-COMBINATION TITRATIONS
PRECIPITATIONTITRATIONS-
When V , ml of a solution of a substance (A), with original concentration Clo, is titrated
View Article Online
+
X A yB = A,B, . .. .. .. .. . .
I. (29)
As long as A is present in excess:
..
.. .. .. .. (30a)
.. (31)
.. .. .. .. (31a)
or .. .. .. .. (334
v o +v
View Article Online
When x = y = n, = 1, equations (35) and (39) are analogous to equations (7) and (ll),
respectively .
If the potential is controlled, not by the concentration of A, but by the concentration
of B, it can be shown that the equations-
Y
(V, + V ) x 102x17n~(k17-E)
= k,, (Ve - V ) .. .. .. (40)
and
+
(V, V ) x 1017”B(E-k19) = k,, (V - V e ) .. .. .. (41)
hold before and after the equivalence point, respectively.
COMPLEX-FORMATION TITRATIONS-
When V , ml of a solution of a substance A, with original concentration Cd,,is titrated
with a solution of a substance B, of concentration CBoa complex is formed according to the
reaction-
X A+ yB = A,$,. .. .. .. .. .. ..
The extent to which this reaction proceeds is given by the relationship-
cz,cy, =I K,, .. .. .. .. .. .. ..
CAzRV
c* -- y- x - V , + V
cBo (Vo+ V ) .. .. .. .. ..
This equation leads to the resul s (34)and (35)in the preceding section.
When B is present in excess-
.. .. .. ..
and .. .. .. ..
Equations (36a), (43) and (44) together give-
r CB,IJe 1;
.. .. .. ..
L v,+v_l
which, together with (33c), gives-
.. .. .. ..
.. ..
.. ..
View Article Online
or, if x = 1-
V x 1 0 X~17ng(kz.r- E ) = k2s(V - Ve) -- .. .. .. (48a)
hold before, and equation (41) after, the equivalence point is reached.
When V oml of a solution of a substance A in its reduced state, with original concentration
CA, is titrated with a solution of a substance 13 in its oxidised state, of concentration CB,
the following reactions take place in the solution-
.. ..
and
.. ..
Up to the equivalence point-
cA,x =
%3
-x-
nA v~+ v
cB .. .. .. .. ..
and
.. .. ..
.. ..
The potential is given by-
.. ..
which, by analogy with equation (31), can be rewritten to give-
.. .. ..
Equations (51), (52) and (54) together give-
V-
vo+ v - K", x 1 0 1 7 n ~ ~ , ..
-- .. .. .. ..
which can be transformed to the more general form-
V x 10'' " ~ ( ~ 2 9 - = ,, (V,
~ ) k -V) .. .. .. ..
When the equivalence point has been passed-
.. .. ..
.. .. ..
and
.. .. ..
-
-- cB ( V - VJ. .. .. .. .. ..
vo+ v
By analogy with equation (54)-
.. .. ..
View Article Online
DISCUSSION
Many rather complicated expressions have been put forward in the preceding theoretical
section and it may be thought that considerable work would be involved in using the proposed
method for finding the equivalence point. In most instances, however, all the calculations
required can be made with the help of a slide rule. Further, if the dilution during the titration
is negligible, the correction for the dilution can usually be dispensed with. For weak
electrolyte systems-titrations of weak acids and bases, complex formation and redox
titrations-the correction factor should preferably be included. Most trouble is experienced
in complex-formation titrations in systems of the type-
where x f y f 1, and in such systems, the method developed previously1 is often simpler.
The great advantage of both these methods is that they lead to linear graphs, which can
be extrapolated if necessary.
APPENDIX
EXPRESSIONS
TO BE CALCULATED AND PLOTTED AGAINST VOLUME V
OF TITRANT ADDED
Corrected form giving
Titration Simple form straight lines
A. STRONGACID - STRONG BASE-
1. Before end-point . . 1Ok-p” (V,+ V ) x 1 O k - P R
,.
2. After end-point 10PH-k +
(V, V ) x
B. WEAKACID - STRONG BASE-
(a) Monobasic acid-
1. Before end-point . . A.l V x 10k-pH
2. After end-point .. A.2 A.2
(b) Dibasic acid-
1. Before 1st end-point A.l B (41
2. After 1st end-point . . A.2 (Ve2- V ) x l o p H
3. Before 2nd end-point A.l (V - V e J x 10’‘ ~ pH
4. After 2nd end-point A.2 A.2
View Article Online
2. After end-point ..
10 17 ng ( k - 2 0
2. After end-point 10 nB (k - “pH”
REFERENCES
1. Gran, G., Acta Chem. Scand., 1950, 4, 559.
2. Sarensen, P., Kern. Maanedsbl., 1951, 32, 73.
3. Ssrensen, P., private communication.
4. Katchalsky, A., and Spitnik, P., J . Polymer Sci., 1947, 2,432.
NOTE.-ReferenCe 1 is to part I of this series.
DEPARTMENT CHEMISTRY
OF ANALYTICAL
SWEDISH
FORESTPRODUCTSRESEARCHLABORATORY
STOCKHOLM0, SWEDEN ApviZ 2 1 4 1952
View Article Online