ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2017, Vol. 91, No. 12, pp. 2366–2369.

© Pleiades Publishing, Ltd., 2017.

Original Russian Text © S.S. Lysova, T.A. Skripnikova, Yu.E. Zevatskii, 2017, published in Zhurnal Fizicheskoi Khimii, 2017, Vol. 91, No. 12, pp. 2072–2076.

PHYSICAL CHEMISTRY
OF SOLUTIONS

Algorithm for Calculating the Dissociation Constants

of Weak Electrolytes and Ampholites in Water Solutions
S. S. Lysovaa,*, T. A. Skripnikovaa, and Yu. E. Zevatskiia,b,c
a
St. Petersburg State University of Industrial Technologies and Design, St. Petersburg, 191186 Russia
b
AO Novbytkhim, Gatchina, 188304 Russia
c
St. Petersburg State Electrotechnical University (LETI), St. Petersburg, 197376 Russia
*е-mail: lusovass@mail.ru
Received December 19, 2016

Abstract—An algorithm for calculating the dissociation constants of weak organic acids and bases in water
solutions is developed on the basis of spectrophotometric data on the UV and visible regions without mea-
suring the рН of the medium or using buffer solutions. The proposed algorithm is tested experimentally for
six single-base acids and single-acid bases of different strengths. The relative error in determining the disso-
ciation constants does not exceed 5% and is in agreement with the literature data.

Keywords: thermodynamic dissociation constant, spectrophotometry, UV/visible region, weak electrolytes,

water solutions
DOI: 10.1134/S0036024417110139

INTRODUCTION ered to be close to ideal, so the values of concentration

Multiwave spectrophotometric pH titration is cur-
rently used in combination with different approaches
to processing experimental data for determining disso-
ciation constants pKa of different organic acids and
bases. In many works, authors use MCR-ALS, PLS
and PCR, SPECFIT and SQUAD [1–4], and other
approaches and programs [5, 6]. In all of these works,
however, dependences A (optical density)/pH, nor-
mally obtained by taking the spectra of an investigated
compound at one concentration in a number of buffer
solutions with different рН values at a constant ionic
strength, were used as the primary experimental data.
The accuracy of determining pKa thus depends not
only on the approach used to process the spectropho-
tometric data but also on the error of pH measure-
ment.
In the method proposed in this work, dependences
А (optical density)/C (the concentration of a weak
electrolyte), obtained by recording the spectra of an
investigated compound at different concentrations
with the addition of a strong acid (base), are used as
the primary experimental data. It should be noted that
during an experiment, the concentration of the strong
electrolyte is constant and is normally an order of
magnitude lower than the concentration of the inves-
tigated weak electrolyte (in many cases, it is no higher
than 10–3 mol/L). Intermolecular interactions and
association in solutions with very low ionic strength
(I → 0) are usually ignored; such solutions are consid-
constants coincide with those of thermodynamic con-
stants. Compared to standard spectrophotometric pH
titration, the proposed technique thus has a number of
advantages.
• It does not require measuring the рH of the
medium.
• It does not require the use of buffer solutions
with constant ionic strength.
• It does not require introducing corrections for
ionic strength according to the Debye–Hückel,
Stokes–Robinson, or other equations.
• It allows us to perform simple, time-effective
experiments.
THEORETICAL
In this work, we propose a new algorithm for calcu-
lating thermodynamic dissociation constants p K aT
(p K bT ) for weak single-base acids and single-acid bases
in water solutions. A schematic of the algorithm is
shown in Fig. 1.
The protolytic equilibrium of a weak electrolyte is
characterized by a thermodynamic dissociation con-
stant. For a single-base acid, it is
K a = a A − aH+ / aHA ,
T
for a single-acid base, it is

2366
 ALGORITHM FOR CALCULATING THE DISSOCIATION CONSTANTS 2367

Single-base acid AH Single-acid base B

AH + H2O  A− + H3O+ B + H2O  BH+ + OH−
2H2O  H3O+ + OH− 2H2O  H3O+ + OH−

Determined experimentally: εi, εAH, εA− Determined experimentally: εi, εB, εBH +

αi < 0.2 0.2 # αi # 0.8 αi > 0.8

AH + H2O  A− + H3O B + H2O  BH+ + OH− AH + H2O  A− + H3O+ B + H2O  BH+ + OH−
YOH → Y+ + OH− HX → H+ + X− HX → H+ + X YOH → Y+ + OH−
AH + H2O  A− + H3O+
or
B + H2O  BH+ + OH−
CYOH(HX) Ks (1 − αi ) Ka (b ) (1 − αi ) K a (b ) CHX(YOH) Ks
Cith = − + (5) Cith = 2
− − (6)
αi K a( b) (1 − αi ) αi2 αi αi K a (b ) (1 − αi )
K a (b ) (1 − αi ) Ks
Cith = − (4)
αi2 K a (b ) (1 − αi )

S= ∑ (C i
ex
− Cith ) 2 → min

∂S ⎛ Ks 1 − αi ⎞
∂K a (b )
= ∑ (C i
ex
− Cith ) ⎜ 2
⎜ K a (b ) (1 − αi )
+
αi2
⎟=0
⎟
⎝ ⎠

( )
K aT , K bT

Fig. 1. Algorithm for calculating p K aT(b) of a monobasic acid or a single acid base in water solutions.

K b = aBH+ aOH − / aB ,
T
The value of thermodynamic constant K aT of the
single-base acid or K bT of the single-acid base is found
where a A− , aH+ , aOH
− +
, aAH, aBH , aB are the activities of numerically using a unique equation obtained from
the corresponding particles. the law of electroneutrality and Ostwald’s equation:
The extent of the dissociation of an investigated
compound in ith solution αi is determined for a single- ⎛ 1 − αi ⎞
∑ (C
K
− C ith ) ⎜⎜ 2 s
i
ex
+ 2 ⎟⎟ = 0, (3)
base acid as
i ⎝ K a( b ) (1 − α i ) α i ⎠
ε i − ε AH where Ks is the constant of the autoprotolysis of water;
αi = . (1)
ε A − − ε AH C iex is the experimental molar concentration of the ith
For a single-acid base, solution of the investigated compound, mol/L; and
C ith is the calculated molar concentration of the ith
α i = (ε i − ε B )/(ε BH+ − ε B ) , (2)
solution of the investigated compound, mol/L.
where εAH, εB, and ε −A , ε BH
+
are the molar absorption The values of molar concentrations C ith are calcu-
coefficients of the nonionized and ionized forms of the lated as a function of the nature of the investigated
molecule, respectively; εi is calculated according to the compound and the conditions under which the exper-
Bouguer–Lambert–Beer law iment is performed.
ε i = Ai /( C i l ), If the extent of the dissociation of the weak single-
base acid (single-acid base) varies in the interval of
where Ci is the molar concentration of the ith solution 0.2 ≤ αi ≤ 0.8, the dispersion of the relative deviations
of the investigated compound, mol/L; Ai is the optical
density the investigated compound; and l is the length in experimental values C iex of molar concentrations
of the optical layer, cm. from calculated values C ith is minimal. The values of

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 91 No. 12 2017