Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 3, pp. 398−403.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © D.A. Novikov, Yu.G. Dobryakov, N.A. Smirnova, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86, No. 3, pp. 429−434.
AND INDUSTRIAL ORGANIC CHEMISTRY
Distribution Coefﬁ cients
between Aqueous and Hydrocarbon Liquid Phases
D. A. Novikov, Yu. G. Dobryakov, and N. A. Smirnova
St. Petersburg State University, St. Petersburg, Russia
Received December 28, 2012
Abstract—Gas-liquid chromatography was used to study the distribution of 2,2-dimethyl-4-hydroxymethyl-1,3-
dioxolane between aqueous and organic liquid phases for seven binary solvents water–hydrocarbon (n-heptane,
n-octane, n-decane, benzene, toluene, p-xylene). The distribution coefﬁ cients at low solute contents were measured
in the temperature range 283–313 K. In all the systems, the ratio between the solute concentrations in the organic
and aqueous phases is substantially smaller than unity and grows with increasing temperature. The ratios between
the limiting activity coefﬁ cients of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane in the hydrocarbon and aqueous
phases were estimated.
Experimental studies of the distribution coefﬁ cients
of organic substances between liquid layers of
stratifying aqueous-organic mixtures are necessary for
analysis of extraction processes in systems with organic
solvents of various classes, development of analytical
procedures and various technological processes
involving extraction, concentration, separation, and
identiﬁ cation of substances. The nature of a substance
distribution between immiscible solvents is directly
related to differences in the interaction of solute and
solvent molecules. Evidence concerning the distribution
coefﬁ cients is of great interest for physical chemistry
of solutions. Data on the distribution coefﬁ cients can
be used to obtain information about thermodynamic
characteristics, such as ionization, hydration, and
association constants and activity coefﬁ cients.
Numerous articles and monographs concerned with
the fundamental aspects of interphase distribution
processes (e.g., [1, 2]) and reference books on distribution
coefﬁ cients [3–5] have been published. Of special
interest are improvement of methods for determining
the distribution coefﬁ cients and development of
simple, sufﬁ ciently precise, and versatile procedures
for this purpose. Chromatographic analysis methods
are advantageous in being more versatile and providing
an additional information about presence of impurities,
formation of emulsions, and occurrence of hydrolysis
and other chemical reactions. The capacity of direct
chromatographic analysis of equilibrium coexisting
phases has been employed previously to determine the
temperature dependence of the distribution coefﬁ cients
of phenol between water and hydrocarbons .
The cyclic ketal 2,2-dimethyl-4-hydroxymethyl-1,3-
can be synthesized from glycerol and acetone [7, 8].
This water-soluble high-boiling oxygen-containing
cyclic compound is promising, in particular, as an anti-
icing agent and a component of motor fuel additives
raising the octane rating and making less possible the