ISSN 1061-933X, Colloid Journal, 2006, Vol. 68, No. 6, pp. 757–760. © Pleiades Publishing, Inc., 2006.
Original Russian Text © A.G. Ramazanova, V.V. Korolev, E.V. Ivanov, 2006, published in Kolloidnyi Zhurnal, 2006, Vol. 68, No. 6, pp. 829–832.
757
INTRODUCTION
It has been shown earlier [1, 2] that, upon the
adsorption of oleic, linolic, and linolenic acids on finely
dispersed magnetite from solutions in n-hexane and
carbon tetrachloride, molecules of solute and solvent
compete for the active sites on the adsorbent surface. In
this case, the decisive effect on the adsorption of afore-
mentioned unsaturated fatty acids (UFAs) is imparted
by the number of double bonds in their molecules, as
well as by the desolvation of adsorbent surface and
adsorbate molecules. With allowance for the latter cir-
cumstance, the conclusion drawn in [2–4] that, upon
the passage from one solvating medium (n-C
6
H
14
) to
another (CCl
4
), the inversion occurs in the sequence of
the position of isotherms of adsorption on magnetite for
this series of acids, seems to be most interesting. For
example, upon the adsorption from carbon tetrachlo-
ride (hexane) solutions, the values of limiting adsorp-
tion a
m
, characteristic energy of adsorption E
a
, and vol-
ume of porous space V
p
of magnetite increase
(decrease) in the oleic, linolic, and linolenic acids
series.
Evidently, the effect of the nature of apolar solvent on
the processes occurring on the ferroparticle surface is
directly related with the specific features of intermolecu-
lar interaction between the adsorbate and solvation envi-
ronment. At a macroscopic level, these features are
exhibited in the thermodynamic characteristics of disso-
lution (solvation) of UFAs. The most important among
them are the volumetric or packing effects that depict
structural changes in a solvent due to the desolvation of
acid molecules and the formation of UFA–n-C
6
H
14
(CCl
4
) solvation complexes with different sizes (vol-
umes) and compositions [5, 6]. The elucidation of corre-
lations in changes of adsorption and partial volumetric
characteristics of studied UFAs in n-hexane and tetra-
chloride should promote the understanding of processes
that are responsible for the stability and efficiency of dif-
ferent magnetite-containing colloidal systems.
In this work, we analyzed volume effects of dissolu-
tion (solvation) of oleic, linolic, and linolenic acids in
n-C
6
H
14
and CCl
4
at 298.15 K to establish interrelations
between these thermodynamic parameters and adsorp-
tion properties of studied UFAs on the surface of finely
dispersed magnetite.
RESULTS OF EXPERIMENTS
AND CALCULATIONS
We used n-hexane, high purity grade, and tetrachlo-
ride, special purity grade, additionally purified from
admixtures by the corresponding procedures [7, 8]. The
purity of solvents was verified by the IR spectrometry (in
cells made of CaF
2
) and densimetry. Densities of sol-
vents (n-C
6
H
14
and CCl
4
) prepared for experiments were
equal at 298.15 K to 0.655195 and 1.584995 g cm
–3
,
respectively, that is well consistent with reliable pub-
lished data [9].
Oleic, linolic, and linolenic acids (with general
structural formula C
18:n
, where n is the number of C=C
bonds in cis-9-, cis-6-, and cis-3- positions with respect
to “end” methyl group) were purified in accordance
with the procedure described in [3] to the residual con-
tent of impurities of no higher than 0.1 wt %. The qual-
ity of UFAs was estimated by the integral intensity of
IR absorption bands in thin films on plates made of
KRS-5. Data on the properties and structure of acids
studied are listed in Table 1.
ρ
1
*
Interrelation between Parameters of Isotherms of Adsorption
of Fatty Acids on the Surface of Magnetite and Volume Effects
of Their Dissolution in n-Hexane and Carbon Tetrachloride
at 298.15 K
A. G. Ramazanova, V. V. Korolev, and E. V. Ivanov
Institute of Chemistry of Solutions, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045 Russia
Received March 15, 2006
Abstract—The adsorption of unsaturated C
18:n
fatty acids on magnetite and volume effects of their dissolution
in n-hexane and carbon tetrachloride are studied. It is established that an increase in the values of limiting
adsorption of a series of oleic, linolic, and linolenic acids corresponds to positive volume effects of their disso-
lution in CCl
4
. Opposite picture of the adsorption behavior of studied acids in n-hexane corresponds to negative
volume effects of the dissolution of the acids in this solvent.
DOI: 10.1134/S1061933X06060135