СЕКЦИЯ 4. «ГИБРИДНЫЕ НЕОРГАНИЧЕСКИЕ И ОРГАНО-
НЕОРГАНИЧЕСКИЕ ЗОЛЬ-ГЕЛЬ МАТЕРИАЛЫ»
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member equations of TVFM and at this date calculated by equations are in good correlation with
experimental data.
By equation of Gibbs-Gelmgolz the molar differential entropy of water adsorption in hybrid
nanocompositional materials DAC-silica and PAN-silica was calculated.
Values of the molar
differential entropy have shown that station of water on surface is ice-similar (entropy of ice – 26
J/mole∙K). Middle molar integral entropy of water adsorpted on surface of DAC-silica has equaled –
70,3 J/mole∙K and for PAN-silica it has equlaled -36 J/mole∙K. Value of the midde-molar integral
entropy for DAC-silica has indicated on the fact that mobility of molecules of adsorbited water is
strongly braked in hybrid nanocomposite and in case of PAN-silica has approached to value of ice
entropy.
The isotherm of water adsorption in PAN-silica hybrid nanocomposite materials is satisfactory
and fully described by the three-term equation of TOZM:
а= 0,365 ехр [-(A/13,93)]
4
+ 2,893 exp [-(A/4,08)]
2
+ 0,625 exp [-(A/0,59)]
Parameters of the equation:
the fraction of the first term a
01
= 0.365 mmol/g, E
01
= 13.93 kJ/mol, n
1
= 4;
for the second term a
02
= 2.893 mmol/g, E
02
= 4.08 kJ/mol, n
2
= 2;
for the third term, a
03
= 0.625 mmol/g, E
03
= 0.59 kJ/mol, n
3
= 1.
The TVFM equation could be considered
as three-dimensional, where the water molecule is
firmly located in the pore space of the hybrid PAN-silica nanocomposite. The high initial energy and
high energy level of the interaction of water with nanocomposites indicate that water molecules
adsorbed on a PAN-silica hybrid nanocomposite
are in an ice-like state, which indicates inhibition of
adsorbed water molecules. Further, water molecules adsorbs on nanocomposites with relatively low
energy forms clusters, located on the surface of a PAN-silica hybrid nanocomposite.
The three-term
equation of TOZM describes the main region of adsorption by high values degree under the exponent,
indicating a high uniformity of the sorption system [8,9].
TVFM involves three adsorption mechanisms: approximately 85% of the sorption space of
hybrid nanocomposites is filled by the first mechanism, then filling another part of the sorption space,
which differs from the first, by adsorption interaction.
The use of the method for compensating heat fluxes by the Peltier allows to increase the
accuracy of measuring the adsorption heat by more than an order of magnitude. Adsorption
measurements were carried out on a universal high-vacuum volumetric equipment,
which made it
possible to carry out adsorption measurements and dosage of the adsorbate with high accuracy.
Thus isotherms and differential heats of water adsorption by hybrid nanocompositions
polymer – silica have been investigated. Precizional adsorptionno – calorimetrical installation was
used. This installation besides thermodinamical characteristies has given full information about
physical, chemical and crystallo-chemical nature of adsorbent surface and also about mechanism and
thermokinetics of adsorption and state of adsorbate in matrixe of adsorbent. Isotherms were treated by
equations of theory of volume filling of microporuse. Isotherm of
water adsorption in hybride
nanocompositional materials is described in good degree by equation of TVFM
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