V. V. Korolev

The sorption isotherms of oleic, linoleic, and linolenic acids from solutions in cyclohexane and heptane on magnetite

The adsorption-desorption isotherms of oleic, linoleic, and linolenic acids from solutions in cyclohexane and heptane on the surface of magnetite were obtained by the equilibrium adsorption method. The adsorption of fatty acids was described in terms of the theory of volume filling of micropores. This theory was used to calculate the limiting adsorption values, characteristic energy, and volume of the pore space. In solutions in cyclohexane, the adsorption-desorption isotherm of oleic acid was situated above the isotherms of linoleic and linolenic acids. The situation was opposite with adsorption from heptane. The conclusion was drawn that the limiting adsorption and characteristic energy values increased from linolenic to oleic acid in adsorption from cyclohexane and decreased from linolenic to oleic acid in adsorption from heptane. The adsorption-desorption isotherms exhibited hystereses.

The magnetocaloric effect and the heat capacity of aqueous suspensions of porphyrin complexes of rare earth elements according to microcalorimetric data

The magnetocaloric effect (MCE) and heat capacity during the magnetization process of (5,10,15,20-tetraphenylporphyrinato)acetatogadolinium(III), (AcO)GdTPP, and (5,10,15,20-tetraphenylporphyrinato)chlorogadolinium(III) complexes, (Cl)GdTPP, in the form of 6%-aqeous suspensions are determined by the microcalorimetric method in a range of temperatures from 278 to 318 K and magnetic fields from 0 to 1 T. It is found that MCE for all the complexes are positive, i.e., at applying a magnetic field in the adiabatic conditions temperature of a suspension of complex increases. It is established that MCE increases with an increase in magnetic induction at all temperatures and decreases with an increase in temperature at all magnetic fields. It is shown that the substitution of chloride ligand by acetate in (X)GdTPP leads to a significant increas in MCE and its temperature dependence; in the case of (Cl)GdTPP actually MCE does not depend on temperature. Relationships between magnetothermal properties and structure of the complexes are analyzed. The conclusion is argumented that the reason of changes in magnetothermal properties after the replacement of axial ligand in gadolinium complexes and complexes of lanthanides with an unsymmetrically filled f-shell is non-planar geometry of the coordination site and specific electronic properties of the central ion. It is concluded that heat capacity of the complexes slightly increases with an increase in temperature and more noticeably in the case of (AcO)GdTPP; a magnetic component of heat capacity is revealed only in (AcO)GdTPP at temperatures above 298 K, which is connected perhaps with a temperature change in the crystal lattice of the complex and influence of the magnetic properties of gadolinium ion on this change.

Oleic acid adsorption-desorption isotherms on the surface of high-dispersity ferrites from a solution in carbon tetrachloride

The equilibrium adsorption method was used to comparatively study the adsorption-desorption isotherms of oleic acid on the surfaces of manganese and copper ferrites from a solution in carbon tetrachloride. The adsorption isotherms of the fatty acid were described in terms of the theory of volume filling of micropores. The theory was used to calculate the limiting adsorption values, characteristic energy, and porous space volumes. The isotherm of oleic acid adsorption on the surface of manganese ferrite from a solution in carbon tetrachloride was similar to the isotherms of fatty acid adsorption from solutions in heptane, whereas the isotherm of adsorption on the surface of copper ferrite was similar to the isotherms of fatty acid adsorption from hexane. The limiting adsorption from carbon tetrachloride was higher on the surface of manganese ferrite than on the surface of copper ferrite. The adsorption-desorption isotherms contained hysteresis loops.

Magnetocaloric effect and heat capacity of ferrimagnetic nanosystems: Magnetite-based magnetic liquids and suspensions

The magnetocaloric effect (MCE) and heat capacity of magnetite-based magnetic liquids and suspensions of magnetite in cyclohexane and water were studied calorimetrically at various temperatures and magnetic inductions. It was found that the magnetocaloric effect in the systems under study increases nonlinearly with the magnetic induction. In contrast to monocrystalline magnetite, the inverse temperature dependence was observed for the MCE in the nanosystems studied over the entire temperature range covered; i.e., the effect decreases with increasing temperature. It was found that the dependence of the specific heat on the magnetic induction passes through a maximum for all the systems at all temperatures tested; its height increases with the temperature. The extremal character of the dependence can be explained by the formation of chain structures of magnetite nanoparticles in the presence of a magnetic field.

A microcalorimeter for studying the magnetocaloric effect and the heat capacity in magnetic fields

The design of an automated microcalorimeter for determining the magnetocaloric effect and the heat capacity of suspensions and magnetic colloids in magnetic fields of from 0 to 1 T over a wide temperature range and the corresponding experimental procedure were described.

Magnetocaloric effect and heat capacity of high-spin manganese complexes in a disperse state

Magnetothermal properties of high-spin chloro(2,3,7,8,12,13,17,18-octaethylporphyrinato)manganese(III), chloro(5,10,15,20-tetraphenylporphyrinato) manganese(III), bromo(5,10,15,20-tetraphenylporphyrinato)manganese(III), and (acetato)(5,10,15,20-tetraphenylporphyrinato)manganese(III) complexes as 6% water suspensions were determined by the microcalorimetric method at 298 K in a magnetic field of 0–1.0 T. It was established that when the magnetic field was applied, the temperature of the systems increases, leading to positive values of the magnetocaloric effect: the higher the magnetic field induction, the higher the values. It is shown that the dependences of the heat capacity of the complexes’ solid particles on the magnetic field induction are of an extreme nature with a heat capacity in the area above 0.6 T less than that in the zero field. The regularities of the dynamics of the numerical values of the change in enthalpy and magnetic entropy of the manganese complexes when a growing magnetic field was applied and the regularities of the influence of the acidoligand in pentacoordinated complexes on their magnetothermal properties were considered.

Adsorption of naphthenic acid on magnetite at different temperatures

Isotherms of naphthenic acid adsorption from heptane solutions on highly dispersed magnetite are studied using the adsorption equilibrium approach. The isosteric heats of naphthenic acid adsorption from heptane solutions are calculated over a temperature range of 293–308 K. The adsorption isotherms can be approximated using the equation for a straight line. Experimental adsorption isotherms are shown to be linear in the coordinates of the equation for the theory of volume filling of micropores (TVFM).

The magnetothermal properties of substituted (tetraazoporphynato)manganese(III) in aqueous suspension

The magnetocaloric effect (MCE), heat capacity, and enthalpy and entropy of magnetization of the high-spin (acetato)(2,3,7,8,12,13,17,18-octa-para-tert-butylphenyltetraazaporphynato)manganese(III) complex in a 6% aqueous suspension were determined microcalorimetrically at 298 K in magnetic fields of 0.1–1.0 T, that is, under the conditions comparable with those used with (2,3,7,8,12,13,17,18-octaethylporphynato)chloromagnanese(III) studied earlier. High-dispersity complex particles were found to have paramagnetic properties. Positive MCE values were obtained. These values grew as magnetic field induction increased. MCE sensitivity to the nature and electronic structure of the aromatic macroring was studied. The presence of aza groups in the structure of the complex decreases the MCE value compared with the porphyrin complex. The specific heat capacity of the complex strongly depended on the magnetic field value; field dependences had a maximum close to 0.3 T. Changes in the ΔSm(H, T) molar entropy part were also extremal and had maxima at 0.3–0.4 T. Prospects for the use of magnetothermal properties in the quantitative determination of thermodynamic characteristics and for revealing trends of changes in the magnetic activity of porphyrin complexes are discussed.

Magnetocaloric properties of dendrimer complexes of Fe(III) with substituted Schiff base

ABSTRACT In dendrimer complexes of iron (III) with Schiff base (three complexes of iron (III) based on azomethine 4,4′-dodecyloxybenzoyloxybenzoyl-4-salicylidene-2-aminopyridine, a significant magnetocaloric effect (MCE) and heat capacity was found the first time. It was found that the magnitude of MCE depends on the nature of the counter-ion of the complex. MCE were measured with a microcalorimeter over the temperature range of 278–320 K and in a magnetic induction of 0–1.0 T. The temperature dependences of the MCE dendrimer complexes of iron (III) with Schiff base were obtained for the first time. For all the samples studied, the existence of extreme temperature dependence of MCE in the range of temperatures 300–350 K, which is possibly the result of the magnetic phase transition, is shown. The correlation between the thermotropic mesomorphism with the magnetic phase transition in complexes has been established. Graphical Abstract

The Magnetocaloric Effect and Heat Capacity of Suspensions of High-Dispersity Samarium Ferrite

The magnetocaloric effect and specific heat capacity of an aqueous suspension of samarium ferrite were determined calorimetrically over the temperature range 288–343 K in magnetic fields of 0–0.7 T. The data obtained were used to calculate changes in the magnetic component of the molar heat capacity and entropy of the magnetic phase and changes in the enthalpy of the process under an applied magnetic field. The magnetocaloric effect was found to increase nonlinearly as the magnetic field induction grew. The corresponding temperature dependences contained a maximum at 313 K related to the second-order magnetic phase transition at the Curie point. The field and temperature dependences of heat capacity contained a maximum in fields of 0.4 T and a minimum at the magnetic phase transition temperature.