Anomalies in the thermodynamic properties of mixtures near the liquid-vapor critical point

The behavior of the specific heat at constant volume and the derivative (?P/?T)_{ρ, x} has been studied experimentally near the liquid-vapor critical point of the methane-propane-pentane mixture. It has been shown that the derivative ?P/?T)_{ρ, x} for mixtures, in contrast to one-component systems, has a characteristic anomaly directly associated with an anomaly in the specific heat at constant volume. It is impossible to distinguish between the infinite increase in the specific heat or finite peak when processing of the experimental data only for the heat capacity. However, according to the joint analysis of the experimental data for both indicated quantities, both the specific heat of the mixture and the derivative ?P/?T)_{ρ, x} are singular finite quantities.     

Heat capacity anomaly in the vicinity of the tricritical and upper critical points

The anomalous behavior of the isochoric heat capacity of a mixture of methane, pentane and heptane is studied experimentally in the vicinity of the liquid-vapor critical point in the cases when (a) the critical temperature T _c approaches the tricritical point T _TCP and (b) the critical temperature approaches the upper critical end point T _U . It is shown that in all cases, the singular part of the heat capacity of the mixture has the form C_sing=A¦τ¦^?α, where τ=(T ? T _c )/T _c and α≈0.11. When T _c →T _U , amplitude A of the heat capacity anomaly is found to be approximately constant. At the same time, the amplitude of the anomaly tends to zero in the vicinity of the tricritical point: A∝¦τ_c¦^ε, where τ_c=(T _c ? T _TCP )/T _TCP and ε=1.6?1.7. The inevitable vanishing of this mode of the heat capacity anomaly leads to a negative value of the critical index \(\tilde \alpha\) characterizing the heat capacity anomaly at the tricritical point, while the tricritical point theory and the isomorphism hypothesis predict \(\tilde \alpha = 0.5\).     

Thermodynamic properties of multicomponent mixtures near the liquid-vapor critical point

A new method has been proposed to describe the physical properties of multicomponent mixtures near their critical points. The method is based on the transition from the experimental thermodynamic variables to scaling fields, is applicable to a mixture with any number of the components, and is, thus, universal. For the previously studied methane-propane-pentane mixture, it has been shown that the anomalies of the specific heat at a constant volume and derivative (?P/?T)_ρ,x can be quantitatively described in this approach in a wide vicinity of a critical point, including noncritical isochores.     

Heat capacity of the La<Subscript>0.9</Subscript>Ag<Subscript>0.1</Subscript>MnO<Subscript>3</Subscript> manganite near the curie temperature

The heat capacity of the La_0.9Ag_0.1MnO₃ manganite is measured in the temperature range 77–350 K and studied in detail in the vicinity of the Curie temperature for the first time. The regularities of the variation in the universal critical parameters in the vicinity of the phase transition point are established. The critical exponent and the amplitude of the heat capacity are calculated to be α = ?0.127 and A ⁺/A ^? = 1.146 with due regard for the scaling corrections. These parameters correspond to the critical behavior within the three-dimensional Heisenberg model. The size of ferromagnetic droplets in the paramagnetic range at T > T _C is estimated as ξ ≈ 19 Å. The results obtained are analyzed thoroughly and compared with theoretical data for a number of model systems.     

Anomalous critical behavior of NaV2O5

The temperature dependences and critical behavior of the dielectric constant were studied in NaV₂O₅ along the c axis in a frequency range of 1 MHz-1GHz and a temperature range of 4.2–300 K. An analysis of the data obtained, along with literature data on the heat capacity, magnetic losses, and the ultrasound velocity, indicates that the various physical quantities demonstrate similar temperature dependences in the vicinity of the transition, which corroborates the conclusion on the universality of the critical behavior in NaV₂O₅. Deviations from the predictions of the standard theory of second-order phase transitions were found, such as the asymmetry of the critical behavior above and below the transition and the presence of an anomalous base line.     

Heat capacity of a Cr2O3 antiferromagnet near the critical temperature

The heat capacity of a Cr₂O₃ antiferromagnet near the critical temperature is precisely measured by ac calorimetry. The critical behavior of the heat capacity is examined. The regularities of variations in the universal critical parameters near the critical point are determined, and their values are calculated. A crossover from the Heisenberg (n=3) to the Ising (n=1) critical behavior is revealed.     

Magnetic Anisotropy and Hidden Martensitic Transition in V3Si

Magnetization, electrical resistivity and heat capacity have been measured on a single crystal V₃Si in the range of (2-25) K and in magnetic field up to 14 T. A different behavior of magnetization for two orientations of the crystal has been found. In one orientation the magnetization displays a clear ferromagnetic character and below T _c coexistence of ferro-magnetism and superconductivity with a peak-effect in the vicinity of upper critical field H _c2. The specific heat measurements show sharp lambda anomaly corresponding to a transition to superconductive state and an additional anomaly around 15 K when applied field suppresses the superconductivity below this temperature.     

Thermodynamic and magnetic properties of LaSn3

Thermal expansion coefficient between 77 and 900K, isothermal compressibility in the 0–80 Kbar pressure range, magnetic susceptibility between 77 and 1300 K and heat capacity at constant pressure in the 20–300 K temperature range were determined for the LaSn₃ compound. From the experimental data, the specific heat at constant volume was calculated and the thermal dependence of the Debye's parameter θ_D was obtained. The electron contribution to the heat capacity was also determined from the high temperature data. The magnetic properties confirm that there is no evidence of the existence of a magnetic moment localized on La atoms, in contrast with a previous report and in agreement with the general assumptions. A little anomaly found in the expansion coefficient, in the isothermal compressibility and in the specific heat is discussed in terms of a lattice order-disorder phenomenon.     

Properties of the adsorption layer in a binary liquid mixture near the critical point

A method for the determination of parameters of the surface layer (thickness and refraction index) at the liquid-vapor interface in binary liquid mixtures was developed. The parameters of the surface layer for the C₇H₁₄-C₇F₁₄ liquid mixture in the vicinity of the critical point, which was studied by means of ellipsometry in [1], were calculated using the proposed method. The temperature dependences of the thickness and refraction index that were determined in the homogeneous isotropic layer approximation at the interface liquid-vapor, show structural peculiarities that were not observed earlier. Their appearance is explained by the possible influence of hydrodynamic processes at the boundary.     

Specific heat of Sm0.55Sr0.45MnO3 manganite in magnetic fields up to 15 T: An anomalous critical behavior of the ferromagnet in magnetic field and the observation of a tricritical point

The specific heat of Sm_0.55Sr_0.45MnO₃ manganite is measured in the vicinity of the ferromagnetic phase transition in strong magnetic fields up to 15 T. An anomalous critical behavior of the Sm_0.55Sr_0.45MnO₃ ferromagnet in magnetic field is predicted and experimentally observed. The anomalous behavior manifests itself in that, in magnetic fields up to 4 T, the field favors fluctuations and the specific-heat anomaly increases with the field and sharpens, becoming λ-shaped. In fields above 4 T, the behavior becomes classical: the field suppresses the fluctuations and the specific-heat peak is smeared out. The hysteresis of the transition temperature measured in the heating and cooling runs is about 15 K in zero magnetic field. As the field increases, it narrows gradually and vanishes completely when the field reaches 4 T. The results of the experiments are explained in terms of the competition between the hysteresis and the fluctuations of the magnetic order parameter. The H-T phase diagram of Sm_0.55Sr_0.45MnO₃ certainly indicates that, at 4 T, Sm_0.55Sr_0.45MnO₃ has a tricritical point, at which the ferromagnetic and paramagnetic phases of Sm_0.55Sr_0.45MnO₃ are leveled.     

Critical absorption in binary liquid systems

The refractive index of coexisting phases in two binary liquid systems, viz., perfluorodekalineheptane (PFD-H) and acetic anhydride-pentane (AA-P), in the vicinity of the critical consolution temperature of the system T _c was measured. It was shown that it is possible to observe (using the refractometry method, if the instrument is updated appropriately) critical absorption phenomena; a surface layer enriched by perfluorodekaline (in the PFD-H system) and by pentane (in the AA-P system) occurs at the liquid-vapor interface near the critical consolute point under T > T _c .     

Effect of γ irradiation on the heat capacity of (CH3)2NH2Al(SO4)2 · 6H2O crystals near the ferroelectric phase transition

The heat capacity of dimethyl ammonium-aluminum sulfate crystals (DMAAS), both nonirradiated and γ-irradiated to fluences of 10⁷, 5×10⁷, and 10⁸ R, has been measured by the adiabatic method near the ferroelectric phase transition (PT) within the 80–300 K temperature range. The C _p =f(T) curve exhibits a λ-shaped anomaly near the phase-transition point T _C =152 K. The PT temperature and the magnitude of the anomaly are shown to decrease with increasing γ-irradiation fluence. It has been established that the ferroelectric PT at T _C =152 K, which lies close to the tricritical point, shifts progressively more under γ irradiation toward the second-order PT, and that the behavior of the anomalous part of the heat capacity in the ferroelectric phase is described by the thermodynamic theory of Landau. The experimental heat-capacity data have been used to calculate the variation of the thermodynamic functions of the DMAAS crystal.     

Low temperature properties of the metallic antiferromagnet ErZn12

The metallic antiferromagnet ErZn₁₂ orders magnetically at 2·76°K. We report measurements of the susceptibility, magnetisation, resistivity and specific heat of polycrystalline specimens of it in the vicinity of the magnetically ordered regime. We find evidence for a metamagnetic or spin-flop transition in fields of 3–7KOe. The resistivity increases monotonically from low temperature to the Néel point and has a power-law dependence on temperature of Tⁿ, where n～6·5. The specific heat shows a lambda anomaly at the Néel point and the divergences which appear above and below it are compared with those reported previously in the resistivity. The magnetic entropy indicates that the ordering process involves only one crystal-field doublet.     

Phase transition in gauge theories and multiple-point model

The phase transition in the regularized U(1) gauge theory is investigated by using the dual Abelian Higgs model of scalar monopoles. The corresponding-renormalization-group-improved effective potential, analogous to the Coleman-Weinberg one, is considered in the two-loop approximation for β functions, and the phase-transition (critical) dual and nondual couplings are calculated in the U(1) gauge theory. It is shown that the critical value of the renormalized electric fine-structure constant,α _crit≈0.208, obtained in this study agrees with the lattice result for compact QED: α _crit ^lat ≈0.20±0.015. This result and the behavior of α in the vicinity of the phase-transition point are compared with the multiple-point-model prediction for the values of α near the Planck scale. Such a comparison is very encouraging for the multiple point model assuming the existence of the multiple critical point at the Planck scale.     

Effect of an organic dye on the ferroelectric phase transition in KH2PO4 (KDP)

This paper reports on the first measurement of the dielectric permittivity and heat capacity of a KDP crystal doped by Chicago Sky Blue organic dye within a temperature interval including the ferroelectric phase transition at T _c =122 K. Similar measurements were made on a pure KDP crystal under the same conditions for the sake of comparison. The heat capacities of the pure and doped crystals were shown to differ substantially within an interval 1 K wide in the vicinity of T _c , where an anomaly in the heat capacity of the doped crystal was observed to wash out without producing any change in the temperature position of its maximum. The doping reduces the permittivity in the polar phase markedly. The observed effects are associated with the influence of nonisomorphic defects on the ferroelectric phase transition in a piezoelectric crystal.     

The effect of Er doping on the spin reorientation transition in Ho1−xErxAl2

The magnetothermal properties of pseudo binary Ho_1−xEr_xAl₂ alloys have been investigated by heat capacity measurements. Two anomalies are observed in the heat capacity of HoAl₂. A sharp peak at 20 K represents the first order spin reorientation transition, and a second order anomaly occurs in the vicinity of the ferromagnetic transition at 32 K. As Ho is partially replaced by Er in Ho_1−xEr_xAl₂ the sharpness of the first order heat capacity peak diminishes with increasing Er concentration, while the temperature of this transition remains practically unaffected. The second order ferromagnetic transition shifts to higher temperature region with increasing Er concentration. The observed behaviors are explained considering the geometry of 4f charge densities of Ho³⁺ and Er³⁺ and the easy magnetization directions of HoAl₂ and ErAl₂.     

Specific heat studies of high-Tc superconductor YBa2Cu3O7−x

Specific heat studies of the high-T_c superconducting compound YBa₂Cu₃O_7−x with bulk transition temperature at 92K are reported. A distinct anomaly of electronic origin in the specific heat is observed with granular-like behavior corresponding to a Sommerfeld constant γ = 7±2mJ(moleCuK²)^±1 Debye temperature (φo ≈ 400K) is obtained by fitting the experimental data with the theoretical Debye specific heat.     

Thermodynamic behavior of a water model with a liquid-liquid critical point

In this paper we calculate the constant pressure specific heat response of a water model with a liquid-liquid critical point. We show how, due to the existence of the critical point, there is a secondary maximum in the specific heat at some temperature T_*>T_h for any pressure P>P_c, being T_h the first order transition temperature between the high and the low density liquid phases and P_c the pressure of the critical point. This secondary maximum does not correspond to any long range correlated phase transition and does not show up in the temperature dependence of the isothermal compressibility.     

Electron spectrum and heat capacity of heavy fermions in the canted phase of antiferromagnetic intermetallides

The energy spectrum of heavy fermions in an external magnetic field is calculated for canted magnetic sublattices of antiferromagnetic intermetallides. This makes it possible to determine low-temperature features of electronic heat capacity of heavy-fermion antiferromagnets with the metal-type ground state taking into account the structural rearrangement of the magnetic subsystem. The calculated temperature dependences of the magnetization, heat capacity, and Sommerfeld constant in the vicinity of the point of transition to the antiferromagnetic phase correlate with experimental data obtained for heavy-fermion antiferromagnets PuGa₃, Ce₂Au₂Cd, YbNiSi₃, and PuPd₅Al₂.     

Heat capacity and electrical resistivity of some lanthanide-nickel (LnNi5) compounds between 5 and 300°K

Results of heat capacity measurements for LnNi₅ compounds with Ln  La, Ce, Nd and Gd are presented for the temperature range 5–300°K. Electrical resistivities are given for the Ce, Nd and Gd compounds over the same temperature range. The heat capacities are consistent with the previously observed magnetic behavior of LaNi₅, CeNi₅ and NdNi₅. The La compound is a Pauli paramagnet and its heat capacity behavior is that of a solid exhibiting only vibrational and electronic excitation. CeNi₅ remains paramagnetic to 4°K and its C_p behavior closely resembles that of LaNi₅. NdNi₅ exhibits a A-type thermal anomaly peaking at 6·4°K, which is ascribed to the break-up of ferromagnetism. It also shows excess heat capacity at higher temperatures resulting from excitation in the crystal field spectrum. Results for GdNi₅, are unusual. Magnetic entropy is introduced over an anomalously wide range of temperature. The process culminates in two λ-type thermal anomalies peaking at 29·8 and 30·6°K, suggesting that the development of the cooperative phase occurs in two stages. The magnetic transformations are also evident in the resistivity-temperature behavior of NdNi₅ and GdNi₅, the loss of the spin-disorder resistivity being readily apparent in the former material. The usual thermodynamic properties are computed from the heat capacity data. Magnetic entropies of NdNi₅ and GdNi₅ at 300°K are observed to be 95 and 86 per cent, respectively, of R In(2J + 1).