Equilíbrio líquido-líquido de sistemas aquosos com tensoativos polietoxilados: dados experimentais e modelagem

The nonionic surfactants when in aqueous solution, have the property of separating into two phases, one called diluted phase, with low concentration of surfactant, and the other one rich in surfactants called coacervate. The application of this kind of surfactant in extraction processes from aqueous solutions has been increasing over time, which implies the need for knowledge of the thermodynamic properties of these surfactants. In this study were determined the cloud point of polyethoxylated surfactants from nonilphenolpolietoxylated family (9,5 , 10 , 11, 12 and 13), the family from octilphenolpolietoxylated (10 e 11) and polyethoxylated lauryl alcohol (6 , 7, 8 and 9) varying the degree of ethoxylation. The method used to determine the cloud point was the observation of the turbidity of the solution heating to a ramp of 0.1 ° C / minute and for the pressure studies was used a cell high-pressure maximum ( 300 bar). Through the experimental data of the studied surfactants were used to the Flory - Huggins models, UNIQUAC and NRTL to describe the curves of cloud point, and it was studied the influence of NaCl concentration and pressure of the systems in the cloud point. This last parameter is important for the processes of oil recovery in which surfactant in solution are used in high pressures. While the effect of NaCl allows obtaining cloud points for temperatures closer to the room temperature, it is possible to use in processes without temperature control. The numerical method used to adjust the parameters was the Levenberg - Marquardt. For the model Flory- Huggins parameter settings were determined as enthalpy of the mixing, mixing entropy and the number of aggregations. For the UNIQUAC and NRTL models were adjusted interaction parameters aij using a quadratic dependence with temperature. The parameters obtained had good adjust to the experimental data RSMD < 0.3 %. The results showed that both, ethoxylation degree and pressure increase the cloudy points, whereas the NaCl decrease

Teoria cinética não extensiva: efeitos físicos em gases e plasmas

The standard kinetic theory for a nonrelativistic diluted gas is generalized in the spirit of the nonextensive statistic distribution introduced by Tsallis. The new formalism depends on an arbitrary q parameter measuring the degree of nonextensivity. In the limit q = 1, the extensive Maxwell-Boltzmann theory is recovered. Starting from a purely kinetic deduction of the velocity q-distribution function, the Boltzmann H-teorem is generalized for including the possibility of nonextensive out of equilibrium effects. Based on this investigation, it is proved that Tsallis' distribution is the necessary and sufficient condition defining a thermodynamic equilibrium state in the nonextensive context. This result follows naturally from the generalized transport equation and also from the extended H-theorem. Two physical applications of the nonextensive effects have been considered. Closed analytic expressions were obtained for the Doppler broadening of spectral lines from an excited gas, as well as, for the dispersion relations describing the eletrostatic oscillations in a diluted electronic plasma. In the later case, a comparison with the experimental results strongly suggests a Tsallis distribution with the q parameter smaller than unity. A complementary study is related to the thermodynamic behavior of a relativistic imperfect simple fluid. Using nonequilibrium thermodynamics, we show how the basic primary variables, namely: the energy momentum tensor, the particle and entropy fluxes depend on the several dissipative processes present in the fluid. The temperature variation law for this moving imperfect fluid is also obtained, and the Eckart and Landau-Lifshitz formulations are recovered as particular cases

Setor escuro do universo: uma análise termodinâmica

Significant observational effort has been directed to unveiling the nature of the so-called dark energy. However, given the large number of theoretical possibilities, it is possible that this a task cannot be based only on observational data. In this thesis we investigate the dark energy via a thermodynamics approach, i.e., we discuss some thermodynamic properties of this energy component assuming a general time-dependent equation-of-state (EoS) parameter w(a) = w0 + waf(a), where w0 and wa are constants and f(a) may assume different forms. We show that very restrictive bounds can be placed on the w0 - wa space when current observational data are combined with the thermodynamic constraints derived. Moreover, we include a non-zero chemical potential μ and a varying EoS parameter of the type ω(a) = ω0 + F(a), therefore more general, in this thermodynamical description. We derive generalized expressions for the entropy density and chemical potential, noting that the dark energy temperature T and μ evolve in the same way in the course of the cosmic expansion. The positiveness of entropy S is used to impose thermodynamic bounds on the EoS parameter ω(a). In particular, we find that a phantom-like behavior ω(a) < −1 is allowed only when the chemical potential is a negative quantity (μ < 0). Thermodynamically speaking, a complete treatment has been proposed, when we address the interaction between matter and energy dark

Fundamentação cinética da estatística não gaussiana : efeitos em politrópicas

Considering a non-relativistic ideal gas, the standard foundations of kinetic theory are investigated in the context of non-gaussian statistical mechanics introduced by Kaniadakis. The new formalism is based on the generalization of the Boltzmann H-theorem and the deduction of Maxwells statistical distribution. The calculated power law distribution is parameterized through a parameter measuring the degree of non-gaussianity. In the limit = 0, the theory of gaussian Maxwell-Boltzmann distribution is recovered. Two physical applications of the non-gaussian effects have been considered. The first one, the -Doppler broadening of spectral lines from an excited gas is obtained from analytical expressions. The second one, a mathematical relationship between the entropic index and the stellar polytropic index is shown by using the thermodynamic formulation for self-gravitational systems

Análise tribo-termodinâmica da aplicação de nanopartículas de Al2O3 como aditivo lubrificante em compressor hermético de refrigeração

The thermodynamic performance of a refrigeration system can be improved by reducing the compression work by a particular technique for a specific heat removal rate. This study examines the effect of small concentrations of Al2O3 (50 nm) nanoparticles dispersion in the mineral oil based lubricant on the: viscosity, thermal conductivity, and lubrication characteristics as well as the overall performance (based on the Second Law of Thermodynamics) of the refrigerating system using R134a or R600a as refrigerants. The study looked at the influences of variables: i) refrigerant charge (100, 110, 120 and 130 g), ii) rotational speed of the condenser blower (800 and 1100 RPM) and iii) nanoparticle concentration (0.1 and 0.5 g/l) on the system performance based on the Taguchi method in a matrix of L8 trials with the criterion "small irreversibility is better”. They were carried pulldown and cycling tests according to NBR 12866 and NBR 12869, respectively, to evaluate the operational parameters: on-time ratio, cycles per hour, suction and discharge pressures, oil sump temperature, evaporation and condensation temperatures, energy consumption at the set-point, total energy consumption and compressor power. In order to evaluate the nanolubricant characteristics, accelerated tests were performed in a HFRR bench. In each 60 minutes test with nanolubricants at a certain concentration (0, 0.1 and 0.5 g/l), with three replications, the sphere (diameter 6.00 ± 0.05 mm, Ra 0.05 ± 0.005 um, AISI 52100 steel, E = 210 GPa, HRC 62 ± 4) sliding on a flat plate (cast iron FC200, Ra <0.5 ± 0.005 um) in a reciprocating motion with amplitude of 1 mm, frequency 20 Hz and a normal load of 1,96 N. The friction coefficient signals were recorded by sensors coupled to the HFRR system. There was a trend commented bit in the literature: a nanolubricant viscosity reduction at the low nanoparticles concentrations. It was found the dominant trend in the literature: increased thermal conductivity with increasing nanoparticles mass fraction in the base fluid. Another fact observed is the significant thermal conductivity growth of nanolubricant with increasing temperature. The condenser fan rotational speed is the most influential parameter (46.192%) in the refrigerator performance, followed by R600a charge (38.606%). The Al2O3 nanoparticles concentration in the lubricant plays a minor influence on system performance, with 12.44%. The results of power consumption indicates that the nanoparticles addition in the lubricant (0.1 g/L), together with R600a, the refrigerator consumption is reduced of 22% with respect to R134a and POE lubricant. Only the Al2O3 nanoparticles addition in the lubricant results in a consumption reduction of about 5%.

Análise tribo-termodinâmica da aplicação de nanopartículas de Al2O3 como aditivo lubrificante em compressor hermético de refrigeração

The thermodynamic performance of a refrigeration system can be improved by reducing the compression work by a particular technique for a specific heat removal rate. This study examines the effect of small concentrations of Al2O3 (50 nm) nanoparticles dispersion in the mineral oil based lubricant on the: viscosity, thermal conductivity, and lubrication characteristics as well as the overall performance (based on the Second Law of Thermodynamics) of the refrigerating system using R134a or R600a as refrigerants. The study looked at the influences of variables: i) refrigerant charge (100, 110, 120 and 130 g), ii) rotational speed of the condenser blower (800 and 1100 RPM) and iii) nanoparticle concentration (0.1 and 0.5 g/l) on the system performance based on the Taguchi method in a matrix of L8 trials with the criterion "small irreversibility is better”. They were carried pulldown and cycling tests according to NBR 12866 and NBR 12869, respectively, to evaluate the operational parameters: on-time ratio, cycles per hour, suction and discharge pressures, oil sump temperature, evaporation and condensation temperatures, energy consumption at the set-point, total energy consumption and compressor power. In order to evaluate the nanolubricant characteristics, accelerated tests were performed in a HFRR bench. In each 60 minutes test with nanolubricants at a certain concentration (0, 0.1 and 0.5 g/l), with three replications, the sphere (diameter 6.00 ± 0.05 mm, Ra 0.05 ± 0.005 um, AISI 52100 steel, E = 210 GPa, HRC 62 ± 4) sliding on a flat plate (cast iron FC200, Ra <0.5 ± 0.005 um) in a reciprocating motion with amplitude of 1 mm, frequency 20 Hz and a normal load of 1,96 N. The friction coefficient signals were recorded by sensors coupled to the HFRR system. There was a trend commented bit in the literature: a nanolubricant viscosity reduction at the low nanoparticles concentrations. It was found the dominant trend in the literature: increased thermal conductivity with increasing nanoparticles mass fraction in the base fluid. Another fact observed is the significant thermal conductivity growth of nanolubricant with increasing temperature. The condenser fan rotational speed is the most influential parameter (46.192%) in the refrigerator performance, followed by R600a charge (38.606%). The Al2O3 nanoparticles concentration in the lubricant plays a minor influence on system performance, with 12.44%. The results of power consumption indicates that the nanoparticles addition in the lubricant (0.1 g/L), together with R600a, the refrigerator consumption is reduced of 22% with respect to R134a and POE lubricant. Only the Al2O3 nanoparticles addition in the lubricant results in a consumption reduction of about 5%.