0000000000222377
AUTHOR
Javier Garrido
Thermodynamics of electrokinetic processes—II. systems with different kinds of electrodes
Abstract In this work Haase's Formulation of Electrokinetic Processes is applied to special systems: those working with two different electrodes and those where gaseous phases are formed. Phenomenological equations are always written in terms of directly observable variables. The extrinsic character of Haase's Formulation is clearly shown. Some special results on streaming current in dielectric liquids are explained.
Relation of Malnutrition and Nosocomical Infections in Cancer Patients in Hospital: An Observational Study
Aim. To investigate the relation between malnutrition and nosocomial infections (NI) in hospitalized cancer patients. Methods. This observational, cross-sectional, noninterventional, descriptive study was conducted in a 500-bed university hospital in Valencia (Spain). Adult cancer patients admitted to the oncology ward were consecutively enrolled regardless of their nutritional status between November 2019 and March 2020. Patients were nutritionally assessed 24 to 48 hours after admission. Body weight, height and BMI, body composition through measurement of bioelectrical impedance analysis (BIA), and muscle strength and functionality using hand grip strength (HGS) were prospectively collect…
Heat and work fluxes in thermoelectric coolers
Abstract Thermodynamics considers heat and work as the observables of energy. Then, in a non-equilibrium process, the fluxes of heat, work and energy are related. The expressions for the heat and energy flux densities are well known; although several conventions have been adopted. The work flux density defined from the heat and energy flux densities can be very useful in describing the energy balance when chosen to emphasize observable quantities. This paper discusses the advantages of the use of the conduction heat flux density given by Fourier’s law and a work flux density defined from it. As a case study, heat and work fluxes are evaluated in the elements of a thermoelectric cooler using…
True and Apparent Oxygen Permeabilities of Contact Lenses
We studied the passage of oxygen through some commercially available contact lenses. Oxygen diffusion coefficients were determined by the time-lag method and a 201T Redher permeometer was used to measure the oxygen permeability and transmissibility by the polarographic method. The measurements were carried out at room temperature with 0.09% sodium chloride physiologic solution. The following types of lenses were tested: (1) 12 lenses of cellulose acetate butyrate (CAB) of a mean thickness of 0.194 mm (observed Dk approximately 6.3 barrers) (1 barrier is equivalent to 10(-11) cm3 of O2 (STP).cm2/cm3.s.mm Hg). (2) 13 lenses of a cross-linked polyhydroxyethyl methacrylate (2-HEMA), manufacture…
Electrical magnitudes in gravitational and centrifugal systems
Abstract A new formulation to study the non-equilibrium processes in gravitational and centrifugal electrochemical systems is developed. The driving forces and the fluxes are measurable quantities. The electrical equilibrium and the pure electrical conduction are described in an evident, simple and exact manner. Theoretical expressions of the emf for several gravitational cells are shown. Some differences are observed with those given in the literature ( eg the terminals density does not appear). The electrochemical potential of ion species is the basic piece in this study.
Central role of the observable electric potential in transport equations.
Nonequilibrium systems are usually studied in the framework of transport equations that involve the true electric potential (TEP), a nonobservable variable. Nevertheless another electric potential, the observable electric potential (OEP), may be defined to construct a useful set of transport equations. In this paper several basic characteristics of the OEP are deduced and emphasized: (i) the OEP distribution depends on thermodynamic state of the solution, (ii) the observable equations have a reference value for all other transport equations, (iii) the bridge that connects the OEP with a certain TEP is usually defined by the ion activity coefficient, (iv) the electric charge density is a non…
Observable Quantities for Electrodiffusion Processes in Membranes
Electrically driven ion transport processes in a membrane system are analyzed in terms of observable quantities, such as the apparent volume flow, the time dependence of the electrolyte concentration in one cell compartment, and the electrical potential difference between the electrodes. The relations between the fluxes and these observable quantities are rigorously deduced from balances for constituent mass and solution volume. These relations improve the results for the transport coefficients up to 25% with respect to those obtained using simplified expressions common in the literature. Given the practical importance of ionic transport numbers and the solvent transference number in the ph…
Peltier’s and Thomson’s coefficients of thermoelectric phenomena in the observable formulation
Four transport coefficients characterize the thermoelectric properties of materials. Three of them are widely measured and studied. But the number of references on the Peltier coefficient are very limited. This unequal result is a consequence of the Onsager reciprocal relation (ORR). A review on the preciseness and accuracy of Peltier coefficient measurements has been developed in this paper. Thus we can appreciate a low level in the experimental confirmation for the ORR. In order to describe the thermoelectric processes in an advantageous way, the observable formulation has been used. This is characterized by the electric potential measured at the probe terminals and for the heat flux whic…
Transport equations of electrodiffusion processes in the laboratory reference frame.
The transport equations of electrodiffusion processes use three reference frames for defining the fluxes: Fick's reference in diffusion, solvent-fixed reference in transference numbers, and laboratory fluxes in electric conductivity. The convenience of using only one reference frame is analyzed here from the point of view of the thermodynamics of irreversible processes. A relation between the fluxes of ions and solvent and the electric current density is deduced first from a mass and volume balance. This is then used to show that (i) the laboratory and Fick's diffusion coefficients are identical and (ii) the transference numbers of both the solvent and the ion in the laboratory reference fr…
Transport coefficients in desalting processes by electrodialysis
Abstract In this work a thermodynamic analysis on the transport equations in the processes of electrodiffusion (EF) and electrodialysis (ED) has been developed. The transport equations are classified in two sets according to the information they contain: i ) fundamental and ii ) complementary. We determine that there are four fundamental transport coefficients needed to characterize these membrane systems. We also conclude that this number is not reduced to three when the Onsager reciprocal relation (ORR) is assumed. I have also obtained a new expression for the concentration rate in EF and ED processes from the mass and volume balance. This relation provides a new way for evaluating the ap…
Thermodynamics of electrokinetic processes—I. Formulations
Abstract The phenomenological equations of electrokinetic processes are studied according to five different formulations. Transformation matrices with Haase's formulation are given. A study of the measurable character of fluxes, forces and phenomenological coefficients in those formulations is also made. The extrinsic character, if so, of the formulations is examined and a general definition of formulations established only for binary solutions is given. Finally, a review of the literature is included, aiming to clarify the possible misunderstandings arising from the application of these five formulations.
Observable Streaming Potential in Membranes
Theories describing the electrokinetic processes in membranes usually involve nonobservable variables. One of these phenomena is the streaming potential, i.e., the electric potential generated by a pressure difference imposed across the membrane system. In this work the streaming potential is successfully described by using observable variables in the framework of thermodynamics of irreversible processes. The observable electric potential is the central quantity of the transport equations. The relaxation with time of this electric potential difference is well explained by the solute flux in these transport equations. The fluxes and forces defined in the formulation permit one to analyze the…
Proton Transport in Membranes Prepared from Sulfonated Polystyrene-Poly(vinylidene fluoride) Blends
The preparation of new cation-exchange membranes from polymer composites based on poly(vinylidene fluoride), sulfonated polystyrene-co-divinylbenzene, and antimonic acid is reported. The thermal properties of the composites have been characterized by differential scanning calorimetry. Values of the transport number of protons in the membranes were obtained from the observable electric potential. It is defined from the potential difference measured between the electrodes reversible to one of the constituent ions in equilibrium with the system. When compared with Nafion cation-exchange membranes, the membranes described in this work exhibit interesting proton transport properties that could m…
A finite-difference method for numerical solution of the steady-state nernst—planck equations with non-zero convection and electric current density
Abstract A computer algorithm has been developed for digital simulation of ionic transport through membranes obeying the Nernst—Planck and Poisson equations. The method of computation is quite general and allows the treatment of steady-state electrodiffusion equations for multiionic environments, the ionic species having arbitrary valences and mobilities, when convection and electric current are involved. The procedure provides a great flexibility in the choice of suitable boundary conditions and avoids numerical instabilities which are so frequent in numerical methods. Numerical results for concentration and electric potential gradient profiles are presented in the particular case of the t…
Observable Variables in Thermoelectric Phenomena
New transport equations for the thermoelectric phenomena have been deduced. All of the variables in this formulation are observable quantities. The limitations of the usual formulations, which work with nonobservable quantities, have been overcome. The electric potential can be measured by using auxiliary probes which connect the electronic conductor to a potentiometer. This observable electric potential depends on the nature of the probes but not on the room temperature where the potentiometer is placed. Also, we emphasize that absolute values for the thermoelectric power are in contradiction with the thermodynamic limitation of measuring electric potential differences in these systems. Th…
Thermodynamics of Electrochemical Systems
A discussion of the fundamentals of thermodynamic theory describing electrochemical systems is presented. The basic relationships are deduced as properties of the electrochemical potential. The theory introduces an observable electric potential that is defined at every position within the electrochemical system as the potential of a reversible electrode placed there. To provide a good test of the formalism, five systems have been studied including equilibrium and nonequilibrium. The formalism emphasizes the advantages of the electric current density in order to characterize one of the degrees of irreversibility and the electrical equilibrium. Finally, the electrostatic potential is discusse…
Determination of the glass transition temperature of poly(cyclohexyl acrylate) from oxygen permeability measurements
Abstract The glass transition temperature ( T g ) of poly(cyclohexyl acrylate) (PCA) has been obtained from measurements of the oxygen permeability ( P = 0.60 barrers, T g = 23.5 ± 2.0°C) using a potentiostatic electrochemical sensor, and from the oxygen diffusion coefficient ( D = 0.12 × 10 −8 cm 2 s −1 , T g = 24.0 ± 1.8°C) by the time-lag method. A T g of 25 ± 1°C was found by differential scanning calorimetry and a T g of 25.0 ± 3.5°C was obtained from the specific volume by dilatometry. The fractional free volume ( v f ) at T g is 0.020 ± 0.002, which is slightly below (∼ 20%) most glassy polymers. A linear correlation has been observed between ln D and the reciprocal of v f , which su…