Solubilities, Vapor Pressures, and Heat Capacities of the Water + Lithium Bromide + Lithium Nitrate + Lithium Iodide + Lithium Chloride System

The optimum mole ratio of lithium salts in the H₂O + LiBr + LiNO₃ + LiI + LiCl system was experimentally determined to be LiBr : LiNO₃ : LiI : LiCl = 5 : 1 : 1 : 2. The solubilities were measured at temperatures from 252.02 to 336.75 K. Regression equations on the solubility data were obtained with a least-squares method. Average absolute deviations of the calculated values from the experimental data were 0.15% at temperatures <285.18 K and 0.05% at temperatures 285.18 K. The vapor pressures were measured at concentrations ranging from 50.0 to 70.0 mass% and at temperatures from 330.13 to 434.88 K. The experimental data were correlated with an Antoine-type equation, and the average absolute deviation of the calculated values from the experimental data was 2.25%. The heat capacities were measured at concentrations from 50.0 to 65.0 mass% and temperatures from 298.15 to 328.15 K. The average absolute deviation of the values calculated by the regression equation from the experimental data was 0.24%.     

Thermodynamic properties for the quaternary system H2O + CH3OH + LiBr + ZnCl2

The thermodynamic properties (solubility, vapour pressure, density, viscosity, heat capacity and heat of mixing) of the H₂O + CH₃OH + LiBr + ZnCl₂ (9:1 H₂O:CH₃OH and 1:1 LiBr:ZnCl₂ by mass) system using H₂O + CH₃OH as the working media and LiBr + ZnCl₂ as the absorbents were measured. The solubility data were obtained in the temperature range from 270.35 to 389.55 K. The measurements of vapour pressure, density, viscosity and heat capacity were carried out at various temperatures and absorbent concentrations. The differential heat of dilution and differential heat of solution at 298.15 K were measured for solutionw with absorbent concentrations from 0 to 75.2 wt%. The integral heat of mixing data at 298.15 K were obtained from both sets of experimental data. The integral heats of mixing for this quaternary system showed exothermic behaviour. The vapour pressure data were correlated with an Antoine-type equation. An empirical formula for the heat capacity was obtained from experimental data. The experimental data for the basic thermodynamic properties of this quaternary system were compared with those of the basic H₂O + LiBr system.     

Estimation of differential heat of dilution for aqueous lithium (bromide,iodide, nitrate,chloride) solution and aqueous (lithium,potassium, sodium) nitrate solution used in absorption cooling systems

The differential heat of dilution data are estimated theoretically using Duhring's diagrams for water/LiBr, water/(LiBr + LiI + LiNO₃ + LiCl) with mass compositions in salts of 60.16%, 9.55%, 18.54% and 11.75%, respectively, and water/(LiNO₃ + KNO₃ + NaNO₃) with mass compositions in salts of 53%, 28% and 19%, respectively, as these can be potentially utilized as working fluids in absorption cooling systems. The differential heat of dilution data obtained were correlated with simple polynomial equations for the three working fluids as a function of the solution concentration and temperature. The results showed that the differential heat of dilution of the non-conventional working fluid mixtures is lower than that of water/LiBr at typical operating temperature and concentration of interest in absorption cooling cycles employing these working fluid mixtures. The correlations developed could be useful in predicting the differential heat of dilution value while performing heat and mass transfer analyses of these potential non-conventional working fluid mixtures in absorption cooling systems.     

Surface Tensions and Thermal Conductivities of Aqueous LiBr-Based Solutions Containing n-Octanol and 2-Ethyl-1-Hexanol: Application to an Absorption Heat Pump

Surface tensions and thermal conductivities were measured for LiBr+1,3-propanediol+water and LiBr+LiI+1,3-propanediol+water. These two mixtures were chosen as one of the potential candidates for working fluids for absorption heat pumps. Surface tensions and thermal conductivities were measured by the capillary rise method equipped with a cathetometer and the transient hot wire method with a coated tantalum wire, respectively. The measured surface tension and thermal conductivity data were well correlated with a simple polynomial function of temperature and absorbent concentration. In addition, the surface tensions of LiBr+1,3-propanediol+water containing a small amount of alcohol-based surfactants, n-octanol and 2-ethyl-1-hexanol, were also measured at 298.15 K by the ring method. An increase in the surfactant concentration up to about 500 ppm leads to a gradual decrease in the mixture surface tensions.     

Thermodynamic Properties and Decomposition of Lithium Hexafluoroarsenate, LiAsF6

The heat capacity of lithium hexafluoroarsenate is determined in the temperature range 50–750 K by adiabatic and differential scanning calorimetry techniques. The thermodynamic properties of LiAsF₆ under standard conditions are evaluated: C _p ⁰(298.15 K) = 162.5 ± 0.3 J/(K mol), S ⁰(298.15 K) = 173.4 ± 0.4 J/(K mol), ⁰(298.15 K) = 81.69 ± 0.20 J/(K mol), and H ⁰(298.15 K) – H ⁰(0) = 27340 ± 60 J/mol. The C _p(T) curve is found to contain a lambda-type anomaly with a peak at 535.0 ± 0.5 K, which is due to the structural transformation from the low-temperature, rhombohedral phase to the high-temperature, cubic phase. The enthalpy and entropy of this transformation are 5.29 ± 0.27 kJ/mol and 10.30 ± 0.53 J/(K mol), respectively. The thermal decomposition of LiAsF₆ is studied. It is found that LiAsF₆ decomposes in the range 715–820 K. The heat of decomposition, determined in the range 765–820 K using a sealed crucible and equal to the internal energy change U _r(T), is 31.64 ± 0.08 kJ/mol.     

Solubilities and vapor pressures of the lithium bromide+calcium nitrate+water system

Solubilities and vapor pressures of the lithium bromide+calcium nitrate+water system [LiBr/Ca(NO₃)₂ mass ratio=1.0] were measured in various absorbent (lithium bromide+calcium nitrate) concentration and temperature ranges. Solubilities were measured by a visual polythermal method in the temperature range from 282.55 to 343.45 K and the experimental values were correlated with two least-squares regression equations as a function of temperature. The average absolute deviation between the experimental and the calculated solubilities was 0.23%. Vapor pressures were measured by the boiling point method in the temperature range from 334.65 to 385.85 K and in the absorbent concentration range from 44.9 to 70.3 mass%. The experimental values were correlated with an Antoine-type equation and the overall average absolute deviation was found to be 1.06%.     

Performance research of self regenerated absorption heat transformer cycle using TFE-NMP as working fluids

A heat transformer is proposed in order to upgrade low-temperature-level energy to a higher level and to recover more energy in low-temperature-level waste heat. It is difficult to achieve both purposes at the same time using a conventional heat transformer cycle and classical working pairs, such as H₂O–LiBr and HN₃–H₂O. The new organic working pair, 2,2,2-trifluoroethanol (TFE)-N-methylpyrolidone (NMP), has some advantages compared with H₂O–LiBr and NH₃–H₂O. One of the most important features is the wide working range as a result of the absence of crystallization, the low working pressure, the low freezing temperature of the refrigerant and the good thermal stability of the mixtures at high temperatures. Meanwhile, it has some negative features like NH₃–H₂O. For example, there is a lower boiling temperature difference between TFE and NMP, so a rectifier is needed in refrigeration and heat pump systems. Because TFE–NMP has a wide working range and does not cause crystallization, it can be used as the working pair in the self regenerated absorption heat transformer (SRAHT) cycle. In fact, the SRAHT cycle is the generator–absorber heat exchanger (GAX) cycle applied in a heat transformer cycle. In this paper, the SRAHT cycle and its flow diagram are shown and the computing models of the SRAHT cycle are presented. Thermal calculations of the SRAHT cycle under summer and winter season conditions have been worked out. From the results of the thermal calculations, it can be found that there is a larger temperature drop when the waste hot water flows through the generator and the evaporator in the SRAHT cycle but the heating temperature can be kept the same. That means more energy in the waste heat source can be recovered by the SRAHT cycle.     

Physical properties of the lithium bromide + 1,3-propanediol + water system

The experimental measurements of the basic four physical properties (solubility, vapor pressure, density and viscosity) of the lithium bromide + 1,3-propanediol + water system (LiBr/HO(CH₂)₃OH mass ratio = 3.5), a possible new working fluid for absorption heat pump, were carried out. Solubility was measured by the visual polythermal method in the temperature range from 264.65 to 358-95 K, and vapor pressure by the boiling point method from 330.75 to 408.45 K. Densities and viscosities were also measured by using a set of hydrometers and Ubbelohde-type capillary viscometers in the temperature range from 283.15 to 343.15 K. Each measured data set was correlated with a proper equation, and all the correlation results showed good agreement between measured and calculated values. Using the correlation results the Dühring chart was constructed and thus the system was found to be able to have a high absorber temperature, which is essential for the design of air-cooled absorption chiller.     

Thermodynamic properties by levitation calorimetry — V. High-temperature heat content of liquid gallium

The heat content (enthalpy) of liquid gallium relative to the supercooled liquid state at 298.15 K has been measured by levitation calorimetry over the temperature range 1412–1630 K. Thermal energy increments were determined using an aluminum block calorimeter of conventional design. The sharp decrease of C _p with increasing temperature observed just above the melting point does not persist up to the high temperatures of the present work. When combined with recent laser-flash calorimetry results from the literature, the present work indicates that C _p is 26.46 ± 0.71 J · g-atom^–1 · K^–1 over the temperature range 587–1630 K.Paper presented at the Japan-United States Joint Seminar on Thermophysical Properties, October 24–26, 1983, Tokyo, Japan.     

Measurement of solubility and density of water + lithium bromide + lithium chloride and water + lithium bromide + sodium formate systems

Solubility of aqueous solutions containing lithium bromide + lithium chloride and lithium bromide + sodium formate were measured (LiBr/NaHCO₂ = 2 and LiBr/LiCl = 2 by mass ratio) at different temperatures. Visual polythermal method was used in the temperature range of (283.15–340.15) K and mass fraction range of (0.4–0.8). Also density of mentioned systems was reported in the temperature range of (288.15–333.15) K. Each set of experimental measurements were correlated using least-square regression as a function of temperature. Our results indicate that solubility of LiBr + LiCl is higher than LiBr and its density is lower than density of aqueous solution of LiBr.     

Measurements of Gaseous PVTx Properties and Saturated Vapor Densities of Refrigerant Mixture R-125+R-143a

The experimental PVTx properties of a binary refrigerant mixture, R-125 (pentafluoroethane)+R-143a (1,1,1-trifluoroethane), have been measured for a composition of 50 mass% R-125 by a constant-mass method coupled with an expansion procedure in a range of temperatures from 305 to 400 K, pressures from 1.5 to 6.1 MPa, and densities from 92 to 300 kg·m^–3. The experimental uncertainties of the present measurements are estimated to be within ±7.2 mK in temperature, ±3.0 kPa in pressure, ±0.12 kg·m^–3 in density, and ±0.040 mass% in composition. The sample purities are 99.953 mass% for R-125 and 99.998% for R-143a. Seven saturated vapor densities and dew point pressures of the R-125+R-143a system were determined, on the basis of rather detailed PVTx properties measured in the vicinity of the saturation boundary as well as the thermodynamic behavior of isochores near saturation. The second and third virial coefficients for temperatures from 330 to 400 K were also determined.     

Review of advanced absorption cycles: performance improvement and temperature lift enhancement

The objective of this study is to propose and evaluate advanced absorption cycles for the coefficient of performance (COP) improvement and temperature lift enhancement applications. The characteristics of each cycle are assessed from the viewpoints of the ideal cycle COP and its applications. The advanced cycles for the COP improvement are categorized according to their heat recovery method: condensation heat recovery, absorption heat recovery, and condensation/absorption heat recovery. In H₂O–LiBr systems, the number of effects and the number of stages can be improved by adding a third or a fourth component to the solution pairs. The performance of NH₃–H₂O systems can be improved by internal heat recovery due to their thermal characteristics such as temperature gliding. NH₃–H₂O cycles can be combined with adsorption cycles and power generation cycles for waste heat utilization, performance improvement, panel heating and low temperature applications. The H₂O–LiBr cycle is better from the high COP viewpoints for the evaporation temperature over 0°C while the NH₃–H₂O cycle is better from the viewpoint of low temperature applications. This study suggests that the cycle performance would be significantly improved by combining the advanced H₂O–LiBr and NH₃–H₂O cycles.     

Solid-State Interaction of Aluminium Hydroxide with Lithium Salts

The solid-state synthesis of [LiAl₂(OH)₆]Cl · mH₂O at room and elevated temperatures from powdered solid reagents, lithium chloride and gibbsite, is described. The synthesis is performed with the help of different devices including a laboratory mixer, large-scale laboratory arm mixer, and planetary centrifugal mill. The interaction of the components depends on both the dispersity of Al(OH)₃ and the nature of lithium chloride. At the initial stage, the interaction is limited by the rate of lithium chloride diffusion through the layer of the product formed. Activation energy, calculated according to the Valency–Carter equation, is 53 ± 5 kJ/mol.     

Isochoric Heat Capacity Measurements for 0.5 H2O+0.5 D2O Mixture in the Critical Region

The isochoric heat capacity C _V of an equimolar H₂O+D₂O mixture was measured in the temperature range from 391 to 655 K, at near-critical liquid and vapor densities between 274.05 and 385.36 kgm^–3. A high-temperature, high-pressure, nearly constant-volume adiabatic calorimeter was used. The measurements were performed in the one- and two-phase regions including the coexistence curve. The uncertainty of the heat-capacity measurement is estimated to be ±2%. The liquid and vapor one- and two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from the experimental data for each measured isochore. The critical temperature and the critical density for the equimolar H₂O+D₂O mixture were obtained from isochoric heat capacity measurements using the method of quasi-static thermograms. The measurements were compared with a crossover equation of state for H₂O+D₂O mixtures. The near-critical isochoric heat capacity behavior for the 0.5 H₂O+0.5 D₂O mixture was studied using the principle of isomorphism of critical phenomena. The experimental isochoric heat capacity data for the 0.5 H₂O+0.5 D₂O mixture exhibit a weak singularity, like that of both pure components. The reliability of the experimental method was confirmed with measurements on pure light water, for which the isochoric heat capacity was measured on the critical isochore (321.96 kgm^–3) in both the one- and two-phase regions. The result for the phase-transition temperature (the critical temperature, T _{C, this work}=647.104±0.003 K) agreed, within experimental uncertainty, with the critical temperature (T _{C, IAPWS}=647.096 K) adopted by IAPWS.     

Experimental researches on characteristics of vapor–liquid equilibrium of NH3–H2O–LiBr system

An improved system of NH₃–H₂O–LiBr was proposed for overcoming the drawback of NH₃–H₂O absorption refrigeration system. The LiBr was added to NH₃–H₂O system anticipating a decrease in the content of water in the NH₃–H₂O–LiBr system. An equilibrium cell was used to measure thermal property of the ternary NH₃–H₂O–LiBr mixtures. The pressure–temperature data for their vapor–liquid equilibrium (VLE) data were measured at ten temperature points between 15–85 °C, and pressures up to 2 MPa. The LiBr concentration of the solution was chosen in the range of 5–60% of mass ratio of LiBr in pure water. The VLE for the NH₃–H₂O–LiBr ternary solution was measured statically. The experimental results show that the equilibrium pressures reduced by 30–50%, and the amount of component of water in the gas phase reduced greatly to 2.5% at T=70 °C. The experimental results predicted much better characteristics of the new ternary system than the NH₃–H₂O system for the applications.     

Synthesis and Properties of Lithium Manganese Spinels

Li_{1 – x} Mn_{2 – y} Co _y O₄(x= 0–0.06, y= 0–0.15) spinels were prepared by solid-state reactions and sol–gel processing and were characterized by x-ray diffraction and scanning electron microscopy. The spinels offer satisfactory electrochemical performance and are potentially attractive as cathode materials for rechargeable lithium batteries.     

Extended temperature–entropy (T–s) diagrams for aqueous lithium bromide absorption refrigeration cycles

Temperature–entropy (T–s) diagrams have the unique capability of being able to quantify processes in terms of both the first and second laws of thermodynamics. Although use of generalised T–s diagrams has been made to indicate or represent generalised absorption cycles, with the exception for NH₃/water systems, these diagrams have not been specifically tailored to scale to quantify LiBr/water systems. The main barrier for this is that the diagram needs to represent the necessary properties of both the refrigerant (water) and of the solution (LiBr/water). This paper describes the use of the T–s diagram of water extended with additional curves to represent real and ideal LiBr/water absorption cycles. An explanation is provided on several methods available, including details of the thermodynamic justification of the method that was used, to construct the extended diagrams. Finally, the extended T–s diagram is provided with the representation of a real single-effect LiBr/water absorption refrigeration cycle. This should prove to be a valuable tool for design and research engineers to study and optimise LiBr/water chillers.     

Heat transfer enhancement by Marangoni convection in the NH3–H2O absorption process

The objectives of this paper are to quantify the effect of Marangini convection on the absorption performance for the ammonia–water absorption process, and to visualize Marangoni convection that is induced by adding a heat transfer additive, n-octanol. A real-time single-wavelength holographic interferometer is used for the visualization using a He–Ne gas laser. The interface temperature is always the highest due to the absorption heat release near the interface. It was found that the thermal boundary layer (TBL) increased faster than the diffusion boundary layer (DBL), and the DBL thickness increased by adding the heat transfer additive. At 5 s after absorption started, the DBL thickness for 5 mass% NH₃ without and with the heat transfer additive was 3.0 and 4.5 mm, respectively. Marangoni convection was observed near the interface only in the cases with heat transfer additive. The Marangoni convection was very strong just after the absorption started and it weakened as time elapsed. It was concluded that the absorption performance could be improved by increasing the absorption driving potential (x_vb−x_vi) and by increasing the heat transfer additive concentration. The absorption heat transfer was enhanced as high as 3.0–4.6 times by adding the heat transfer additive that generated Marangoni convection.     

The Effect of Gd Concentration on the Physical and Magnetic Properties of Bi1.7Pb0.3-xGdxSr2Ca3Cu4O12+y Superconductors

Bi–Pb–Gd–Sr–Ca–Cu–O bulk samples with nominal composition Bi_1.7Pb _0.3-xGd_xSr₂Ca₃Cu₄O_12+y (x=0.01, 0.05, 0.075, 0.10) were prepared by the melt-quenching method. The effects of different Gd doping on the structure have been investigated by electrical resistance, scanning electron micrographs, XRD, magnetization and magnetic hysteresis loop measurements. The magnetization measurements have been carried out as a function of magnetic field for fields up to 5 kOe at temperatures well below the zero resistance temperatures of the annealed samples. It has been found that the high-T_c superconducting phase, (2 2 2 3), is formed in the sample A with concentration x = 0.01, annealed at 840°C for 120 h. However, with increasing Gd³⁺ doping for Pb²⁺ the (2 2 2 3) phase gradually transforms into the (2 2 1 2) phase. The magnitudes of magnetization and initial susceptibility, | M | and | dM/dH|, and the hysteresis loop areas decrease with increasing Gd concentration x and/or temperature T. The fast decreases in | M|, | dM/dH |, and the hysteresis loop areas related to the superconducting volume, with increasing x and/or T seem to imply an existence of flux pinning centres in our samples. In order to support this implication the critical current densities J_c, of the samples, have been estimated at two fixed temperatures, 9 and 30 K. Our data have indicated that J_c decreases with increasing temperature and/or Gd concentration, as expected.     

Electrical Conductance, Density, and Viscosity in Mixtures of Alkali-Metal Halides and Glycerol

This paper presents the results of density, viscosity, and electrical conductivity measurements for glycerol solutions of some alkali-metal halides at 25°C. The apparent and partial molar volumes (V and V ₁) in mixtures of KCl, NaCl, KBr, KI, and glycerol were calculated from the density data. The Debye–Hückel limiting law was assumed to be valid at low concentrations, and values of the molar volumes at infinite dilution were obtained by extrapolation. The viscosity data were analyzed by means of the Jones–Dole equation. The Kaminsky method, based on reference electrolyte (on B_K+ = B_Cl-), was used in glycerol. Viscosity B-coefficients are compared with those calculated applying existing theories based on the model of hard-charged spheres moving in a solvent continuum. Specific agreement between theory and experiment was not generally good. The electrical conductivities of solutions of salts (KCl, NaCl, KBr, NaBr, NaI, KI, and LiBr) in glycerol have been measured at three concentrations (approximately 0.01, 0.1, and 0.3 M) at 25°C. Values of the molar conductivity at infinite dilution were obtained by extrapolation using the conductance equation of Onsager. Using previously measured transference numbers for KCl and NaCl in glycerol, values of limiting Walden products for the individual alkali-metal and halide ions in glycerol have been derived and compared with those in aqueous and other alcohol solutions.