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.     

Thermal Property Measurements and Enthalpy Calculation of the Lithium Bromide+Lithium Iodide+1,3-Propanediol+Water System

The lithium bromide+lithium iodide+1,3-propanediol+water [LiBr/LiI mole ratio=4 and (LiBr+LiI)/HO(CH₂)₃ OH mass ratio=4] solution is being considered as a potential working fluid for an absorption chiller. Heat capacities at four temperatures, 283.15, 298.15, 313.15, and 333.15 K, were measured in the range from 50 to 70 mass%. In addition, the differential heats of dilution at 298.15 K were measured in the range from 45.3 to 71.8 mass%. Each individual data set was correlated with a proper regression equation with a high accuracy. A new enthalpy calculation method for the working fluids containing organics was proposed. The calculation method correlated the heat capacity (at various temperatures and concentrations) and the differential heat of dilution (at ambient temperature and various concentrations). The present method was applied for the construction of enthalpy–concentration (H–T–X) diagrams with high confidence.     

Thermodynamic properties of lithium bromide–water solutions at high temperatures

Emerging triple-effect LiBr–water absorption chillers operate at higher temperatures and pressures than traditional double-effect chillers. However, there is not enough data about thermodynamic properties of LiBr–water solutions at such high temperatures. Using recently measured data of vapor pressure and heat capacity, we have developed the equations which can calculate the vapor pressure, enthalpy and entropy of LiBr solutions at such high temperatures. The developed equations are valid from concentrations of 40–65 wt.% and also from temperatures of 40–210°C. These equations will be very helpful for the modeling and design of triple-effect LiBr–water chillers.     

Experimental correlation of falling film absorption heat transfer on micro-scale hatched tubes

The objectives of this paper are to investigate the effect of surface roughness of micro-hatching tubes on the absorption performance and to develop an experimental correlation of Nusselt number as a function of the roughness. Two different micro-scale hatched tubes and a bare tube are tested to quantify the effect of the surface roughness on the absorption performance. The roughness of the micro-scale hatched tubes ranges 0.386–11.359 μm. The working fluid is H₂O/LiBr solution with inlet concentration of 55, 58 and 61 wt.% of LiBr. The absorber heat exchanger consists of 24 horizontal tubes in a column, liquid distributor at the liquid inlet and the liquid reservoir at the bottom of the absorber. It was found that absorption performance of micro-hatching tubes was improved up to two times compared with the bare tube. An experimental correlation of Nusselt number was developed as a function of the film Reynolds number and the roughness with an error band of ±25%.     

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.     

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%.     

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.     

Flow boiling heat transfer to carbon dioxide: general prediction method

An updated version of the Kattan–Thome–Favrat flow pattern based, flow boiling heat transfer model for horizontal tubes has been developed specifically for CO₂. Because CO₂ has a low critical temperature and hence high evaporating pressures compared to our previous database, it was found necessary to first correct the nucleate pool boiling correlation to better describe CO₂ at high reduced pressures and secondly to include a boiling suppression factor on the nucleate boiling heat transfer coefficient to capture the trends in the flow boiling data. The new method predicts 73% of the CO₂ database (404 data points) to within ±20% and 86% to within ±30% over the vapor quality range of 2–91%. The database covers five tube diameters from 0.79 to 10.06 mm, mass velocities from 85 to 1440 kg m⁻² s⁻¹, heat fluxes from 5 to 36 kW m⁻², saturation temperatures from −25 °C to +25 °C and saturation pressures from 1.7 to 6.4 MPa (reduced pressures up to 0.87).     

Physical properties of transparent conducting Cd–Te–In–O thin films: Outlining a thermodynamic system for transparent conducting oxides

Cd–Te–In–O thin films are grown by pulsed laser deposition using a composite target of CdTe powder embedded in an indium matrix. Oxygen pressures range from 2.00 to 6.67 Pa at a substrate temperature of 420 °C. The structure, optical transmission and sheet resistance of the films are measured. Substitutional compounds with In_2 − 2x(Cd,Te)_2xO₃ stoichiometry are found at high oxygen pressures. A ternary phase diagram of the CdO–In₂O₃–TeO₂ system shows the relationship between the structure and the stoichiometry of the films. To evaluate film performance, a figure of merit is proposed based on the relationship between the integral photonic flux and the sheet resistance. The best figure of merit values corresponds to a sample prepared at 3.8 Pa O₂ that consists of (In₂O₃)_0.3(CdTe₂O₅)_0.7 and exhibits an optical band gap of 3.0 eV. This sample is a suitable substrate for electrodeposition due to its good electrochemical stability.     

Ferroelectric phase transition temperatures of self-flux-grown RbTiOPO4 crystals

A series of RTP crystals have been grown by the top-seeded solution growth method from self-fluxes containing different [Rb]/[P] atomic ratios (1.25–2) and solute concentrations (0.55–1.1 g-RTP/g-flux) covering a large portion of the RTP crystallization field in the Rb₂O–P₂O₅–TiO₂ ternary system. The Curie points of as-grown crystals have been determined using the standard dielectric (capacitance) technique, and they show a spread from 770 to 800 °C. This indicates a clear correlation between the crystal stoichiometry and the flux chemical composition in similarity with KTP crystals. The major difference from the KTP case is that each growth sector (solidified simultaneously) in nominally pure RTP crystals exhibits its specific Curie temperature. Chemical analysis and intentional doping experiments show that trace impurities may have a very limited influence on this effect. The abrupt changes of the Curie temperatures along simultaneously grown surfaces are discussed in terms of the diverse incorporation mechanisms of the stoichiometric components or native defects into specific crystallographic faces during growth.     

The effect of micro-scale surface treatment on heat and mass transfer performance for a falling film H2O/LiBr absorber

The objectives of this paper are to develop a new method of wettability measurement, to study the effect of micro-scale surface treatment on the wettability across horizontal tubes and to apply it for numerical analysis of heat and mass transfer in a H₂O/LiBr falling film absorber. Three types of tubes with roughness are tested in a test rig. Inlet solution temperature (30–50 °C), concentration (55–62 wt.% of LiBr) and mass flow rate (0.74–2.71 kg/min) are considered as key parameters. Reynolds number ranged from 30 to 120 by controlling the inlet mass flow rate. The wettability on the roughened tubes was higher than that for the smooth tubes. The wettability decreased linearly along the vertical location but was proportional to the solution temperature and mass flow rate. The experimental correlations of the wettability for the smooth and the roughened tubes were developed with error bands of ±20 and ±10%, respectively. These are used for the heat and mass transfer analysis of absorbers with micro-scale hatched tubes.     

Ferrimagnetic and semiconducting CaCu3Fe2Sb2O12 by first principles

CaCu₃Fe₂Sb₂O₁₂ is mechanically stable, thermodynamically stable at pressures above 18 GPa. Both GGA and GGA + U methods predict that it is a ferrimagnetic semiconductor with Fe³⁺ in high spin state (S = 5/2). The coupling of Fe–Cu is antiferromagnetic, while that of Cu–Cu is ferromagnetic. The calculated total spin moment is 6.17 μ_B.     

Experimental evaluation of the performances of a H2O–LiBr absorption refrigerator under different service conditions

The paper describes an experimental plant aimed at simulating and verifying the performances of a single-stage H₂O–LiBr absorption machine. The machine is water cooled and it is supplied by hot water produced by an electrical boiler; it is possible to simulate different service conditions by varying the temperatures and the flow rate of water in the external circuits. Measurement facilities allow to record in real time all the main operating parameters of internal and external circuits (temperatures, pressures and flow rates). The paper illustrates the characteristics of the machine and of the plant and the results of various experimental campaigns. In particular, the acquisitions on the plant have tested different service conditions by varying the flow rate and the temperature of the supplying hot water; the energy and energy performances of the plant are presented and compared with data from literature and from a simulation code developed for the plant.The results show that the absorption machine can work, with acceptable efficiency, with input temperatures of about 65–70 °C; this result is interesting for a future supply of the machine with solar energy.     

Determination of thermal properties of dilute LiBr-water solutions

We are developing an absorption air cooling system which can supply 2°C chilled water for air cooling by the usage of dilute solutions of LiBr in water with an evaporating temperature of −6°C as a nonfreezing refrigerant. However, there are few published data for the thermal properties of dilute LiBr water solutions (0 to 30%) below 10°C. In this paper, the freezing temperature and the saturated vapor pressure are reported. The results clearly show the possibility of developing a new type of LiBr absorption refrigerating machine to generate evaporating temperatures below 0°C. To obtain accurate data for the design of this new type of absorption refrigerating machine, an apparatus has been developed to measure the thermal properties of dilute LiBr water solutions below 10°C. The experimental arrangement consists of a cooling bath (340×240×190 mm) filled with fluorocarbon, a glass measuring bottle (ϕ120×100 mm), and an absolute pressure gauge (0–1.3 kPa). The accuracy of the temperature, pressure, and density are within ±0.1°C, 0.01 kPa, and ±0.005%, respectively. Paper presented at the Fourth Asian Thermophysical Properties Conference, September 5–8, 1995, Tokyo, Japan.     

Corrosion behaviour of copper in LiBr solutions – surface examination

Optical microscope (O.M) and scanning electron microscope (SEM) equipped with energy dispersive X‐ray (EDX) were used to follow the changes that occurred on the surfaces of copper after treated electrochemically in concentrated solutions of LiBr (up to 9 M). Results showed the existence of protective film of CuO and Cu(OH)₂ which are recorded during the passive film formation in 5 × 10^–1 M LiBr at 200 mV. At 1 M LiBr and during the partial passive region (600 mV) a porous film of Cu₂O with a small ratio of CuOH and Cu(OH)₂ were detected which confirmed the higher current density recorded. On the other hand and at the same concentration (1 M LiBr at 1000 mV), surface examination confirmed the detection of CuBr₂ with small ratio of CuO which explain the deleterious effect of bromide and the autocatalytic dissolution of Cu at this higher potential. At higher concentrations from 4 to 9 M, the film formed is non homogeneous with a more porous structure which is mainly CuBr and some area of the film suffered from cracking. This proves the general dissolution through the complexing formation of soluble CuBr₂^–.     

Salt effect of lithium bromide on the solution polymerization of acrylonitrile

Abstract

In this paper, the salt effect of lithium bromide (LiBr) on the dimethyl formamid (DMF) solution polymerization of acrylonitrile was studied. From the experimental data, we proposed a possible mechanism and derived its rate expression to determine the kinetic parameters for this system. The results show that the values of k_v/k_tr (1.984～79.365) and k_t/k² _tr (3.311×l0²～3.156×l0⁵ sec·mole/1) of the DMF‐LiBr solution polymerization of acrylonitrile are larger than those of the DMF‐LiCl solution polymerization of acrylonitrile shown by Bamford and others. These results can be explained by the basicity of salt and the dissociation of polyacrylonitrile in the DMF‐LiBr solution.     

Structure, Phonon Vibration, and Spin Correlation of LaBa2Cu3?xCoxOy

Polycrystalline samples LaBa₂Cu_3–xCo _x O _y (0 x 1.0) were synthesized by solid state reaction method. The structure, phonon vibration, conduction, and spin correlation were investigated by means of X-ray diffraction, infrared spectra, resistivity, and electron spin resonance. It is found that there are orthorhombic–tetragonal and tetragonal–orthorhombic structural transitions with Co doping, and the conduction behavior changes from metallic to semiconducting. With the increase of Co content, the Cu(1)—O(1) phonon mode around 531 cm^–1 softens, the Cu(2)—O(2) phonon mode around 657 cm^–1 hardens, and the Cu(1)—O(4) mode around 583 cm^–1 is nearly unchanged. The Cu²⁺ spins tend to localize with Co doping. The changes in structure, phonon vibration, and spin correlation with Co doping are analyzed and discussed.     

Saturated liquid densities and bubble-point pressures of the binary HFC 152a+HCFC 142b system

Forty-eight sets of the saturated liquid densities and bubble-point pressures of the binary HFC 152a + HCFC 142b system were measured with a magnetic densimeter coupled with a variable-volume cell. The measurements obtained at four compositions, 20, 40, 60, and 80 wt%, of HFC 152a cover a range of temperatures from 280 to 400 K. The experimental uncertainties in temperature, pressure, density, and composition were estimated to be within ±15mK, ±20kPa, ±0.2%, and between –0.14 and ±0.01 wt% HFC 152a (–0.01 and + 0.14 wt% HCFC 142b), respectively. The purities of the samples were 99.9 wt% for HFC 152a and 99.8 wt% for HCFC 142b. A binary interaction parameter, k _ij , in the Peng-Robinson equation of state was determined as a function of temperature for representing the bubble-point pressures. On the other hand, two constant binary-interaction parameters, k _ij and l _ij , were introduced into the mixing rule of the Hankinson-Brobst-Thomson equation for representing the saturated liquid densities.     

Vapor pressures of new fluorocarbons

The vapor pressures of four fluorocarbons have been measured at the following temperature ranges: R123 (2,2-dichloro-l,l,l-trifluoroethane), 273–457 K; R123a (1,2-dichloro-1,1,2-trifluoroethane), 303–458 K; R134a (1,1,1,2-tetrafluoroethane), 253–373 K; and R132b (l,2-dichloro-l,l-difluoroethane), 273–398 K. Determinations of the vapor pressure were carried out by a constant-volume apparatus with an uncertainty of less than 1.0%. The vapor pressures of R123 and R123a are very similar to those of R11 over the whole experimental temperature range, but the vapor pressures of R134a and R132b differ somewhat from those of R12 and R113, respectively, as the temperature increases. The numerical vapor pressure data can be fitted by an empirical equation using the Chebyshev polynomial with a mean deviation of less than 0.3 %.     

Thermal conductivity and viscosity of 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123)

The thermal conductivity and the viscosity data of CFC alternative refrigerant HCFC-123 (2,2-dichloro-1,1,1-trifluoroethane: CHCI₂-CF₃) were critically evaluated and correlated on the basis of a comprehensive literature survey. Using the residual transport-property concept, we have developed the three-dimensional surfaces of the thermal conductivity-temperature-density and the viscosity-temperature-density. A dilute-gas function and an excess function of simple form were established for each property. The critical enhancement contribution was taken no account because reliable crossover equations of state and the thermal conductivity data are still missing in the critical region. The correlation for the thermal conductivity is valid at temperatures from 253 to 373 K, pressures up to 30 MPa, and densities up to 1633 kg m^–3. The correlation for the viscosity is valid at temperatures from 253 to 423 K, pressures up to 20 MPa. and densities up to 1608 kg·m^–3. The uncertainties of the present correlations are estimated to be 50% for both properties, since the experimental data are still scarce and somewhat contradictory in the vapor phase at present.