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1.
Densities of amino acids in aqueous and in aqueous electrolyte solutions have been measured by a high precision vibrating tube digital densitometer at T = 298.15 K under atmospheric pressure. The investigated systems contained amino acids of zwitterionic glycine peptides: glycine (Gly), diglycine (Gly2), triglycine (Gly3), and tetraglycine (Gly4) and cyclic glycylglycine (c(GG)) with electrolytes of potassium chloride (KCl), potassium bromide (KBr) and potassium acetate (KAc). In this series of measurements, the aqueous samples were prepared with various concentrations of the amino acids, up to saturated conditions, and over salt concentrations from 1 to 4 M. The density increments resulting from the addition of the different model compounds of amino acids and the ionic salts were investigated, respectively. An empirical linear combination equation with an augmented term to account the interactions between amino acid and ionic salt was used to quantitatively correlate the experimental densities over the entire concentration ranges.  相似文献   

2.
We have measured the densities of aqueous solutions of serine, serine plus equimolal HCl, and serine plus equimolal NaOH at temperatures 278.15  T/K  368.15, molalities 0.01  m/mol · kg−1  1.0, and at the pressure p = 0.35 MPa, using a vibrating tube densimeter. We have also measured the heat capacities of these solutions at 278.15  T/K  393.15 and at the same m and p using a fixed-cell differential temperature-scanning calorimeter. We used the densities to calculate apparent molar volumes Vϕ and the heat capacities to calculate apparent molar heat capacities Cp,ϕ for these solutions. We used our results and values from the literature for Vϕ(T,m) and Cp,ϕ(T,m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change ΔrCp,m(T,m) for ionization of water to calculate ΔrCp,m(T,m) for proton dissociations from protonated aqueous cationic serine and from the zwitterionic form. We integrated these results in an iterative algorithm using Young’s rule to account for the effects of speciation and chemical relaxation on the observed Vϕ(T,m) and Cp,ϕ(T,m) of the solutions. This procedure yielded parameters for Vϕ(T,m) and Cp,ϕ(T,m) for serinium chloride {H2Ser+Cl(aq)} and for sodium serinate {Na+Gly(aq)} which successfully modeled our observed results. We have then calculated ΔrCp,m, ΔrHm, ΔrVm and pQa for the first and second proton dissociations from protonated aqueous serine as functions of T and m.  相似文献   

3.
Measurements of thermophysical properties (vapour pressure, density, and viscosity) of the (water + lithium bromide + potassium acetate) system LiBr:CH3COOK = 2:1 by mass ratio and the (water + lithium bromide + sodium lactate) system LiBr:CH3CH(OH)COONa = 2:1 by mass ratio were measured. The system, a possible new working fluid for absorption heat pump, consists of absorbent (LiBr + CH3COOK) or (LiBr + CH3CH(OH)COONa) and refrigerant H2O. The vapour pressures were measured in the ranges of temperature and absorbent concentration from T = (293.15 to 333.15) K and from mass fraction 0.20 to 0.50, densities and viscosities were measured from T = (293.15 to 323.15) K and from mass fraction 0.20 to 0.40. The experimental data were correlated with an Antoine-type equation. Densities and viscosities were measured in the same range of temperature and absorbent concentration as that of the vapour pressure. Regression equations for densities and viscosities were obtained with a minimum mean square error criterion.  相似文献   

4.
Vapour pressures, densities, and viscosities of (jojoba oil + n-hexane) were measured and correlated over the temperature interval (298.15 to 318.15) K and used to calculate the activity coefficients of the components, excess thermodynamics functions, excess molar volumes, isobaric thermal expansibilities, excess viscosities, and the excess Gibbs free energies of activation for viscous flow. The reported results are compared with the corresponding values for commercial (oil + n-hexane) mixtures (cottonseed, soybean, sunflower, corn, olive, grape pip, Vaseline, and linalool oils) reported in the literature. As a by-product of this investigation, the vapour pressures of 1-methoxy-2-propanol from T = (298 to 392) K, 2-ethyl-6-methylaniline from T = (313 to 448) K, and N-methoxyisopropanol-6-ethyl-2-methylaniline from T = (407 to 535) K were measured using an ebulliometric method. A remarkable similarity between the excess properties for all oils is observed, but the behaviour of the excess thermodynamic functions in the case of (n-hexane + jojoba oil), especially in the n-hexane rich region, is quite different.  相似文献   

5.
Densities (p, ρ, T, x1) of two binary n-alkane systems are reported from T = (313 to 363) K in the compressed liquid phase up to 25 MPa over the whole range of composition. The binary mixtures {x1n-heptane + (1 ? x1)n-decane} and {x1n-octane + (1 ? x1)n-decane} were prepared at compositions of (x1 = 0.0531, 0.2594, 0.5219, 0.777, 0.952), and (x1 = 0.0616, 0.2801, 0.5314, 0.7736, 0.9623), respectively. A measuring system based on a vibrating tube densimeter, DMA HPM from Anton Paar with data acquisition system was developed in order to obtain experimental densities. Water and nitrogen were used as reference fluids to calibrate the densimeter. Experimental methodology was checked by comparing the n-heptane and n-decane densities against multi-parameter equations proposed in the literature. Differences between both sets of data show a maximum deviation of 0.07%. Excess molar volumes, isothermal compressibility and isobaric thermal expansivity were computed from experimental densities.  相似文献   

6.
We have measured the densities of aqueous solutions of l-methionine, l-methionine plus equimolal HCl, and l-methionine plus equimolal NaOH at temperatures 278.15  T/K  368.15, at molalities 0.0125  m/mol · kg−1  1.0 as solubilities allowed, and at p = 0.35 MPa using a vibrating tube densimeter. We have also measured the heat capacities of these solutions at 278.15  T/K  393.15 and at the same m and p using a twin fixed-cell differential temperature-scanning calorimeter. We used the densities to calculate apparent molar volumes Vϕ and the heat capacities to calculate apparent molar heat capacities Cp,ϕ for these solutions. We used our results and values from the literature for Vϕ(T, m) and Cp,ϕ(T, m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change ΔrCp,m(T, m) for ionization of water to calculate parameters for ΔrCp,m(T, m) for the two proton dissociations from protonated aqueous cationic l-methionine. We integrated these results in an iterative algorithm using Young’s Rule to account for the effects of speciation and chemical relaxation on Vϕ(T, m) and Cp,ϕ(T, m). This procedure yielded parameters for Vϕ(T, m) and Cp,ϕ(T, m) for methioninium chloride {H2Met+Cl(aq)} and for sodium methioninate {Na+Met(aq)} which successfully modeled our observed results. Values are given for ΔrCp,m, ΔrHm, pQa, ΔrSm, and ΔrVm for the first and second proton dissociations from protonated aqueous l-methionine as functions of T and m.  相似文献   

7.
Liquid densities for 2-propanol have been measured at T = (280, 300, 325, 350, 375, and 393) K from about atmospheric pressure up to 10 MPa using a vibrating tube densimeter. The period of vibration has been converted into density using the Forced Path Mechanical Calibration method. The R134a has been used as reference fluid for T ? 350 K and water for T > 350 K. The uncertainty of the measurements is lower than ±0.05%. The measured liquid densities have been correlated with a Starling BWR equation with an overall AAD of 0.025%. The same BWR equation agrees within an AAD lower than 0.2% with the experimental values available in the literature over the same temperature and pressure range.  相似文献   

8.
A flow-mixing isothermal microcalorimeter was used to measure excess molar enthalpies for four binary systems of {diethyl oxalate + (methanol, + ethanol, + 1-propanol, and + 2-propanol)} at T = (288.2, 298.2, 313.2, and 328.2) K and p = 101.3 kPa. The densities of the diethyl oxalate at different temperature were measured by using a vibrating-tube densimeter. All systems exhibit endothermic behaviour over the whole composition range, which means that the rupture of interactions is energetically the main effect. The excess molar enthalpies increase with temperature and the molecular size of the alcohols. The experimental results were correlated by using the Redlich–Kister equation and two local-composition models (NRTL and UNIQUAC).  相似文献   

9.
Apparent molar volumes Vϕ and apparent molar heat capacities Cp,ϕ were determined at the pressure 0.35 MPa for aqueous solutions of magnesium nitrate Mg(NO3)2 at molalities m = (0.02 to 1.0) mol · kg−1, strontium nitrate Sr(NO3)2 at m = (0.05 to 3.0) mol · kg−1, and manganese nitrate Mn(NO3)2 at m = (0.01 to 0.5) mol · kg−1. Our Vϕ values were calculated from solution densities obtained at T = (278.15 to 368.15) K using a vibrating-tube densimeter, and our Cp,ϕ values were calculated from solution heat capacities obtained at T = (278.15 to 393.15) K using a twin fixed-cell, differential, temperature-scanning calorimeter. Empirical functions of m and T were fitted to our results, and standard state partial molar volumes and heat capacities were obtained over the ranges of T investigated.  相似文献   

10.
We have measured the densities of aqueous solutions of alanine, alanine plus equimolal HCl, and alanine plus equimolal NaOH at temperatures 278.15  T/K  368.15, at molalities 0.0075  m/mol · kg−1  1.0, and at the pressure p = 0.35 MPa using a vibrating tube densimeter. We have also measured the heat capacities of these solutions at 278.15  T/K  393.15 and at the same m and p using a twin fixed-cell differential temperature-scanning calorimeter. We used the densities to calculate apparent molar volumes Vϕ and the heat capacities to calculate apparent molar heat capacities Cp,ϕ for these solutions. We used our results and values from the literature for Vϕ(T, m) and Cp,ϕ(T, m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change ΔrCp,m(T, m) for ionization of water to calculate parameters for ΔrCp,m(T, m) for the two proton dissociations from protonated aqueous cationic alanine. We integrated these results in an iterative algorithm using Young’s Rule to account for the effects of speciation and chemical relaxation on Vϕ(T, m) and Cp,ϕ(T, m). This procedure yielded parameters for Vϕ(T, m) and Cp,ϕ(T, m) for alaninium chloride {H2Ala+Cl(aq)} and for sodium alaninate {Na+Ala(aq)} which successfully modeled our observed results. Values are given for ΔrCp,m, ΔrHm, pQa, ΔrSm, and ΔrVm for the first and second proton dissociations from protonated aqueous alanine as functions of T and m.  相似文献   

11.
Densities (ρ) and viscosities (η) of aqueous 1-methylpiperazine (1-MPZ) solutions are reported at T = (298.15 to 343.15) K. Refractive indices (nD) are reported at T = (293.15 to 333.15) K, and surface tensions (γ) are reported at T = (298.15 to 333.15) K. Derived excess properties, except excess viscosities (Δη), are found to be negative over the entire composition range. The addition of 1-MPZ reduces drastically the surface tension of water. The temperature dependence of surface tensions is explained in terms of surface entropy (SS) and enthalpy (HS). The measured and derived properties are used to probe the microscopic liquid structure of the bulk and surface of the aqueous amine solutions.  相似文献   

12.
We have measured the densities of aqueous solutions of isoleucine, threonine, and equimolal solutions of these two amino acids with HCl and with NaOH at temperatures 278.15  T/K  368.15, at molalities 0.01  m/mol · kg−1  1.0, and at the pressure 0.35 MPa using a vibrating tube densimeter. We have also measured the heat capacities of these solutions at 278.15  T/K  393.15 and at the same m and p using a twin fixed-cell differential temperature-scanning calorimeter. We used the densities to calculate apparent molar volumes Vϕ and the heat capacities to calculate apparent molar heat capacities Cp,ϕ for these solutions. We used our results and values from the literature for Vϕ(T, m) and Cp,ϕ(T, m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change ΔrCp,m(T, m) for ionization of water to calculate parameters for ΔrCp,m(T, m) for the two proton dissociations from each of the protonated aqueous cationic amino acids. We used Young’s Rule and integrated these results iteratively to account for the effects of equilibrium speciation and chemical relaxation on Vϕ(T, m) and Cp,ϕ(T, m). This procedure gave parameters for Vϕ(T, m) and Cp,ϕ(T, m) for threoninium and isoleucinium chloride and for sodium threoninate and isoleucinate which modeled our observed results within experimental uncertainties. We report values for ΔrCp,m, ΔrHm, pQa, ΔrSm, and ΔrVm for the first and second proton dissociations from protonated aqueous threonine and isoleucine as functions of T and m.  相似文献   

13.
The densities of tetraalkylammonium perchlorates R4NClO4(R  =  methyl, or ethyl, or propyl, or butyl) and ammonium perchlorate solutions in N, N - dimethylacetamide, dimethyl sulfoxide, and triethylphosphate have been measured over the whole composition range atT =  298.15 K. From these densities, apparent and limiting partial molar volumes of the electrolytes and ions have been evaluated and used to obtain the partial molar volume for theClO4   anion.  相似文献   

14.
The (p, ρ, T) properties and apparent molar volumes Vϕ of CaCl2 in methanol at T = (298.15 to 398.15) K, at pressures up to 40 MPa are reported, and apparent molar volumes have been evaluated. The experimental (p, ρ, T) values were described by an equation of state. The experiments were carried out at m = (0.10819, 0.28529, 0.65879 and 2.39344) mol · kg−1 of calcium chloride.  相似文献   

15.
A calorimetric and thermodynamic investigation of two alkali-metal uranyl molybdates with general composition A2[(UO2)2(MoO4)O2], where A = K and Rb, was performed. Both phases were synthesized by solid-state sintering of a mixture of potassium or rubidium nitrate, molybdenum (VI) oxide and gamma-uranium (VI) oxide at high temperatures. The synthetic products were characterised by X-ray powder diffraction and X-ray fluorescence methods. The enthalpy of formation of K2[(UO2)2(MoO4)O2] was determined using HF-solution calorimetry giving ΔfH° (T = 298 K, K2[(UO2)2(MoO4)O2], cr) = −(4018 ± 8) kJ · mol−1. The low-temperature heat capacity, Ср°, was measured using adiabatic calorimetry from T = (7 to 335) K for K2[(UO2)2(MoO4)O2] and from T = (7 to 326) K for Rb2[(UO2)2(MoO4)O2]. Using these Ср° values, the third law entropy at T = 298.15 K, S°, is calculated as (374 ± 1) J · K−1 · mol−1 for K2[(UO2)2(MoO4)O2] and (390 ± 1) J · K−1 · mol−1 for Rb2[(UO2)2(MoO4)O2]. These new experimental results, together with literature data, are used to calculate the Gibbs energy of formation, ΔfG°, for both phases giving: ΔfG° (T = 298 K, K2[(UO2)2(MoO4)O2], cr) = (−3747 ± 8) kJ · mol−1 and ΔfG° (T = 298 K, Rb2[(UO2)2(MoO4)], cr) = −3736 ± 5 kJ · mol−1. Smoothed Ср°(Т) values between 0 K and 320 K are presented, along with values for S° and the functions [H°(T)  H°(0)] and [G°(T)  H°(0)], for both phases. The stability behaviour of various solid phases and solution complexes in the (K2MoO4 + UO3 + H2O) system with and without CO2 at T = 298 K was investigated by thermodynamic model calculations using the Gibbs energy minimisation approach.  相似文献   

16.
The thermodynamic properties ofZn5(OH)6(CO3)2 , hydrozincite, have been determined by performing solubility and d.s.c. measurements. The solubility constant in aqueous NaClO4media has been measured at temperatures ranging from 288.15 K to 338.15 K at constant ionic strength (I =  1.00 mol · kg  1). Additionally, the dependence of the solubility constant on the ionic strength has been investigated up to I =  3.00 mol · kg  1NaClO4at T =  298.15 K. The standard molar heat capacity Cp, mofunction fromT =  318.15 K to T =  418.15 K, as well as the heat of decomposition of hydrozincite, have been obtained from d.s.c. measurements. All experimental results have been simultaneously evaluated by means of the optimization routine of ChemSage yielding an internally consistent set of thermodynamic data (T =  298.15 K): solubility constant log * Kps 00 =  (9.0  ±  0.1), standard molar Gibbs energy of formationΔfGmo {Zn5(OH)6(CO3)2 }  =  (  3164.6  ±  3.0)kJ · mol  1, standard molar enthalpy of formation ΔfHmo{Zn5(OH)6(CO3)2 }  =  (  3584  ±  15)kJ · mol  1, standard molar entropy Smo{Zn5(OH)6(CO3)2 }  =  (436  ±  50)J · mol  1· K  1and Cp,mo / (J · mol  1· K  1)  =  (119  ±  11)  +  (0.834  ±  0.033)T / K. A three-dimensional predominance diagram is introduced which allows a comprehensive thermodynamic interpretation of phase relations in(Zn2 +  +  H2O  +  CO2) . The axes of this phase diagram correspond to the potential quantities: temperature, partial pressure of carbon dioxide and pH of the aqueous solution. Moreover, it is shown how the stoichiometric composition{n(CO3) / n(Zn)} of the solid compoundsZnCO3 and Zn5(OH)6(CO3)2can be checked by thermodynamically analysing the measured solubility data.  相似文献   

17.
Density data for dilute aqueous solutions of two diols (1,6-hexanediol, 2,2-dimethyl-1,3-propanediol) and two polyhydric alcohols (2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,3,4,5-pentanepentaol) are presented together with partial molar volumes at infinite dilution calculated from the experimental data. The measurements were performed at temperatures from T = 298 K up to T = 573 K and at pressure close to the saturated vapour pressure of water, at pressures between 15 and 20 MPa and at p = 30 MPa. While temperature dependences of partial molar volumes of both diols are monotonous, maxima are observed on the curves for polyhydric alcohols. The data were obtained using a high-temperature high-pressure flow vibrating-tube densimeter.  相似文献   

18.
Solubility isotherms of the ternary system (LiCl + CaCl2 + H2O) were elaborately determined at T = (283.15 and 323.15) K. Several thermodynamic models were applied to represent the thermodynamic properties of this system. By comparing the predicted and experimental water activities in the ternary system, an empirical modified BET model was selected to represent the thermodynamic properties of this system. The solubility data determined in this work at T = (283.15 and 323.15) K, as well as those from the literature at other temperatures, were used for the model parameterization. A complete phase diagram of the ternary system was predicted over the temperature range from (273.15 to 323.15) K. Subsequently, the Gibbs free energy of formation of the solid phases CaCl2 · 4 H2O(s), CaCl2 · 2 H2O(s), LiCl · 2H2O(s), and LiCl · CaCl2 · 5H2O(s) was estimated and compared with the literature data.  相似文献   

19.
The bromide minerals solubility in the mixed system (m1NaBr + m2MgBr2)(aq) have been investigated at T = 323.15 K by the physico-chemical analysis method. The equilibrium crystallization of NaBr·2H2O(cr), NaBr(cr), and MgBr2·6H2O(cr) has been established. The solubility-measurements results obtained have been combined with all other experimental equilibrium solubility data available in literature at T = (273.15 and 298.15) K to construct a chemical model that calculates (solid + liquid) equilibria in the mixed system (m1NaBr + m2MgBr2)(aq). The solubility modeling approach based on fundamental Pitzer specific interaction equations is employed. The model gives a very good agreement with bromide salts equilibrium solubility data. Temperature extrapolation of the mixed system model provides reasonable mineral solubility at high temperature (up to 100 °C). This model expands the previously published temperature variable sodium–potassium–bromide and potassium–magnesium–bromide models by evaluating sodium–magnesium mixing parameters. The resulting model for quaternary system (Na + K + Mg + Br + H2O) is validated by comparing solubility predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solution models due to data insufficiencies at high temperature are discussed.  相似文献   

20.
Phase transitions for (water + 1-methylnaphthalene + light aromatic hydrocarbon) ternary systems are observed at their (liquid + liquid) equilibria at T = (563, 573, and 583) K and (8.6 to 25.0) MPa. The phase transition pressures at T = (563, 573, and 583) K were measured for the five species of light aromatic hydrocarbons, o-, m-, p-xylenes, ethylbenzene, and mesitylene. The measurements of the phase transition pressures were carried out by changing the feed mole fraction of water and 1-methylnaphthalene in water free, respectively. Effects of the feed mole fraction of water on the phase transition pressures are very small. Increasing the feed mole fraction of 1-methylnaphthalene results in decreasing the phase transition pressures at constant temperature. The slopes depending on the feed mole fraction for 1-methylnaphthalene at the phase transition pressures are decreased with increasing temperature for (water + 1-methylnaphthalene + p-xylene), (water + 1-methylnaphthalene + o-xylene), and (water + 1-methylnaphthalene + mesitylene) systems. For xylene isomers, the highest and lowest of the phase transition pressures are obtained in the case of p- and o-xylenes, respectively. The phase transition pressures for ethylbenzene are lower than those in the case of p-xylene. The similar phase transition pressures are given for p-xylene and mesitylene.  相似文献   

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