Solubilities of l-glutamic acid, 3-nitrobenzoic acid,p-toluic acid,calcium-l-lactate,calcium gluconate,magnesium-dl-aspartate,and magnesium-l-lactate in water

Solubilities of l -glutamic acid, 3-nitrobenzoic acid, p -toluic acid, calcium-l -lactate, calcium gluconate, magnesium- dl -aspartate, and magnesium- l -lactate in water were determined in the temperature range 278 K to 343 K. The apparent molar enthalpies of solution at T =  298.15 K as derived from these solubilities areΔ_solH_m (l -glutamic acid,m_sat =  0.0565 mol · kg ^− 1)  =  30.2 kJ · mol ^− 1,Δ_solH_m (3-nitrobenzoic acid, m =  0.0188 mol · kg ^− 1)  =  28.1 kJ · mol ^− 1, Δ_solH_m( p - toluic acid, m =  0.00267 mol · kg ^− 1)  =  23.9 kJ · mol ^− 1,Δ_solH_m (calcium- l -lactate tetrahydrate,m =  0.2902 mol · kg ^− 1)  =  25.8 kJ · mol ^− 1,Δ_solH_m (calcium gluconate, m =  0.0806 mol · kg ^− 1)  =  22.1 kJ · mol ^− 1, Δ_solH_m(magnesium-dl -aspartate tetrahydrate, m =  0.1469 mol · kg ^− 1)  =  11.5 kJ · mol ^− 1, andΔ_solH_m (magnesium- l -lactate trihydrate,m =  0.3462 mol · kg ^− 1)  =  3.81 kJ · mol ^− 1.     

The solubility measurements of sodium dicarboxylate salts; sodium oxalate,malonate, succinate,glutarate, and adipate in water from T = (279.15 to 358.15) K

The solubility measurements of sodium dicarboxylate salts; sodium oxalate, malonate, succinate, glutarate, and adipate in water at temperatures from (278.15 to 358.15 K) were determined. The molar enthalpies of solution at T = 298.15 K were derived: Δ_solH_m (m = 2.11 mol · kg^?1) = 13.86 kJ · mol^?1 for sodium oxalate; Δ_solH_m (m = 3.99 mol · kg^?1) = 14.83 kJ · mol^?1 for sodium malonate; Δ_solH_m (m = 2.45 mol · kg^?1) = 14.83 kJ · mol^?1 for sodium succinate; Δ_solH_m (m = 4.53 mol · kg^?1) = 16.55 kJ · mol^?1 for sodium glutarate, and Δ_solH_m (m = 3.52 mol · kg^?1) = 15.70 kJ · mol^?1 for sodium adipate. The solubility value exhibits a prominent odd–even effect with respect to terms with odd number of sodium dicarboxylate carbon numbers showing much higher solubility. This odd–even effect may have implications for the relative abundance of these compounds in industrial applications and also in the atmospheric aerosols.     

Ternary mutual diffusion coefficients of aqueous {l-dopa (1) + β-CD (2)} solutions at T = 298.15 K

Ternary mutual diffusion coefficients (D₁₁, D₂₂, D₁₂ and D₂₁) measured by the Taylor dispersion method are reported for aqueous solutions of {levodopa (l-dopa) + β-cyclodextrin (β-CD)} solutions at T = 298.15 K and concentrations up to 0.007 mol · dm⁻³. Significant effects on the diffusion were observed, suggesting interactions between this carbohydrate and l-dopa. Support for this came from ¹H NMR spectroscopy, which shows that these effects are due to formation of 1:1 (β-CD:l-dopa) complexes.     

The molar enthalpies of solution and vapour pressures of saturated aqueous solutions of some cesium salts

Vapour pressures of water over saturated solutions of cesium chloride, cesium bromide, cesium nitrate, cesium sulfate, cesium formate, and cesium oxalate were determined as a function of temperature. These vapour pressures were used to evaluate the water activities, osmotic coefficients and molar enthalpies of vapourization. Molar enthalpies of solution of cesium chloride, Δ_solH_m(T = 295.73 K; m = 0.0622 mol · kg⁻¹) = (17.83 ± 0.50) kJ · mol⁻¹; cesium bromide, Δ_solH_m(T = 293.99 K; m = 0.0238 mol · kg⁻¹) = (26.91 ± 0.59) kJ · mol⁻¹; cesium nitrate, Δ_solH_m(T = 294.68 K; m = 0.0258 mol · kg⁻¹) = (37.1 ± 2.3) kJ · mol⁻¹; cesium sulfate, Δ_solH_m(T = 296.43 K; m = 0.0284 mol · kg⁻¹) = (16.94 ± 0.43) kJ · mol⁻¹; cesium formate, Δ_solH_m(T = 295.64 K; m = 0.0283 mol · kg⁻¹) = (11.10 ± 0.26) kJ · mol⁻¹ and Δ_solH_m(T = 292.64 K; m = 0.0577 mol · kg⁻¹) = (11.56 ± 0.56) kJ · mol⁻¹; and cesium oxalate, Δ_solH_m(T = 291.34 K; m = 0.0143 mol · kg⁻¹) = (22.07 ± 0.16) kJ · mol⁻¹ were determined calorimetrically. The purity of the chemicals was generally greater than 0.99 mass fraction, except for HCOOCs and (COOCs)₂ where purities were approximately 0.95 and 0.97 mass fraction, respectively. The uncertainties are one standard deviations.     

The vapour pressures of saturated aqueous solutions of magnesium,calcium, nickel and zinc acetates and molar enthalpies of solution of magnesium,calcium, zinc and lead acetates

Vapour pressures of water over saturated solutions of magnesium, calcium, nickel and zinc acetates were determined as a function of temperature. The vapour pressures served to evaluate the water activities, osmotic coefficients and molar enthalpies of vaporization. Molar enthalpies of solution of magnesium acetate tetrahydrate,Δ_solH_m (T =  294.71K ;m =  0.01 mol · kg ^− 1)  =  − (15.65  ±  0.97)kJ · mol ^− 1; calcium acetate,Δ_solH_m (T =  297.18K ;m =  0.01 mol · kg ^− 1)  =  − (28.15  ±  0.28)kJ · mol ^− 1; zinc acetate dihydrate,Δ_solH_m (T =  297.36K ;m =  0.01 mol · kg ^− 1)  =  − (22.49  ±  0.90)kJ · mol ^− 1and lead acetate trihydrate,Δ_solH_m (T =  297.36K ;m =  0.0086 mol · kg ^− 1)  =  (22.46  ±  0.94)kJ · mol ^− 1, were determined calorimetrically.     

Thermodynamic properties,detonation characterisation and free radical of N-acetyl-3,3-dinitroazetidine

N-acetyl-3,3-dinitroazetidine (ADNAZ) is an important precursor for synthesizing new multinitroazetidine energetic compounds. Its thermal behaviour was studied under a non-isothermal condition by DSC and TG/DTG methods, the results show that there are one melting process and one endothermic decomposition process. The specific molar heat capacity (C_p,m) of ADNAZ was determined by a continuous C_p mode of micro-calorimeter and theoretical calculation, and the C_p,m of ADNAZ was 240.37 J · K⁻¹ · mol⁻¹ at T = 298.15 K. The detonation velocity (D) and detonation pressure (P) of ADNAZ were estimated using the nitrogen equivalent equation according to the experimental density, the value of D and P are (6685.83 ± 3.12) m · s⁻¹ and (18.36 ± 0.02) GPa, respectively. The free radical signals of ADNAZ were detected by electron spin resonance (ESR) technique, which is used to estimate its sensitivity.     

Thermodynamics of proton dissociations from aqueous l-methionine at temperatures from (278.15 to 393.15) K,molalities from (0.0125 to 1.0) mol · kg−1, and at the pressure 0.35 MPa: Apparent molar heat capacities and apparent molar volumes of l-methionine,methioninium chloride,and sodium methioninate

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 V_ϕ and the heat capacities to calculate apparent molar heat capacities C_p,ϕ for these solutions. We used our results and values from the literature for V_ϕ(T, m) and C_p,ϕ(T, m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change Δ_rC_p,m(T, m) for ionization of water to calculate parameters for Δ_rC_p,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 V_ϕ(T, m) and C_p,ϕ(T, m). This procedure yielded parameters for V_ϕ(T, m) and C_p,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 Δ_rC_p,m, Δ_rH_m, pQ_a, Δ_rS_m, and Δ_rV_m for the first and second proton dissociations from protonated aqueous l-methionine as functions of T and m.     

Buffer standards for the physiological pH of N-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]glycine (TRICINE) from T = (278.15 to 328.15) K

The pH values of two buffer solutions without NaCl and seven buffer solutions with added NaCl, having ionic strengths (I = 0.16 mol · kg⁻¹) similar to those of physiological fluids, have been evaluated at 12 temperatures from T = (278.15 to 328.15) K by way of the extended form of the Debye–Hückel equation of the Bates–Guggenheim convention. The residual liquid junction potentials (δE_j) between the buffer solutions of TRICINE and saturated KCl solution of the calomel electrode at T = (298.15 and 310.15) K have been estimated by measurement with a flowing junction cell. For the buffer solutions with the molality of TRICINE(m₁) = 0.06 mol · kg⁻¹, NaTRICINE(m₂) = 0.02 mol · kg⁻¹, and NaCl(m₃) = 0.14 mol · kg⁻¹, the pH values at T = 310.15 K obtained from the extended Debye–Hückel equation and the inclusion of the liquid junction correction are 7.342 and 7.342, respectively. These are in excellent agreement. The zwitterionic buffer TRICINE is recommended as a secondary pH standard in the region for clinical application.     

Apparent molar volumes and apparent molar heat capacities of aqueous solutions ofα- andβ-cyclodextrins at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa

Apparent molar heat capacities C_{p, φ}and apparent molar volumesV_φ were determined for aqueous solutions of α - and β -cyclodextrins at temperatures from 278.15 K to 393.15 K and at the pressure 0.35 MPa. The molalities investigated ranged from 0.008 mol · kg ^− 1to 0.12 mol · kg ^− 1forα -cyclodextrin and from 0.004 mol · kg ^− 1to 0.014 mol · kg ^− 1for β -cyclodextrin. We used a vibrating-tube densimeter (DMA 512P, Anton PAAR, Austria) to determine the densities and volumetric properties. Heat capacities were obtained using a twin fixed-cell, power-compensation, differential-output, temperature-scanning calorimeter (NanoDSC 6100, Calorimetry Sciences Corporation, Spanish Fork, UT, USA). Equations were fit by regression to our experimental (V_φ, T, m) and (C_{p, φ},T , m) results. Infinite dilution partial molar volumes V₂^oand heat capacities C_p,2^owere obtained over the range of temperatures by extrapolation of these surfaces to m =  0.     

Study on the enthalpy of solution and enthalpy of dilution for the ionic liquid [C3mim][Val] (1-propyl-3-methylimidazolium valine)

A new amino acid ionic liquid (AAIL) [C₃mim][Val] (1-propyl-3-methylimidazolium valine) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar solution enthalpies of the ionic liquid [C₃mim][Val] with known amounts of water and with different concentrations in molality were measured at T = 298.15 K. In terms of standard addition method (SAM) and Archer’s method, the standard molar enthalpy of solution for [C₃mim][Val] without water, ${\mathrm{\Delta }}_{\text{s}}{H}_{\text{m}}^{\circ }$ = (−55.7 ± 0.4) kJ · mol⁻¹, was obtained. The hydration enthalpy of the cation [C₃mim]⁺, ΔH₊ ([C₃mim]⁺) = −226 kJ · mol⁻¹, was estimated in terms of Glasser’s theory. Using the RD496-III heat conduction microcalorimeter, the molar enthalpies of dilution, Δ_DH_m(m_i → m_f), of aqueous [C₃mim][Val] with various values of molality were measured. The values of Δ_DH_m(m_i → m_f) were fitted to Pitzer’s ion-interaction model and the values of apparent relative molar enthalpy, ^φL, calculated using Pitzer’s ion-interaction model.     

Insights into the electro-oxidation of ethylene glycol at Pt/Ru nanocatalysts supported on MWCNTs: Adsorption-controlled electrode kinetics

Electrocatalytic properties of Pt/Ru nanoparticle-electrodecorated MWCNT platform towards the oxidation of ethylene glycol (EG) have been interrogated using cyclic voltammetry and electrochemical impedance spectroscopy. Both forward and reverse oxidative reactions exhibited distinct electrochemical behaviour following changes in EG concentrations, scan rates and during repetitive cyclic voltammetric scanning. Our results suggest that the overall electro-oxidation reaction of EG is governed mainly by adsorption kinetics, with the electrochemical adsorption equilibrium constant (β) and the free energy change (ΔG^o) being 1.47 M^?1 and ?0.95 kJ mol^?1, respectively.     

Synthesis,crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa = hexafluoroacetylacetonate,Phen = o-phenanthroline)

The mixed ligand complex [La(hfa)₃(Phen)₂] (I) was obtained by the interaction of La(hfa)₃ and Phen; its composition does not depend on the stoichiometry of the reagents. According to the X-ray single crystal analysis data, complex I crystallizes in the monoclinic space group P2₁/n, with a = 13.583(3) Å, b = 16.959(3) Å, c = 18.860(4) Å, β = 94.71(3)° and Z = 4. The structure of I consists of isolated mononuclear molecules, the coordination number of La being 10. Thermal behaviour and composition of the vapor phase have been studied for I by thermal analysis and mass-spectrometry using a Knudsen cell. The mixed ligand complex I was found to sublime congruently in the temperature range 370–460 K: [La(hfa)₃(Phen)₂]_(s) = [La(hfa)₃(Phen)]_(g) + Phen_(g), Δ_rH⁰(T) = 316.2 ± 1.8 kJ/mol.     

Thermodynamics of proton dissociations from aqueous alanine at temperatures from (278.15 to 393.15) K,molalities from (0.0075 to 1.0) mol · kg−1, and at the pressure 0.35 MPa: Apparent molar heat capacities and apparent molar volumes of alanine,alaninium chloride,and sodium alaninate

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 V_ϕ and the heat capacities to calculate apparent molar heat capacities C_p,ϕ for these solutions. We used our results and values from the literature for V_ϕ(T, m) and C_p,ϕ(T, m) for HCl(aq), NaOH(aq), and NaCl(aq) and the molar heat capacity change Δ_rC_p,m(T, m) for ionization of water to calculate parameters for Δ_rC_p,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 V_ϕ(T, m) and C_p,ϕ(T, m). This procedure yielded parameters for V_ϕ(T, m) and C_p,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 Δ_rC_p,m, Δ_rH_m, pQ_a, Δ_rS_m, and Δ_rV_m for the first and second proton dissociations from protonated aqueous alanine as functions of T and m.     

Dual-signal anodic stripping voltammetric determination of trace arsenic(III) at a glassy carbon electrode modified with internal-electrolysis deposited gold nanoparticles

A glassy carbon electrode (GCE) modified with internal-electrolysis deposited gold nanoparticles (AuNPs_ied) was applied to sensitively and selectively detect As(III) by anodic stripping linear sweep voltammetry (ASLSV). The AuNPs_ied/GCE was prepared based on the redox replacement reaction between a supporting-electrolyte-free aqueous HAuCl₄ and a copper sheet in saturated KCl separated by a salt bridge. Under optimum conditions (0.5 M aqueous H₂SO₄, 300-s preconcentration at − 0.4 V), the ASLSV peak current for the As(0)–As(III) oxidation responded linearly to As(III) concentration from 0.02 to 3 μM with a limit of detection (LOD) of 0.9 nM (0.07 μg L^− 1) (S/N = 3), while that for the As(III)–As(V) oxidation was linear with As(III) concentration from 0.02 to 1 μM with a LOD of 4 nM (0.3 μg L^− 1) (S/N = 3). An appropriate high-scan-rate for ASLSV can enhance both the sensitivity and signal-to-noise ratio. This method was applied for analyses of As(III) in real water samples.     

Double beryllium iodate dihydrates,M2Be(IO3)4·2H2O (M = K,NH4+, Rb): Preparation,X-ray powder diffraction and vibrational spectra

The solubilities in the three-component systems MIO₃–Be(IO₃)₂–H₂O (M = K, NH₄⁺, Rb, Cs) were studied at 25 °C by the method of isothermal decrease of supersaturation. It has been established that double salts, K₂Be(IO₃)₄·2H₂O, (NH₄)₂Be(IO₃)₄·2H₂O, and Rb₂Be(IO₃)₄·2H₂O, crystallize from the ternary solutions within wide concentration ranges. Both the X-ray powder diffraction and the spectroscopic studies (infrared and Raman) reveal that the title compounds are isostructural. They crystallize in the monoclinic space group P2/m with lattice parameters: K₂Be(IO₃)₄·2H₂O – a = 14.218(5) Å, b = 6.747(2) Å, c = 5.765(2) Å, β = 98.74(4)°, V = 546.6(2) Å³; (NH₄)₂Be(IO₃)₄·2H₂O – a = 14.414(4) Å, b = 6.838(2) Å, c = 5.947(2) Å, β = 99.52(4)°, V = 578.0(2) Å³; Rb₂Be(IO₃)₄·2H₂O – a = 14.423(4) Å, b = 6.867(2) Å, c = 5.743(3) Å, β = 98.15(3)°, V = 562.9(3) Å³.Infrared spectroscopic experiments show that comparatively strong hydrogen bonds are formed in the potassium and rubidium salts as deduced from the wavenumbers of ν_OD of matrix-isolated HDO molecules (isotopically dilute samples) owing to the strong Be–OH₂ interactions (synergetic effect). However, the IO₃⁻ ions in the ammonium compound are involved in hydrogen bonds with NH₄⁺ ions additionally to those with water molecules and as a result of these intermolecular interactions the proton acceptor strength of the iodate ions decreases (anti-cooperative effect), thus leading to the formation of weaker hydrogen bonds in this compound (bonds of moderate strength) as compared to those formed in the potassium and rubidium ones. The normal vibrations of other entities (IO₃⁻ ions and BeO₄ tetrahedra (skeleton vibrations)) are also discussed.     

High-surface-area microporous carbon as the efficient photocathode of dye-sensitized solar cells

This paper reports on the application of cornstalks-derived high-surface-area microporous carbon (MC) as the efficient photocathode of dye-sensitized solar cells (DSCs). The photocathode, which contains MC active material, Vulcan XC–72 carbon black conductive agent, and TiO₂ binder, was obtained by a doctor blade method. Electronic impedance spectroscopy (EIS) of the MC film uniformly coated on fluorine doped SnO₂ (FTO) glass displayed a low charge-transfer resistance of 1.32 Ω cm². Cyclic voltammetry (CV) analysis of the as-prepared MC film exhibited excellent catalytic activity for I₃^?/I^? redox reactions. The DSCs assembled with the MC film photocathode presented a short-circuit photocurrent density (J_sc) of 14.8 mA cm^?2, an open-circuit photovoltage (V_oc) of 798 mV, and a fill factor (FF) of 62.3%, corresponding to an overall conversion efficiency of 7.36% under AM 1.5 irradiation (100 mW cm^?2), which is comparable to that of DSCs with Pt photocathode obtained by conventional thermal decomposition.     

Preparation of activated carbon from Turbinaria turbinata seaweeds and its use as supercapacitor electrode materials

Turbinaria turbinata brown seaweeds were tested as carbon electrode material in symmetric, electrochemical supercapacitors. The electrochemical properties of the carbon materials were characterised for their application as supercapacitors using cyclic voltammetry, galvanostatic charge/discharge method and electrochemical impedance spectroscopic analyses. Our initial results showed that the optimal behaviour was obtained for the sample prepared by pyrolysis at 800 °C. The average surface area of the carbon was 812 m²/g. Electrochemical tests with an organic electrolyte gave the following interesting results: a capacitance of 74.5 F/g, a specific series resistance of 0.5 Ω cm² and an ionic resistivity of 1.3 Ω cm². These results show the promising capacitive properties of carbon derived from seaweeds and their application in electrochemical supercapacitors.     

The standard molar enthalpy of sublimation ofη5-bis-pentamethylcyclopentadienyl iron measured with an electrically calibrated vacuum-drop sublimation microcalorimetric apparatus

A heat-flow Calvet microcalorimeter was adapted for the measurement of sublimation enthalpies by the vacuum-drop method, with samples of masses in the range 1 mg to 5 mg. The electrically calibrated apparatus was tested by determining the enthalpies of sublimation of benzoic acid and ferrocene, at T =  298.15 K. The obtained results, Δ_cr^gH_m^o(C₇H₆O₂)  =  (88.3  ±  0.5)kJ · mol ^− 1and Δ_cr^gH_m^o(C₁₀H₁₀Fe) =  (73.3  ±  0.1)kJ · mol ^− 1, are in excellent agreement with the corresponding values recommended in the literature. Subsequent application of the apparatus to the determination of the enthalpy of sublimation of η⁵-bis-pentamethylcyclopentadyenyl iron, at T =  298.15 K, led to Δ_cr^gH_m^o(C₂₀H₃₀Fe)  =  (96.8  ±  0.6)kJ · mol ^− 1.     

Cross-sections for formation of 195mPt through natPt(n,x)195mPt reaction over neutron energy range 13–15 MeV

The cross-sections for formation of metastable state of ¹⁹⁵Pt (^195mPt, 98.85 keV, 4.02 d) through ^natPt(n,x)^195mPt reaction induced by 13.5–14.6 MeV neutrons were measured. Measurements were corrected for gamma-ray attenuations, random coincidence (pile-up), dead time and fluctuation of neutron flux. The data for ^natPt(n,x)^195mPt reaction cross-sections are reported to be 438±46, 399±44 and 372±43 mb at 13.5±0.2, 14.1±0.1 and 14.6±0.2 MeV incident neutron energies, respectively.     

Electrochemical characterization on cobalt sulfide for electrochemical supercapacitors

High capacitance at a high charge–discharge current density of 50 mA/cm² for a new type of electrochemical supercapacitor cobalt sulfide (CoS_x) have been studied for the first time. The CoS_x was prepared by a very simply chemical precipitation method. The electrochemical capacitance performance of this compound was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge tests with a three-electrode system. The results show that CoS_x has excellent electrochemical capacitive characteristic with potential range −0.3 ∼ 0.35 V (versus SCE) in 6 M KOH solution. Charge–discharge behaviors have been observed with the highest specific capacitance values of 475 F/g at the current density of 5 mA/cm², even at the high current density of 50 mA/cm², CoS_x also shows the high specific capacitance values of 369 F/g.