Thermodynamics of electrolytes. VI. Weak electrolytes including H3PO4

Equations previously developed and widely applied to the thermodynamic properties of strong electrolytes are extended to solutions involving a dissociation equilibrium. Excellent agreement is obtained with the data for pure phosphoric acid to 6M and for phosphate buffer solutions. The parameters of the strong electrolyte components of the buffer solutions are taken from other work, and the remaining parameters for H⁺, H₂PO ₄ ^– , and H₃PO₄ are evaluated, including a pK of 2.146. The present method avoids ambiguities which formerly arose in treating weak acids with as small pK as this.     

Correlation of the extraction constants of the system Cd(II)–H3PO4/Cyanex 302–kerosene at different ionic strengths

Bromley's theory for calculating activity coefficients in order to correlate the values of cadmium extraction constant by Cyanex 302 from phosphoric acid solutions at different ionic strengths has been applied. A chemical model for the aqueous phase including the species H₃PO₄, H₂PO₄⁻, H₅P₂O₈⁻, H₆P₂O₈, CdHPO₄ and CdH₂PO₄⁺ has been considered. The increase observed for the extraction constant value when increasing the phosphoric acid concentration is probably due to the significant increase of the cadmium activity coefficient. A reaction extraction including water as a component has been proposed, and the value of the thermodynamic extraction constant of log K⁰=7.02 for the formation of CdR₂(HR) species, HR being the major component of Cyanex 302, has been obtained.     

A New Investigation of Aqueous Orthophosphoric Acid Speciation Using Raman Spectroscopy

The Raman spectrum of aqueous phosphoric acid has been investigated at apparentconcentrations of 0.3 to 9.7 mol-dm^–3 at 25°C. A quantitative analysis hasbeen made over this concentration range after the determination of the responsecoefficients of the H₂PO^– ₄ and H₃PO₄ species. In the first step, the spectra wereinterpreted assuming that only two species (H₂PO^– ₄ and H₃PO₄) were present inthe system. The dissociation of phosphoric acid obtained in this case is consistentwith the values Preston and Adams⁽¹⁾ obtained, and which was also found fromRaman spectroscopy. However, a discrepancy exists between the representationsfrom spectra and experimental ones. This discrepancy can be removed if anotherspecies, the anionic dimer H₅P₂O^– ₈ is taken into account. Therefore, in the secondstep, a modified interpretation of the spectra, was used to determine theconcentrations of the H₂PO^– ₄, H₅P₂O^– ₈, and H₃PO₄ species and to deduce the correspondingdegree of dissociation of the acid, as well as the speciation of the solutions as afunction of the apparent concentration of phosphoric acid. As in the results Elmoreand co-workers,² which were deduced from pH measurements, the degree ofdissociation reaches a minimum and then increases significantly for apparentphosphoric acid concentrations greater than 1 mol-dm^–3.     

Apparent molar heat capacities of aqueous solutions of phosphoric acid and sulfur dioxide from 303 to 623 K and a pressure of 28 MPa

Heat capacities of aqueous solutions of phosphoric acid from 0.1 to 0.8 mol- kg^-1 and sulfur dioxide from 0.2 to 0.9 mol-kg^-1 have been measured with a flow heat-capacity calorimeter from 303 to 623 K and a pressure of 28 MPa. At the lowest molality single-solute solutions as well as mixtures of either H₃PO₄ or SO₂ with HC1 were measured to repress dissociation. Calculated apparent molar heat capacities were corrected for dissociation reactions and the chemical relaxation effect. Experimental results for mixtures were analyzed using Young’s rule. Standard state partial molar heat capacities of H₃PO₄(aq) and SO₂(aq) were obtained by extrapolation to infinite dilution. A few measurements of the densities of aqueous H₃PO₄ and SO₂ were made at 25°C and a pressure of 28 MPa.     

Isopiestic Studies of H3PO4(aq) at Elevated Temperatures

Isopiestic molalities of aqueous solutions of phosphoric acid have been measured at 383.15 to 523.15 K. NaCl(aq) served as the isopiestic standard for the calculation of osmotic coefficients. The ion-interaction model gave an excellent fit to the experimental osmotic coefficients by treating H₃PO₄(aq) as a 1–1 weak electrolyte. Activity coefficients, both real and stoichiometric, were also obtained from the analysis of the isopiestic results. As expected, the ionization of H₃PO₄(aq) decreased with increasing temperature. However, at higher molalities, the ionization increased with increasing molality (reionization).     

Thermodynamics of aqueous solutions of orthophosphoric acid from the freezing point to 298.15°K

The osmotic coefficients of aqueous phosphoric acid have been determined at 298.15°K, at 273.15°K, and at the freezing point, and for concentrations from about 10^?4 m to 15 m. Phosphoric acid is incompletely dissociated even at very low concentrations, but it was possible to derived mean activity coefficients for the species H⁺ and H₂PO ₄ ^? by treating phosphoric acid as a 1-1 electrolyte.     

A Phosphate-Based Silver–Bipyridine 1D Coordination Polymer with Crystallized Phosphoric Acid as Superprotonic Conductor

Phosphate-based silver–bipyridine (Ag-bpy) 1D coordination polymer {[{Ag(4,4′-bpy)}₂{Ag(4,4′-bpy)(H₂PO₄)}] ⋅ 2 H₂PO₄ ⋅ H₃PO₄ ⋅ 5 H₂O}_n ( 1 ) with free phosphoric acid (H₃PO₄), its conjugate base (H₂PO₄⁻) and water molecules in its lattice was synthesized by room-temperature crystallization and the hydrothermal method. An XRD study showed that coordinated H₂PO₄⁻, lattice H₂PO₄⁻ anions, free H₃PO₄ and lattice water molecules are interconnected by H-bonding interactions, forming an infinitely extended 2D H-bonded network that facilitates proton transfer. This material exhibits a high proton conductivity of 3.3×10⁻³ S cm⁻¹ at 80 °C and 95 % relative humidity (RH). Furthermore, synthesis of this material from commercially available starting materials in water can be easily scaled up, and it is highly stable under extreme conditions of conductivity measurements. This report inaugurates the usage and design principle of proton-conducting frameworks based on crystallized phosphoric acid and phosphate.     

Electrosynthesis of vanadophosphate by anodic oxidation of vanadium in phosphoric acid solutions

Anodic polarisation of vanadium has been studied in aqueous H₃PO₄ solutions. In all solutions, from 1 to 14 M H₃PO₄, vanadium oxidation occurred at +0.2 V/SCE. A passivation behaviour was observed. In all the cases, the polarisation curve showed a current peak followed by a current plateau. The peak current was dependent upon phosphoric acid concentration. It decreased with the increase of acid concentration. Current oscillations occurred for vanadium anode for lowest concentrated solutions. All the electrochemical observations agreed with the formation of an anodic electrodeposit of vanadophosphate. The yellowish product isolated after controlled potential oxidation has been identified to VOPO₄,2H₂O.     

Thermodynamic Properties of Peptide Solutions. Part 18. Partial Molar Isentropic Compressibilities of Gly-X-Gly Tripeptides (X = Tyr,Pro, Gln,Asp and Glu), and the Peptide Salts K[GlyAspGly], Na[GlyGluGly] and GlyLysGly Acetate in Aqueous Solution at 25 <Superscript>∘</Superscript>C

The partial molar isentropic compressibilities at infinite dilution, K∘_S,2, have been determined for several tripeptides of the sequence glycyl-X-glycine, where X is one of the amino acids tyrosine, proline, glutamine, aspartic acid, glutamic acid and lysine in aqueous solution at 25 ^∘C. These results, along with those for triglycine, were used to estimate the contributions of the amino acid side-chains to the partial molar isentropic compressibilities of polypeptides. Values for K∘_S,2 have also been determined for aqueous solutions of the two peptide salts K[glyaspgly] and Na[glyglugly]. The K∘_S,2 results for the peptides and their salts have been combined with literature data for electrolytes to calculate the changes in isentropic compressibility upon ionization of the acidic side-chains. The results are compared with those for other carboxylic acid systems.     

Densities and compressibilities of aqueous sodium carbonate and bicarbonate from 0 to 45°C

The densities and the sound speeds of aqueous NaHCO₃ and Na₂CO₃ solutions were measured from 0.05 to 1.0m and from 0 to 45°C. These data were fitted to functions of molality and temperature and were used to calculate the apparent molal volumes V_? and compressibilites κ_φ of these solutions. Polynomial expression for V_? and κ_φ as functions of molality and temperature have been determined. The partial molal volumes and compressibilities of these solutions and literature data have been used to determine the volume ΔV and compressibility Δκ changes for the ionization of carbonic acid in aqueous solutions. These values of ΔV and Δκ have been used to estimate the effect of pressure on the ionization constants for carbonic acid from 0 to 45°C. The calculated pressure coefficients are in good agreement with the measured values.     

Formation of titanium phosphate composites during phosphoric acid decomposition of natural sphene

Decomposition of mineral sphene, CaTiOSiO₄, by H₃PO₄ is investigated in detail. During the dissolution process, simultaneous calcium leaching and formation of titanium phosphate (TiP) take place. The main product of decomposition is a solid titanium phosphate-silica composite. The XRD, solid-sate NMR, IR, TGA, SEM and BET data were used to identify and characterize the composite as a mixture of crystalline Ti(HPO₄)₂·H₂O and silica. When 80% phosphoric acid is used the decomposition degree is higher than 98% and calcium is completely transferred into the liquid phase. Formation of Ti(HPO₄)₂·H₂O proceeds via formation of meta-stable titanium phosphate phases, Ti(H₂PO₄)(PO₄)·2H₂O and Ti(H₂PO₄)(PO₄).The sorption affinities of TiP composites were examined in relation to caesium and strontium ions. A decrease of H₃PO₄ concentration leads to formation of composites with greater sorption properties. The maximum sorption capacity of TiP is observed when 60% H₃PO₄ is used in sphene decomposition.The work demonstrates a valuable option within the Ti(HPO₄)₂·H₂O-SiO₂ composite synthesis scheme, to use phosphoric acid flows for isolation of CaHPO₄·2H₂O fertilizer.     

Carbon-13 kinetic isotope effects in the decarbonylation of formic acid of natural isotopic composition in phosphoric acid media

The¹³C kinetic isotope effect (K.I.E.) in the decarbonylation of formic acid of natural isotopic composition in 85% orthophosphoric acid, in 100% H₃PO₄, and in pyrophosphoric acid has been measured in different temperature intervals ranging from 19 to 133 °C. In 85% H₃PO₄ the carbon-13 K.I.E. is determined by the fractionation of carbon isotopes expected for C–O bond rupture (k ₁₂/k ₁₃=1.0531 at 70°C). In 100% H₃PO₄ the¹³C K.I.E. indicates that C–H bond rupture is the major component of the reaction coordinate motion (thek ₁₂/k ₁₃ lay in the range of 1.026–1.017 over the range 30–70 °C). In pyrophosphoric acid the fractionation factor for¹³C equals 1.010 at 19 °C. Activation parameters for the decarbonylation of H¹²COOH in phosphoric acid media have been determined also and suggestions concerning the intimate mechanisms of decarbonylation of formic acid in dilute and concentrated phosphoric acids are made.     

Determination of uranium in wet phosphoric acid by extraction with octylphenylphosphoric acid

A method for quantitative determination of uranium in phosphoric acid and wet phosphoric acid has been developed. After reduction with Fe, uranium(IV) is extracted with a kerosene solution of octylphenylphosphoric acid. The uranium was stripped with 10M H₃PO₄, containing H₂O₂, and then determined spectrophotometrically with Arsenazo III and by direct uranium(IV)-phosphoric acid solution measurements.     

Thermodynamics of aqueous phosphate solutions: Apparent molar heat capacities and volumes of the sodium and tetramethylammonium salts at 25°C

A Picker flow microcalorimeter and a flow densimeter were used to obtain apparent molar heat capacities and apparent molar volumes of aqueous solutions of Na₃PO₄ and mixtures of Na₂HPO₄ and NaH₂PO₄. Identical measurements were also made on solutions of tetramethylammonium salts to evaluate the importance of anion-cation interaction. The experimental apparent molar properties were analyzed in terms of a simple extended Debye-Hückel model and the Pitzer ion-interaction model, both with a suitable treatment for the effect of chemical relaxation on heat capacities, to derive the partial molar properties of H₂PO ₄ ^– (aq), HPO ₄ ^2– (aq) and PO ₄ ^3– (aq) at infinite dilution. The volume and heat capacity changes for the second and third ionization of H₃PO₄(aq) have been determined from the experimental data. The importance of ionic complexation with sodium is discussed.     

Investigation of Uranium(VI) Extraction Mechanisms from Phosphoric and Sulfuric Media by 31P-NMR

Uranium extraction using DEHCNPB (butyl-1-[N,N-bis(2-ethylhexyl)carbamoyl]nonyl phosphonic acid, a bifunctional cationic extractant) has been studied to better understand mechanism differences depending on the original acidic solution (phosphoric or sulfuric). Solvent extraction batch experiments were carried out and the organic phases were probed using ³¹P-NMR. This technique enabled to demonstrate that phosphoric acid is poorly extracted by DEHCNPB ([H₃PO₄]_org < 2mM), using direct quantification in the organic phase by ³¹P-NMR spectra integration. Moreover, in the presence of uranium in the initial phosphoric acid solution, uranyl extraction by DEHCNPB competes with H₃PO₄ extraction.Average stoichiometries of U(VI)-DEHCNPB complexes in organic phases were also determined using slope analysis on uranium distribution data. Uranium seems to be extracted from a phosphoric medium by two extractant molecules, whereas more than three DEHCNPB on average would be necessary to extract uranium from a sulfuric medium. Thus, uranium is extracted according to different mechanisms depending on the nature of the initial solution.     

Radiation effects on the extraction of americium(III) with di(2-ethylhexyl) phosphoric acid

Radiation effects on the extraction of Am(III) with di (2-ethylhexyl) phosphoric acid (DEHPA) was studied by exposing DEHPA to gamma rays under various conditions. Gamma irradiation of undiluted DEHPA causes an enhancement of extraction of Am(III) due to the formation of mono (2-ethylhexyl) phosphoric acid (MEHPA) similarly to that of Nd(III). The presence of diluent during irradiation brought about a slight difference from the results in the absence of a diluent. The marked change occurred in Df when the organic solvent was exposed to γ-ray while being mixed with nitric acid solution. An initial slight increase of Df for Am(III) and Nd(III) was followed by a subsequent decrease beyond an absorbed dose of approximately 200 Wh·1⁻¹. This phenomenon was explained by the enhanced decomposition of DEHPA and the subsequent strong hydrolytic and radiolytic decomposition of MEHPA to H₃PO₄ in the aqueous phase, and the complex forming nature of H₃PO₄ with Am(III) and Nd(III).     

A new anhydrous proton conducting material based on phosphoric acid doped polyimide

A new anhydrous proton conducting material based on polyimide and phosphoric acid composite was prepared. The interaction between polyimide (PI) and phosphoric acid was investigated by FTIR. The results show that phosphoric acid interacts with polyimides mainly by hydrogen bonds rather than by protonation of PI at room temperature. Environmental scanning electron microscopy (ESEM) was employed to study the surface morphology of the membranes. The results show that the surface of PI-xH₃PO₄ membranes is very compact and homogeneous. Proton conductivity and methanol permeability of PI doped with phosphoric acid (PI-xH₃PO₄) were also studied. Proton conductivity of PI-xH₃PO₄ membranes increases with increasing concentration of phosphoric acid. Hydrogen bond seems to play an important role in the proton conductivity of this system. Effects of osmotic on the direct diffusion process of methanol in the membranes can be negligible due to the absence of micro-pore structure as already shown in ESEM results. Effects of methanol concentration and temperature on the methanol permeability of PI-xH₃PO₄ membranes were also discussed. Methanol permeability in PI-xH₃PO₄ membranes decreases with increasing methanol concentration, and increases with increasing temperature.     

The solubility of ozone in aqueous solutions of sulfuric, phosphoric, and perchloric acids

The solubility of ozone in pure water and aqueous solutions of sulfuric, phosphoric, and perchloric acids was determined at 20°C. An increase in the concentration of H₃PO₄ and HClO₄ (to 14.8 and 9.5 M, respectively) caused a monotonic decrease in the solubility of ozone. The solubility of ozone in sulfuric acid was minimum at a 12 M concentration; the solubility then increased and, in 17.9 M H₂SO₄, reached almost the same value as in pure water. The ratio between the concentrations of O₃ in solution and the gas phase was 0.276 in pure water, 0.122 in 12 M H₂SO₄, and 0.265 in 17.9 M H₂SO₄. The results obtained are compared with the available literature data.     

Extraction studies of Pu(IV) with octylphenyl acid phosphate

Octylphenyl acid phosphate, the commercially available mixture of monooctylphenylphosphoric acid (MOPPA) and dioctylphenylphosphoric acid (DOPPA) in xylene medium has been employed as an extractant for distribution studies on Pu(IV) in different mineral acids including phosphoric acid. It was found possible to extract Pu quantitatively from an acid mixture comprising 2.5M H₃PO₄, 0.75M H₂SO₄ and 0.5M HNO₃. Quantitative stripping was observed with a mixture of 0.25M oxalic acid and 0.2M ammonium oxalate.Parts of this work have been reported at symposie (Refs^1,2)     

The calorimetric investigation of phosphoric acid-N,N-dimethylformamide system

Solution and mixing enthalpies for the orthophosphoric acid (H₃PO₄)-N,N-dimethylformamide (DMF) system were measured over the whole concentration range at 25 °C. The standard value of solution enthalpy of phosphoric acid in DMF and the standard transference enthalpy of H₃PO₄ from water to DMF were calculated. The mixing enthalpy concentration dependence permitted making assumptions on complex formation in the system under investigation.