Proton transport mechanism in ammonium dihydrogen phosphate

Coulometric, transient ionic current, electrical conductivity and IR investigations on polycrystalline and single crystal of ammonium dihydrogen phosphate (ADP) have been carried out. During coulometry, gases evolved both at the cathode (mostly H₂) and at anode (O₂) indicating the electrolysis of the H-O-H bridge. Transient ionic current study suggests the likely presence of two types of mobile ionic charge carriers (H⁺ and O^2–) with mobilities of 1.3×10^–4 and 3.3×10^–5 cm² V^–1 sec^–1. A comparative study of the IR spectra of the original and the electrolysed samples also supports the idea of possible electrolysis. The temperature dependence of the electrical conductivity have also been studied and interpreted in terms of possible deammoniation reaction and phase transformation. Finally, a mechanism for ionic transport in ADP is suggested.     

Mechanochemically synthesized CsH2PO4–H3PW12O40 composites as proton-conducting electrolytes for fuel cell systems in a dry atmosphere

Abstract

Cesium dihydrogen phosphate (CsH₂PO₄, CDP) and dodecaphosphotungstic acid (H₃PW₁₂O₄₀·nH₂O, WPA·nH₂O) were mechanochemically milled to synthesize CDP–WPA composites. The ionic conductivities of these composites were measured by an ac impedance method under anhydrous conditions. Despite the synthesis temperatures being much lower than the dehydration and phase-transition temperatures of CDP under anhydrous conditions, the ionic conductivities of the studied composites increased significantly. The highest ionic conductivity of 6.58×10^?4 Scm^?1 was achieved for the 95CDP·5WPA composite electrolyte at 170 °C under anhydrous conditions. The ionic conduction was probably induced in the percolated interfacial phase between CDP and WPA. The phenomenon of high ionic conduction differs for the CDP–WPA composite and pure CDP or pure WPA under anhydrous conditions. The newly developed hydrogen interaction between CDP and WPA supports anhydrous proton conduction in the composites.     

A Standard for the Measurement of the pH of Blood and Other Physiological Media

A buffer solution containing potassium dihydrogen phosphate (0.008695 molal) and disodium hydrogen phosphate (0.03043 molal) is proposed as a pH standard for the physiologically important range, pH 7 to 8. The proposed standard solution is prepared by dissolving 1.179 g (air weight) of potassium dihydrogen phosphate and 4.303 g (air weight) of disodium hydrogen phosphate in ammonia-free water and diluting to 1 liter at 25 °C. The ionic strength is 0.1.Standard pH values (pH_s) were assigned to this reference solution at temperatures from 0 to 50 °C by means of emf measurements of hydrogen-silver chloride cells without liquid junction. The activity coefficient of chloride ion, upon which the assignment of pH_s depends, was evaluated by means of a recently proposed convention. By this means, standard values precise to ± 0.001 unit could be derived from the emf data. At 25 °C pH_s is 7.414, and at 38 °C it is 7.382. The operational consistency of these standard values with those for the 0.025-m equimolal phosphate buffer (one of the NBS primary standards) was demonstrated.     

Mechanochemically synthesized CsH2PO4–H3PW12O40 composites as proton-conducting electrolytes for fuel cell systems in a dry atmosphere

Cesium dihydrogen phosphate (CsH₂PO₄, CDP) and dodecaphosphotungstic acid (H₃PW₁₂O₄₀·nH₂O, WPA·nH₂O) were mechanochemically milled to synthesize CDP–WPA composites. The ionic conductivities of these composites were measured by an ac impedance method under anhydrous conditions. Despite the synthesis temperatures being much lower than the dehydration and phase-transition temperatures of CDP under anhydrous conditions, the ionic conductivities of the studied composites increased significantly. The highest ionic conductivity of 6.58×10⁻⁴ Scm⁻¹ was achieved for the 95CDP·5WPA composite electrolyte at 170 °C under anhydrous conditions. The ionic conduction was probably induced in the percolated interfacial phase between CDP and WPA. The phenomenon of high ionic conduction differs for the CDP–WPA composite and pure CDP or pure WPA under anhydrous conditions. The newly developed hydrogen interaction between CDP and WPA supports anhydrous proton conduction in the composites.     

Investigation on (100) face of KDP crystal poisoned by MoO4 2? impurity

Potassium dihydrogen phosphate (KDP) single crystals doped with molybdate (MoO₄ ²⁻) were grown via the conventional temperature cooling and rapid growth methods, respectively. MoO₄ ²⁻ made KDP crystals tapering for conventional temperature cooling method. When KDP crystals were grown by rapid growth method, MoO₄ ²⁻ could induce liquid inclusions and simultaneous crystals. The measurement on growth rates indicated that MoO₄ ²⁻ broadened the dead zone and decreased the growth rate of (100) face of KDP crystals. The growth kinetic analysis in terms of two-dimensional nucleus and screw dislocation models implied that the energetic parameter γ/kT decreased with an increase of MoO₄ ²⁻ concentration. The influence of MoO₄ ²⁻ growth steps on (100) face of KDP crystal was observed through ex situ AFM technique. It gave evidence that MoO₄ ²⁻ could postpone the step bunching and make the step edge curving and knaggy to reduce the edge free energy, which was in agreement with the growth kinetics calculations. Additionally, the poisoned mechanism of MoO₄ ²⁻ and Fe³⁺ on step morphologies was detailed contrasted. The interaction process was discussed according to electro negativity analysis, which indicated MoO₄ ²⁻ (actually were HMoO₄ ⁻ and H₂MoO₄) could be absorbed onto (100) face through charge-assisted hydrogen bonds and caused more Mo element distributed in prismatic sector.     

Study of pure and l-tartaric acid doped ammonium dihydrogen phosphate single crystals: A novel nonlinear optical non-centrosymmetric crystal

Single crystals of pure and l-tartaric acid (LTA) C₄H₆O₆ doped ammonium dihydrogen phosphate (ADP) (NH₄) H₂PO₄ were grown by slow evaporation solution technique (SEST) at ambient conditions. Powder X-ray diffraction (PXRD) analysis was carried out to confirm the crystal structure and no additional phase was observed due to doping except a systematic variation in peak intensities. Fourier transform infrared spectral analysis was done to examine the presence of various functional groups in the grown crystals. UV–VIS–NIR spectroscopic analysis was carried out to see the change in optical transparency of pure ADP and crystals due to LTA with different doping concentrations. Second harmonic generation (SHG) efficiency measurement was done to examine the enhancement in the nonlinear optical characteristics of the grown crystals. The effect of LTA dopant on crystal morphology, thermal and mechanical properties of ADP have also been presented in this paper. The above studies reveal the effect of incorporation of LTA into the lattice of ADP crystals.     

Growth and electro-optic studies in mixed (NH4) x K1−x H2PO4 single crystals

Single crystals and mixed crystals of KH₂PO₄ (KDP) and NH₄H₂PO₄ (ADP) were grown with different dopant concentrations of NH₄H₂PO₄ in KH₂PO₄ in solution by Holden’s rotary crystallizer technique. The effect of additives like Borax (Na₂B₄O₇·10H₂O), seed crystal rotation rate and qualities of the crystals were studied. The half-wave voltages (in longitudinal mode) for KDP mixed with 1% ADP (by weight) were found and hence the unclamped (low frequency) electro-optic coefficients (r ₆₃) were calculated for various wavelengths in the visible region of the spectrum. It was noted that the half-wave voltage increases with increase in wavelength and temperature.     

Effect of water on monetite synthesis in the solid state

Synthesis of calcium hydrogen phosphate CaHPO₄ can be carried out with a milling apparatus into which solid calcium dihydrogen phosphate Ca(H₂PO₄)₂.H₂O and tricalcium phosphate Ca₃(PO₄)₂.1/6H₂O mixtures are introduced. The effect of water vapor pressure P_H2O on this reaction has been investigated. At a given temperature (60°C) the curves of degree of conversion as a function of milling time depend on P_H2O. Formation of brushite CaHPO₄.2H₂O during the course of reaction can be noted for a particular range of water vapor pressure.If some amounts of brushite are added to the initial mixture, the kinetics of the reaction developed under water vapor are increased. Experiments on the evolution of products after a milling treatment give evidence of the important dependence of the reaction rate on water vapor pressure.     

Electrical and thermodynamic properties of Cs<Subscript>0.97</Subscript> Rb<Subscript>0.03</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript>

The transport properties of Cs_0.97Rb_0.03H₂PO₄ have been studied using polycrystalline samples and single crystals. The mixed salt is isostructural with cesium dihydrogen phosphate and has slightly smaller unitcell parameters. The cation substitution increases the low-temperature ionic conductivity of the material by about two orders of magnitude but has an insignificant effect on the conductivity of the high-temperature phase. The low-temperature conductivity of single-crystal samples exhibits significant anisotropy, with σ _a < σ _b±c . The conductivity of the polycrystalline material is close to σ _b±c . The substitution reduces the temperature of the superionic phase transition by 20°C and enhances the thermal stability of the high-temperature phase at low humidity (1 mol % H₂O).     

Kinetics of Pu(IV) Reduction with Butanal Oxime

The reduction of Pu(IV) with butanal oxime in nitric acid solution in the presence of excess reductant follows the equation 4Pu^{4 +} + 2C₃H₇CHNOH + H₂O = 4Pu^{3 +} + 2C₃H₇CHO + N₂O + 4H⁺, and its rate is given by the equation -d[Pu(IV)]/dt = k[Pu(IV)]²[C₃H₇CHNOH]/{[Pu(III)][H⁺]}. The rate constant is k = 3.65±0.14 min^{- 1} at 20.2°C and the solution ionic strength = 2. The activation energy is E = 88.8±10.3 kJ mol^{- 1}. The probable reaction mechanism is discussed.     

Size effect and dielectric properties of NH4H2PO4 — porous glass composites

NH₄H₂PO₄ nano-composite antiferroelectric materials in porous glass have been studied by means of dielectric and dilatometric investigations. Dielectric spectroscopy measurements in a wide frequency range are reported here for the first time, for both the antiferro- and paraelectric phases of ammonium dihydrogen phosphate (ADP) embedded in a porous matrix. Low frequency relaxation processes above the phase transition temperature were shown to occur. An investigation of the thermal expansion revealed a negative volume jump at the phase transition point. It was found that the phase transition temperature in ADP crystals embedded in porous glass decreased with the decrease of the mean pore size. The experimentally observed shift of the phase transition temperature is caused by a combination of size and pressure effects.     

Ion transport in some solid state proton conducting composites studied from volta cell e.m.f. and complex impedance spectroscopy

Proton conducting composites of heteropolyacid hydrates (phosphomolybdic acid H₃PMo₁₂O₄₀.nH₂O, PMA; phosphotungstic acid H₃PW₁₂O₄₀.nH₂O, PTA) and salt hydrate like NiCl₂.6H₂O were prepared with insulating Al₂O₃ as dispersoid. The ionic conductivity peaks at two concentrations of Al₂O₃ indicating two percolation thresholds for proton conduction. Two separate experiments were carried out to check the existence of such percolation thresholds viz. the volta battery experiment involving the measurement of e.m.f. of an electrochemical cell with composites of different compositions used as electrolyte and the composition vs conductivity measured by the complex impedance spectroscopy. The presence of two maxima has been attributed to two different percolation thresholds for the two possible mobile protonic species H⁺ (H₃O⁺) and OH^- arising from the hydrates.     

Growth imperfections in NH4H2PO4-KH2PO4 mixed crystals by X-ray topographic analysis

X-ray topographs of ammonium dihydrogen phosphate (ADP)—potassium dihydrogen phosphate (KDP) mixed crystals with various compositions were taken by the Lang transmission method. Growth imperfections such as growth bands, misorientations, lattice deformations at the boundary between two growth sectors and inclusions etc., present in the crystals were analysed. Dislocations were identified by using the g.b criterion.     

Microhardness studies in gel-grown ADP and KDP single crystals

Microhardness studies were carried out on (100) faces of gel-grown ADP and KDP single crystals. Slip lines were observed on (100) face of ADP crystal at the corners of the impressions. Microcracks around the indentation were found on (100) face of KDP crystal from 10g load which spread out as the load increased. Vickers hardness numberH _v decreased with increase in load. ΔH _v at 50g load for solution-grown crystals and gel-grown crystals (present case) was determined. Work hardening indexn for both ADP and KDP crystals was less than 2 showing soft-material characteristics. Using Wooster’s empirical relation, values of C₁₁ from hardness were calculated and found to be close to the reported ones. The work was done under a research project sanctioned by the Council of Scientific and Industrial Research (CSIR), New Delhi.     

Liquid Radioactive Waste Treatment

Phosphate precipitation process is developed for monovalent nuclides. The process includes magnesium addition, providing precipitation of rubidium and cesium along with phosphates of di- and polyvalent ions as poorly soluble salts Cs(Rb)MgPO₄·6H₂O. An additional effect is attained by adding small amounts (2-5 mg l^{- 1}) of stable cesium and rubidium. Introduction of 300 mg l^{- 1} MgO and the equivalent amount of phosphate in LRW containing 45000 Bq l^{- 1} of ¹³⁷Cs provides 90% removal of ¹³⁷Cs.     

Sodium-Ion Substituted Water Molecule in Layered Vanadyl Phosphate Enhancing Electrochemical Kinetics and Stability of Zinc Ion Storage

Vanadyl phosphate (VOPO₄·2H₂O) has been regarded as one of the most promising cathode materials for aqueous Zn-ion batteries due to its distinct layered structure. However, VOPO₄·2H₂O has not yet demonstrated the exceptional Zn ion storage performance owing to the structural deterioration during repeated charging/discharging process and poor intrinsic conductivity. In this work, 2D sodium vanadyl phosphate (NaVOPO₄·0.83H₂O, denoted as NaVOP) is designed as a cathode material for Zn-ion batteries, in which sodium ions are preinserted into the interlayer, replacing part of water. Benefiting from the in situ surface oxidization, improved electronic conductivity, and increased hydrophobicity, the NaVOP electrode exhibits a high discharge capacity of 187 mAh g⁻¹ at 0.1 A g⁻¹ after activation, excellent rate capability and enhanced cycling performance with 85% capacity retention after 1500 cycles at 1 A g⁻¹. The energy storage mechanism of the NaVOP nanoflakes based on the rapid Zn²⁺ and H⁺ intercalation pseudocapacitance are investigated via multiple ex situ characterizations.     

Proton conduction in solids—A Raman spectral study

The mechanism of proton conduction in hydrogen-bonded solids and the importance of Raman investigations to understand it are discussed here. The results of Raman investigations on the protonic conductors (NH₄)₃H(SO₄)₂ and Li₂SO₄·H₂O under small d.c. electric fields have been discussed. The enhancement in intensity of the 859, 829 and 330 cm^?1 bands of(NH₄)₃H(SO₄)₂ has been explained on the basis of proton movement along the N-H...O bond. Spectral changes of the bands due to torsional oscillation of the ammonium ion indicate the probability of hindered rotation of this group. The appearance of new bands at 773 and 1680cm^?1 in Li₂SO₄·H₂O indicates the formation of H₃O⁺ electrolysis. The changes in stretching and bending modes of water are explained on the basis of polarizability changes induced by the migration of proton along the 0-H...0 bond and reorientation motion of water molecules.     

Protonic conduction in Al2(SO4)3·16H2O: coulometry,transient ionic current,infrared and electrical conductivity studies

Proton transport in Al₂(SO₄)₃·16H₂O has been established using different techniques namely coulometry, transient ionic current, i.r., DTA/TGA and electrical conductivity. The possible charge carriers are H⁺ and OH⁻ generated as a result of possible electrolysis of hydrate water molecules. The mobilities of the two charge carriers are approximately 4×10⁻⁵ and 2.4×10⁻⁵cm²V⁻¹s⁻¹. The electrical conductivity shows strong dependence upon humidity and also shows a against 1/T behaviour closely related with its thermal dehydration reaction.     

Electrodeposition of dicalcium phosphate dihydrate coatings on stainless steel substrates

Cathodic reduction of an aqueous solution containing dissolved calcium and phosphate ions results in the deposition of micrometer thick CaHPO₄·2H₂O (dicalcium phosphate dihydrate) coatings on stainless steel substrates. The coating obtained at a low deposition current (8 mA cm^???2) comprises lath-like crystallites oriented along 020. The 020 crystal planes are non-polar and have a low surface energy. At a high deposition current (12 mA cm^???2), platelets oriented along 121? are deposited. CaHPO₄·2H₂O is an important precursor to the nucleation of hydroxyapatite, the inorganic component of bones. Differently oriented CaHPO₄·2H₂O coatings transform to hydroxyapatite with different kinetics, the transformation being more facile when the coating is oriented along 121?. These observations have implications for the development of electrodeposited biocompatible coatings for metal endoprostheses for medical applications.     

Uranium(IV) Complexes Formed in Extraction with Tributyl Phosphate from Nitric Acid Solutions

Speciation of U(IV) in tributyl phosphate (TBP) solutions prepared by extraction of U(IV) from 2 M HNO₃ was studied. The electronic spectra showed that in the solutions containing from 3 to 60% TBP a mixture of disolvate U(NO₃)₄(TBP)₂ and hydrates with hypothetical formula (TBP) _m ...[U(NO₃) _k · (H₂O) _n ]^(4-k)+ (k = 3 or 4) is formed. Within the 70-100% concentration range, the hexanitrate complex (TBP) _n ...2H₅O₂(H₂O) _p ⁺...[U(NO₃)₆]^{2 -} also appears. In undiluted TBP, as the concentration of uranyl nitrate increases, first the hexanitrate complex and then hydrated complexes of U(IV) gradually disappear. At uranium concentration more than 300 g l^-1, only U(IV) tetranitrate disolvate exists in the organic phase.