The homogeneous nucleation rates of H2SO4-H2O aerosol particles in air

The homogeneous nucleation rates for H₂SO₄---H₂O solution droplets at 25, 0 and −55°C are calculated and plotted as a function of H₂SO₄ concentration and H₂O concentration. The plotted contours are very useful for quick estimates of the nucleation rates of H₂SO₄---H₂O aerosols in smog chambers, polluted atmospheres and the stratosphere under different environmental conditions. The effect of the uncertainty in the saturated vapor pressure of H₂SO₄ on the nucleation rate is also discussed.     

Influence of ionic equilibrium in the CuSO4-H2SO4-H2O system on the formation of irregular electrodeposits of copper

The relative concentration of hydrogen ion (H⁺) as a function of sulfuric acid (H₂SO₄) concentration (calculated using Pitzer's model) and the electrochemical processes by which irregular copper deposits are formed were correlated. Irregular deposits are formed by potentiostatic electrodeposition at a high overpotential where the hydrogen evolution reaction occurs parallel to copper electrodeposition. Two sets of acid sulfate solutions were analyzed. In one set of experiments, the concentration of CuSO₄ was constant while the concentration of H₂SO₄ was varied. The other set of experiments was performed with a constant concentration of H₂SO₄ and different concentrations of CuSO₄. Then, the volumes of the evolved hydrogen (calculated as the average current efficiencies of hydrogen evolution) and the morphologies of copper deposits, characterized by the SEM technique, obtained for the same ratio of CuSO₄/H₂SO₄ were mutually compared and discussed in terms of the relative concentrations of hydrogen ions (H⁺) as a function of the H₂SO₄ concentration. Good agreement between the ionic equilibrium in the CuSO₄-H₂SO₄-H₂O system and the results of the electrochemical processes was obtained. In this way, it was shown how this ionic equilibrium can be applied to predict and analyze the solution composition in electrolytic copper deposition processes.     

The time dependent growth of H2O---H2SO4 aerosols by heteromolecular condensation

A theory for the time dependent growth of solution droplets by heteromolecular condensation is presented. The theory is applied to the growth of H₂O---H₂SO₄ aerosols for relative humidites less than 100 per cent. Growth curves (droplet radius as a function of time) for different values of relative humidity are evaluated.     

钛石膏-H2SO4-H2O体系中石膏-硬石膏的相变规律

本文研究了在常压下钛石膏-H₂SO₄-H₂O体系中石膏相向硬石膏相的转化,探索了反应时间、硫酸浓度和温度对石膏-硬石膏转化的影响。结果表明:提高反应温度、增大硫酸浓度和增加反应时间都有利于石膏向硬石膏转化;当石膏转化为硬石膏后,延长反应时间硬石膏不再发生转变;在温度为70 ℃和80 ℃时,体系中石膏与硬石膏共存,二者的微观形貌差异明显,石膏呈片状,硬石膏呈长方板状;当温度升温至90 ℃以上时,石膏完全转变为硬石膏,其微观形貌为长方板状;常压下,在50~100 ℃内,在钛石膏-H₂SO₄-H₂O体系中发生的石膏-硬石膏的相变是石膏直接脱水形成硬石膏,没有中间产物形成。     

The electrochemical oxidation of lead in various H2OH2SO4 mixtures—II. Ring-disc electrode study

The rotating ring-disc electrode technique was used to study the generation of soluble Pb(II) species during the anodic oxidation of the lead electrode in various H₂OSO₄ media. The concentration range extended from 0.06 to 10.3 M H₂SO₄. For every concentration it was possible to detect a small cathodic ring current variation which was attributable to the reduction of Pb(II) to Pb. Quantitative measurements of the collection efficiency showed that the small cycle life of the lead-acid battery in 5.6 M H₂SO₄ cannot be ascribed to the dissolution step.     

The electrochemical oxidation of lead in various H2OH2SO4 mixtures—I. Linear sweep voltammetry

The linear sweep voltammetry technique was used in order to detect a change in the lead oxidation mechanism around 5 M H₂SO₄. This change could explain the strong decrease in cycle life of the lead-acid battery when increasing H₂SO₄ concentration from 4.7 to 5.6 M. In the concentration range studied (3.6–10 M) no change was detected. The same behaviour was observed when cycling the electrode, when increasing sweep rate and when rotating the electrode.     

Pt-Co/C nanoparticles as electrocatalysts for oxygen reduction in H2SO4 and H2SO4/CH3OH electrolytes

The oxygen reduction reaction (ORR) was studied on carbon dispersed Pt and Pt-Co alloyed nanocatalysts with high contents of Co in H₂SO₄ and H₂SO₄/CH₃OH solutions. The characterization techniques considered were transmission electron microscopy (TEM), X-ray diffraction (XRD) and in situ X-ray absorption near edge structure (XANES). The electrochemical activity for the ORR was evaluated from steady state polarization measurements, which were carried out in an ultra thin layer rotating disk electrode. The results showed that with the increase of Co content, the nanoparticle size distributions become sharper and the mean particle diameters become smaller. XRD indicated low degree of alloy formation but significant phase segregation of Co was observed only for Pt-Co/C 1:3 and 1:5 (Pt:Co atomic ratios). The electrochemical measurements indicated that the four-electrons mechanism is mainly followed for the ORR on all materials and the electrocatalytic activities per gram of Pt is higher for the catalysts with higher Co contents. This was explained based on the XANES results which evidenced a decrease of the coverage of oxygenated Pt adsorbates due to the presence of Co. In the methanol-containing electrolyte, the Pt-Co/C 1:5 catalyst showed the highest performance. This was attributed to its low activity for the methanol oxidation due to the smaller probability for presenting three Pt neighboring Pt active sites.     

Anodisches verhalten von chrom in wasserfreien und wasserhaltigen dimethylformamidH2SO4-und methanolH2SO4-Lösungen

The anodic film strongly inhibiting the dissolution of the chromium is formed on the surface of the metal in both the anhydrous and the water containing solution of sulphuric acid in organic solvents. The film results from the parallel solid-state reactions between the metal and sulphate ions, and between the metal and water. In the anhydrous solutions the amorphic salt film is formed. With the increase of the concentration of water the salt film changes into the salt-hydroxide film and at the end, at the highest water concentration, into the film of the hydroxide only. The critical concentration of water, for which the passive film reaches the hydroxide character, could be obtained from the relationship between the potential of passivity and the content of water in the solution.     

Anodic oxidation of bismuth in H2SO4 solutions

Anodic charging curves have been measured on polycrystalline Bi in H₂SO₄ solutions (0·01–6·0 N) at 30°C. The effect of various experimental procedures, eg electrode treatment and stirring, has been established. The anodic behaviour of Bi depends markedly on the acid concentration. In the high range, the results indicate dissolution which follows a Tafel relation. However, in dilute solutions, growth of oxide film occurs, and the potential rises rapidly with time, reaching over 100 V at high cds. Sparking and oxide breakdown start at about 150 V. Oxide growth follows the high field ionic conduction. The reciprocal capacitance is linearly related to the logarithm of cd. The constants of the exponential law, the half-barrier width, and the field strength have been calculated The last lies between 1 and 3 × 10⁶ V/cm at 1 mA/cm². The effect of F⁻ and Cl⁻ ions on oxide growth in H₂SO₄ has been also investigated.     

碳酸钠—过氧化氢—水体系相图的绘制

进行了Na2CO3-H2O2-H2O体系溶解度的测定并绘制成相图,最后对其应用进行了讨论。     

Electrochemical behaviour of titanium in H2SO4-MnSO4 electrolytes

The corrosion of titanium in H₂SO₄ electrolytes (0.001-1.0 M) at temperatures from ambient to 98 °C has been investigated using steady-state polarization measurements. Four distinct regions of behaviour were identified, namely active corrosion, the active-passive transition, passive region and the dielectric breakdown region. The active corrosion and active-passive transition were characterized by anodic peak current (i_m) and voltage (E_m), which in turn were found to vary with the experimental conditions, i.e., d(log?(im))/dpH=−0.8±0.1 and dE_m/dpH which was −71 mV at 98 °C, −58 mV at 80 °C and −28 mV at 60 °C. The activation energy for titanium corrosion, determined from temperature studies, was found to be 67.7 kJ mol⁻¹ in 0.1 M H₂SO₄ and 56.7 kJ mol⁻¹ in 1.0 M H₂SO₄. The dielectric breakdown voltage (E_d) of the passive TiO₂ film was found to vary depending on how much TiO₂ was present. The inclusion of Mn²⁺ into the H₂SO₄ electrolyte, as is done during the commercial electrodeposition of manganese dioxide, resulted in a decrease in titanium corrosion current, possibly due to Mn²⁺ adsorption limiting electrolyte access to the substrate.     

CaO-MgO-SiO2-H2O体系的热力学基础研究

本文从热力学角度系统研究了CaO-MgO-SiO     

Recovery of Na2SO4·10H2O from a reverse osmosis retentate by eutectic freeze crystallisation technology

The increasing amount of waste water and effluent from South Africa's mining industry forms a growing problem, which processing requires sustainable solutions in which both the water and the dissolved component can be re-used. Eutectic freeze crystallisation (EFC) has been identified as a key technology that is not only energy efficient, but also produces ice and salt products of high quality. Unlike reverse osmosis membrane systems, EFC can treat both dilute and concentrated systems minimising waste water volumes. In this paper it is shown that freeze and eutectic freeze crystallisation can be used for the processing of a reverse osmosis retentate stream containing 4% NaSO₄ and a number of impurities (F, Cl, K, Li, Mg, Ca, NO₃ and NH₄), producing both pure water and NaSO₄·10H₂O crystals. The influence of the impurities on the eutectic point and on the crystal structure of mirabilite was investigated using EFC technology investigated for a pure binary system, for a synthetic reverse osmosis retentate as well as for a concentrated NaCl system. In addition, investigations into the recovery and purity of mirabilite for these streams were conducted.     

Anion water in gypsum (CaSO4·2H2O) and hemihydrate (CaSO4·1/2H2O)

The bonding nature of water in gypsum, CaSO₄·2H₂O, and hemihydrate, CaSO₄·1/2H₂O, was suggested by characteristic absorption bands of water and sulphate ions. The infrared spectral data indicate the presence of anion water in gypsum and hemihydrate through hydrogen bonding. Negative shifting of bending vibration of SO₄ ion and lowering and broadening of the O-H stretching vibration at around 3600 cm⁻¹ indicate the presence of both anion water and hydrogen bonding in gypsum and hemihydrate     

The Au/O2 electrode in 1 M H2SO4

Open circuit dependence of potential on oxygen partial pressure as well as potentiostatic behavior in O₂- and He-saturated solution were determined. Stable hydrogen-oxygen species were formed, but potential-determining reversbility was found only in the potential range from 0·64–0·70 V (nhe). This equilibrium could be reasonably explained by an O₂/H₂O₂ exchange. Oxygen, H₂O₂, or other hydrogen-oxygen species may affect open circuit potentials and potentiostatic behavior, but analysis of data assuming reversibility or quasi-equilibrium kinetic theory may be justified only between 0·64 and 0·70 V.     

Electropolishing of NiTi shape memory alloys in methanolic H2SO4

The electropolishing of NiTi shape memory alloys was surveyed electrochemically. Anodic polarization of NiTi up to 8 V was performed in various aqueous and methanolic H₂SO₄ solutions. The passivity could be overcome in methanolic solutions with 0.1 mol dm−3≤CH₂SO₄≤7 mol dm−3. The dissolution kinetics was studied in dependence of the polarization potential, the H₂SO₄-concentration, the water concentration and the temperature. For lower concentrations of sulfuric acids (CH₂SO₄≤0.3 mol dm−3) electropolishing conditions were not observed for potentials up to 8 V. The dissolution remained under Ohmic control. In the concentration range from 1 to 7 mol dm⁻³ a potential independent limiting current was registered depending linearly on the logarithm of concentration. The best results were obtained with a 3 mol dm⁻³ methanolic sulfuric acid at 263 K which yielded an electropolishing current of 500 A m⁻² at a potential of 8 V. Surface roughness as well as current efficiency showed an optimum under these conditions.     

Anodische schichten auf aluminium in wasserfreier 1 M H2SO4-dimethylformamidlosung

AT sufficiently high anodic polarization in a 1 M H₂SO₄-dimethylformamide solution an amorphous layer on the surfaces of aluminium electrodes is formed. This could be proved by electron diffraction methods. The result was supported by characteristic dependences of the anodic current density—potential-curves, potentiostatic switching curves and ohmic resistance on the frequency of rotation of the electrode disc using a interrupter potentiostat. From transmission electron diffraction and energy dispersive microanalytic investigations the existence of amorphous aluminium sulphate could be concluded. Morphological and structural changes of the electrode surface, depending on the potential were investigated additionally by scanning electron microscopy and reflection electron diffraction. A model of the film formation on the aluminum surface will be suggested.     

Oxidative leaching kinetics of molybdenum-uranium ore in H2SO4 using H2O2 as an oxidizing agent

The processing of molybdenum-uranium ore in a sulfuric acid solution using hydrogen peroxide as an oxidant has been investigated. The leaching temperature, hydrogen peroxide concentration, sulfuric acid concentration, leaching time, particle size, liquid-to-solid ratio and agitation speed all have significant effects on the process. The optimum process operating parameters were: temperature: 95°C; H₂O₂ concentration: 0.5 M; sulfuric acid concentration: 2.5 M; time: 2 h; particle size: 74 μm, liquid-to-solid ratio: 14 ∶ 1 and agitation speed: 600 rpm. Under these experimental conditions, the extraction efficiency of molybdenum was about 98.4%, and the uranium extraction efficiency was about 98.7%. The leaching kinetics of molybdenum showed that the reaction rate of the leaching process is controlled by the chemical reaction at the particle surface. The leaching process follows the kinetic model 1 ? (1?X)^1/3 = kt with an apparent activation energy of 40.40 kJ/mole. The temperature, concentrations of H₂O₂ and H₂SO₄ and the mesh size are the main factors that influence the leaching rate. The reaction order in H₂SO₄ was 1.0012 and in H₂O₂ it was 1.2544.     

Effect of the addition of NH4F on anodic behaviors of DSA-type electrodes in H2SO4-(NH4)2SO4 solutions

The effect of NH₄F addition on the high-anodic behaviors of various DSA-type electrodes was investigated in a mixture of sulfuric acid and ammonium sulfate. The pronounced effect of NH₄ addition was observed on DSA-type Ti/RuO₂, Ti/IrO₂?TiO₂ electrodes, but not observed on the other electrodes studied. The close relationship was found between the increment of the electrode potential caused by the NH₄ addition and the quantity of F^? adsorbed on the electrode surface. The effect of NH₄F addition was considered to be resulted from the adsorption of F^? on the electrode surface, and the presence of adsorbed F^? was directly proved.