Study of sulfur heterogeneous nucleation from supersaturated vapor on tungsten oxide and sodium chloride seed particles. Determination of contact angle of critical sulfur nuclei

A procedure has been developed for determining the contact angle of a critical nucleus formed on seed particles during the heterogeneous nucleation of a vapor in a flow chamber. The procedure comprises the determination of the fraction of enlarged particles, as well as the selective separation of nanoparticles over sizes to locate the zone of intense nucleation. The concentration and size distribution of aerosol particles have been measured with a diffusion spectrometer of aerosols. Vapor concentration distributions and supersaturation fields have been determined by solving the mass-transfer problem. The calculated supersaturation fields are in good agreement with the location of the intense nucleation zone experimentally found with the help of selective separation. The fractions of enlarged particles have been determined as functions of supersaturation in the chamber. A formula has been derived for calculating the fraction and size distribution function of enlarged particles at known supersaturation and temperature fields and a preset contact angle. The contact angles are selected in a manner such that the calculated fraction of enlarged particles coincides with that measured experimentally. It has been revealed that the contact angle of critical sulfur nuclei formed on tungsten oxide seed particles with average radii 〈R _p〉 ≈ 5.8?4.4 nm is in a range of 21.2?20.5°, while, in the case of sodium chloride seed particles with 〈R _p〉 ≈ 6.0?4.4 nm, the contact angle is 20.4?17.4°. The size of a critical nucleus has been found to be proportional to calculated average radius of a seed particle 〈R _p〉 in both cases.     

Condition of lead iodide in the medium of lyophilic sols

The condition of lead chromate in gelatin and agar agar medium has been studied. In presence of agar agar medium the colloid formed is stabilised by lead ions and coagulated by the excess of chromate ions. Lead chromate forms a very stable colloid in the presence of gelatin sol which could not be precipitated by excess of lead ions or chromate ions. Due to the formation of a very stable colloid in gelatin medium, well defined rings of lead chromate are not obtained in gelatin gel.     

Physical basis for constrained lattice density functional theory

To study nucleation phenomena in an open system, a constrained lattice density functional theory (LDFT) method has been developed before to identify the unstable directions of grand potential functional and to stabilize nuclei by imposing a suitable constraint. In this work, we answer several questions about the method on a fundamental level, and give a firmer basis for the constrained LDFT method. First, we demonstrate that the nucleus structure and free energy barrier from a volume constraint method are equivalent to those from a surface constraint method. Then, we show that for the critical nucleus, the constrained LDFT method in fact produces a bias-free solution for both the nucleus structure and nucleation barrier. Finally, we give a physical interpretation of the Lagrange multiplier in the constraint method, which provides the generalized force to stabilize a nucleus in an open system. The Lagrange multiplier is found to consist of two parts: part I of the constraint produces an effective pressure, and part II imposes a constraint to counteract the supersaturation.     

Applying the Taguchi Robust Design to Optimization of the Experimental Conditions for Synthesis of Lead Chromate Nanorods

Orthogonal array design was employed as statistical method for controllable, simple, and fast synthesis of highly uniform PbCrO₄ nanorods by precipitation method. Lead chromate nanorods were synthesized by addition of lead solution to chromate reagent. Effect of reaction conditions on the width of lead chromate rods were quantitavely evaluated by analysis of variance. Finally, optimum conditions for synthesis of lead chromate nanorods by this simple and fast method were proposed. The results of analysis of variance showed that 0.001 mol/L lead and chromate ion concentrations are optimum conditions for producing lead chromate nanorods with 87 ± 15 nm width.     

Experimental study of homogeneous nucleation from the bismuth supersaturated vapor: evaluation of the surface tension of critical nucleus

The homogeneous nucleation of bismuth supersaturated vapor is studied in a laminar flow quartz tube nucleation chamber. The concentration, size, and morphology of outcoming aerosol particles are analyzed by a transmission electron microscope (TEM) and an automatic diffusion battery (ADB). The wall deposit morphology is studied by scanning electron microscopy. The rate of wall deposition is measured by the light absorption technique and direct weighting of the wall deposits. The confines of the nucleation region are determined in the "supersaturation cut-off" measurements inserting a metal grid into the nucleation zone and monitoring the outlet aerosol concentration response. Using the above experimental techniques, the nucleation rate, supersaturation, and nucleation temperature are measured. The surface tension of the critical nucleus and the radius of the surface of tension are determined from the measured nucleation parameters. To this aim an analytical formula for the nucleation rate is used, derived from author's previous papers based on the Gibbs formula for the work of formation of critical nucleus and the translation-rotation correction. A more accurate approach is also applied to determine the surface tension of critical drop from the experimentally measured bismuth mass flow, temperature profiles, ADB, and TEM data solving an inverse problem by numerical simulation. The simulation of the vapor to particles conversion is carried out in the framework of the explicit finite difference scheme accounting the nucleation, vapor to particles and vapor to wall deposition, and particle to wall deposition, coagulation. The nucleation rate is determined from simulations to be in the range of 10(9)-10(11) cm(-3) s(-1) for the supersaturation of Bi(2) dimers being 10(17)-10(7) and the nucleation temperature 330-570 K, respectively. The surface tension σ(S) of the bismuth critical nucleus is found to be in the range of 455-487 mN/m for the radius of the surface of tension from 0.36 to 0.48 nm. The function σ(S) changes weakly with the radius of critical nucleus. The value of σ(S) is from 14% to 24% higher than the surface tension of a flat surface.     

Cluster kinetics and dynamics during spinodal decomposition

Spinodal decomposition (barrierless phase transition) is a spontaneous phase separation caused by conditions that force the system to become thermodynamically unstable. We consider spinodal decomposition to occur under conditions of large supersaturation S and/or small ratio of interfacial to thermal energies omega, such that the computed number of monomers in a critical nucleus xi*=(omega/ln S)3 is less than unity. The small critical nucleus size is consistent with a negligible energy barrier for initiating condensation. Thus, in contrast to conventional opinion, it is suggested that the spinodal decomposition is related to the homogeneous nucleation of metastable fluids. Population balance equations show how clusters aggregate and rapidly lead to phase separation. Different mass dependences of aggregation rate coefficients are proposed to investigate the fundamental features of spinodal decomposition. When the mass dependency is an integer, the equations are solved by the moment technique to obtain analytical solutions. When the mass dependency is a noninteger, the general cases are solved numerically. All solutions predict the two time regimes observed experimentally: the average length scale of condensed-phase domains increases as a power law with an exponent of 1/3 at early times, followed by a linear increase at longer times.     

Precipitation of barium chromate from homogeneous solution using complexation and replacement A separation of barium from relatively large amounts of strontium and lead

A new procedure is presented that efficiently separates barium from relatively large amounts of strontium and lead. The barium is precipitated as the chromate from a solution in which the multivalent cations are complexed with EDTA. The barium ions are homogeneously released in solution when magnesium ions are slowly introduced into the solution. The magnesium ions gradually replace the barium ions from their EDTA complexes, bringing about a precipitation of barium chromate from homogeneous solution.

This slow formation of barium chromate crystals holds co-precipitation to a minimum and produces crystals that are easily filtered and washed. More than 99.7% of the barium can be precipitated as the chromate, with less than 0.6% of the strontium, when the two ions are in equal molar concentration.     

Free-energy landscape of nucleation with an intermediate metastable phase studied using capillarity approximation

Capillarity approximation is used to study the free-energy landscape of nucleation when an intermediate metastable phase exists. The critical nucleus that corresponds to the saddle point of the free-energy landscape as well as the whole free-energy landscape can be studied using this capillarity approximation, and various scenarios of nucleation and growth can be elucidated. In this study, we consider a model in which a stable solid phase nucleates within a metastable vapor phase when an intermediate metastable liquid phase exists. We predict that a composite critical nucleus that consists of a solid core and a liquid wetting layer as well as pure liquid and pure solid critical nuclei can exist depending not only on the supersaturation of the liquid phase relative to that of the vapor phase but also on the wetting behavior of the liquid surrounding the solid. The existence of liquid critical nucleus indicates that the phase transformation from metastable vapor to stable solid occurs via the intermediate metastable liquid phase, which is quite similar to the scenario of nucleation observed in proteins and colloidal systems. By studying the minimum-free-energy path on the free-energy landscape, we can study the evolution of the composition of solid and liquid within nuclei which is not limited to the critical nucleus.     

Kinetics of the crystallization of barium chromate

Summary The kinetics of the crystallization of barium chromate have been studied conductometrically at 298 K for both spontaneous and seeded growth systems. The rate of growth follows a quadratic dependence upon the relative supersaturation which suggests a surface-controlled growth mechanism. This rate equation holds fairly well for the various supersaturation and solid/solution ratios used. The presence of seeds in the solution appears to accelerate the growth rate. Analysis of the calculated induction times in unseeded systems corroborates the surface-controlled growth mechanism. The effect of some additives on the kinetics of growth has also been studied. The retarding effect of these inhibitors is interpreted in terms of adsorption of inhibitor ions at the active crystal growth sites.Dedicated to the memory of ProfessorE. N. Rizkalla who passed away on November 29, 1993     

Extended study of molecular dynamics simulation of homogeneous vapor-liquid nucleation of water

Using the simple point charge/extended water model, we performed molecular dynamics simulations of homogeneous vapor-liquid nucleation at various values of temperature T and supersaturation S, from which the nucleation rate J, critical nucleus size n(*), and the cluster formation free energy DeltaG were derived. As well as providing lots of simulation data, the results were compared with theories on homogeneous nucleation, including the classical, semi-phenomenological, and scaled models, but none of these gave a satisfactory explanation for our results. It was found that two main factors made the theories fail: (1) The average cluster structure including the nonspherical shape and the core structure that is not like the bulk liquid and (2) the forward rate which is larger than assumed by the theories by about one order of magnitude. The quantitative evaluation of these factors is left for future investigations.     

SORPTION OF OXYANIONS BY SURFACTANT-MODIFIED ZEOLITE

Zeolite has high internal and external surface areas and high internal and external cation exchange capacities suitable for surface modification by cationic surfactants. When the initial surfactant concentration is less than the critical micelle concentration, the sorted surfactant molecules primarily form a monolayer. Limited chromate sorption indicates that patchy bilayer may also form. When the initial surfactant concentration is greater than the critical micelle concentration and enough surfactant exists in the system, the sorbed surfactant molecules form bilayers, producing maximum chromate sorption. On a meq/kg basis, planar nitrate sorbs more on surfactant-modified zeolite surfaces than tetrahedral chromate. In the presence of sulfate or nitrate, chromate sorption is hindered due to competition for sorption sites. Quantitative sorption of nitrate and chromate and desorption of bromide indicate that the sorption of oxyanions is primarily due to surface anion exchange.     

Rationalization of nanowire synthesis using low-melting point metals

In this paper, we provide a theoretical basis using thermodynamic stability analysis for explaining the spontaneous nucleation and growth of a high density of 1-D structures of a variety of materials from low-melting metals such as Ga, In, or Sn. The thermodynamic stability analysis provides a theoretical estimate of the extent of supersaturation of solute species in molten metal solvent. Using the extent of maximum supersaturation, the size and density of critical nucleus were estimated and compared with experimental results using nucleation and growth of Ge nanowires using Ga droplets. The consistency of the proposed model is validated with the size and density of the resulting nanowires as a function of the synthesis temperature and droplet size. Both the experimental evidence and the theoretical model predictions point that the diameters of the resulting nanowires decrease with the lowering of synthesis temperatures and that the nucleation density decreases with the size of metal droplet diameter and increasing synthesis temperature.     

Calcium Carbonate Deposition on Cellulose

Cellulose powder was found to be a substrate favoring the deposition of calcite crystals from stable supersaturated solutions at pH 8.50 and at 25 degrees C. Kinetic analysis of the initial rates showed that they were proportional with the relative supersaturation with respect to calcite. Analysis of the dependence of the induction periods on the initial solution conditions showed that the number of ions forming the critical nucleus was 5. The second-order dependence of the rate of precipitation of calcite on cellulose on the solution supersaturation suggested a surface controlled mechanism. The surface energy of the calcite nuclei growing on cellulose was calculated to be 46 mJ m(-2) from the dependence of the induction time on the solution supersaturation. The overgrowth of calcite on cellulose was done selectively on the macromolecules possibly through active sites formation at ionizable functional groups (-OH). The nucleating capability of cellulose was found to be comparable with that of sulfonated polystyrene and significantly lower in comparison with sulfonated polystyrene divinyl benzene copolymer on which vaterite was formed. This fact together with the selective growth of the most stable calcite suggested that stereochemical factors are very important in determining both the kinetics and the nature of the polymorph formed. Copyright 2000 Academic Press.     

Detection and imaging of chrome yellow (lead chromate) in latent prints,solid residues,and minerals by laser‐desorption/ionization mass spectrometry (LDI‐MS)

In the past, chrome yellow (lead chromate, PbCrO₄), a bright orange‐red substance, has been widely used as an inorganic pigment in the production of paints, coatings, and plastics. Herein, we demonstrate that laser desorption/ionization mass spectrometry (LDI‐MS) is a powerful tool for the detection of lead chromate in solid residues. In fact, lead chromate in trace amounts is easily detectable by LDI‐MS even from residues left as latent prints. For example, a latent print obtained by stamping the exposed laterally cut surface of a pencil over 50 years old on an acetonitrile‐moistened paper, was successfully imaged for both lead and chromate using a Synapt G2 HDMS mass spectrometer. After rastering the print with a 355 nm laser beam and recording positive‐ and negative‐ion mass spectra over the range m/z 50–1200, we generated false‐color ‘heat maps’ (single‐ion images) for ²⁰⁸Pb^+• (m/z 207.98) and Cr₂O₆^−• (m/z 199.85). The heat maps matched closely with the faint visual image of the pencil imprint. Moreover, our results confirmed that lead chromate was used in the pigment coatings of old pencils. Evidently, LDI‐MS imaging is an efficient procedure to survey for the presence of lead and chromate in minerals and other materials. Copyright © 2017 John Wiley & Sons, Ltd.     

Phasenumwandlung zweiter Art bei der Gelbildung

During theLiesegang ring formation of lead chromate in an agar agar gel it was observed that broad bands are formed in the presence of light whereas finer bands are obtained in dark. This difference in behaviour is due to the fact that lead chromate forms a more stable sol in light as compared to that in the dark.     

Influence of DSC Measurement Conditions on Kinetic Parameters of Thermal Decomposition of 2,4,6-trinitrotoluene

An autocatalytic model involving the limited solubility of volatile catalytic products was applied to the thermal decomposition of 2,4,6-trinitrotoluene. The critical supersaturation of the thermal decomposition products with the catalytic properties was higher at a low heating rate. Decrease of the sample mass led to an increased critical supersaturation of the decomposition products. This is probably a result of the greater contribution of products adsorption on the aluminium pan surface. It is presumed that the differences observed in the rate constant are connected with the uncontrolled critical supersaturation of the volatile thermal decomposition products. This revised version was published online in August 2006 with corrections to the Cover Date.     

The nucleation of calcium phosphate from solution

Dicalcium phosphate was precipitated from homogeneous solution in the pH range 5–6 by using the hydrolysis of cyanate to control the precipitation process. Turbidimetric determination of the onset of precipitation enabled the critical supersaturation to be determined. In this region the average critical supersaturation ratio was found to be 2.3.     

溶液电导率法对碳酸钙结晶动力学的研究

溶液电导率法对碳酸钙结晶动力学的研究;结垢;电导率