Supersaturation Ratio Research Articles

Effect of dustiness in atmospheric air on the formation and characteristics of condensation aerosol

In this work, the simulation of the formation process of condensation aerosol in atmospheric air is carried out. The influence of the initial supersaturation ratio and dustiness content on the formation mechanism and macroscopic characteristics of the aerosol is investigated.

Effects of solvent, supersaturation ratio and silica template on morphology and polymorph evolution of vanillin during swift cooling crystallization

Swift cooling crystallization of vanillin was investigated in water, ethanol, isopropanol and ethyl acetate. Morphology and polymorph evolution of vanillin were discussed in terms of solvent, supersaturation ratio and silica template. PXRD, DSC, FTIR and microscope were used to identify polymorphs of vanillin. Results showed that the nucleated polymorphs of vanillin depended largely on the solvent, supersaturation ratio and silica template. Low supersaturation ratios favor the nucleation of stable form I in water, and high supersaturation ratio exceeds 7 generating 100% metastable form II. However, if the supersaturation ratio is too high (S>8), liquid–liquid phase separation will occur, and no crystals could be obtained. In other solvents such as ethanol, isopropanol and ethyl acetate, only form I was obtained. However, it should be noted that the morphology of form I prepared in ethanol, isopropanol and ethyl acetate is distinct from that obtained in water, the former is flake-like and the latter is rod-like. The nucleation of vanillin from different solution was also studied with the presence of SiO2, SiO2–NH2 and SiO2−COOH templates, which did not change the nucleated polymorph of vanillin, but changed the nucleation and growth rate of stable form I.

Reduction entropy generation and condensation by NaCl particle injection in wet steam supersonic nozzle

The supersonic nozzle is very often used in many technical applications, such as fluid-flow machines or devices. If the medium flowing through a supersonic nozzle is a moist gas, moist air or wet steam, non-equilibrium condensation must occur. Such mediums usually contain impurities which affect the condensation phenomenon. The main purpose of this research is a numerical study on the effect of the content of impurities in steam on the non-equilibrium condensation phenomenon. In order to achieve this purpose, salt (NaCl) is used. Sodium chloride (NaCl) is a very common steam impurity. It may occur in a soluble or crystal form. Different concentrations of salt are considered as the input quantity. The results show that the process of steam condensation on salt particles has a significant impact on two-phase variables and flow parameters. In the presence of salt, steam condensation starts whenever the supersaturation ratio is above one. Latent heat of the condensation changes the flow pattern and reduces the nucleation rate and water droplet production. The presence of 1015 particles of salt reduces the outlet average liquid mass fraction and entropy generation by 14.5 % and 15.2 % respectively. The research results prove that steam impurities have a significant impact on non-equilibrium condensation.

Nucleation and Growth of Iron (II) Oxide Nanoparticles in Thermal Arc Plasma and Their Interaction Study With SARS-CoV-2: A Computational Approach

A computational model for nucleation and growth of iron (II) oxide nanoparticle (IONP) in thermal plasma has been developed. A nondimensional form of the aerosol general dynamic equations (GDEs) along with a discrete volume sectional model assumption is used to numerically solve the coupled system of GDEs. The variation in supersaturation ratio and the mean particle diameter of IONPs with respect to temperature across the plasma reactor has been presented. The scatter plot showing the distribution of particle number density of certain size across the reactor chamber is shown. In silico molecular docking study was performed to reveal the putative interaction of the IONPs with severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) virus. The results revealed significant binding affinity of IONPs with 6LZG (spike receptor-binding domain complexed with its receptor ACE2) and 5RH4 (main protease) of SARS-COV-2 by forming hydrogen and hydrophobic bonds with nearby amino acid residues. The interactions of IONPs are associated with the conformational changes in the protein which could be used to treat and control SARS-CoV-2 infection.

CCN and INP activity of middle eastern soil dust

The term mineral dust encompasses a myriad of particle compositions from both fertile and arid regions. Due to this diversity, the quantitative understanding of mineral dust as Cloud Condensation Nuclei (CCN) and Ice Nucleating Particles (INPs) in the Earth’s atmosphere demand further investigation. This study characterizes the CCN and INP activity of mineral dust particles from samples collected from one of the Earth’s major arid regions, Saudi Arabia. Samples were size selected at particle diameters (Dp) of 300, 700, and 950 nm and introduced into a Cloud Condensation Nuclei Counter (CCNC) and a SPectrometer for Ice Nuclei (SPIN) chamber to investigate cloud nucleation activity. The chemical composition of the particles was analyzed with laser mass spectrometry and mineralogical information was provided by polarized light microscopy. Transmission electron microscopy was used to ascertain particle morphology. Each particle size was exposed to water supersaturations of 0.06–1.0% in the CCNC and to ice supersaturation ratios of 1.1 to 1.5 at temperatures from −25 to −42 °C in SPIN. The CCN activity ranged from hygroscopicity values (κ) of 0.001 to 0.01. This is towards the lower range of critical supersaturations found for other mineral dust samples from e.g. the Sahara, North Africa, China and Asia. The INP activity, defined by fractional activation and supersaturation at the onset of ice nucleation was in the range of other natural mineral dusts (e.g., the Sahara, Canary Islands), and somewhat lower than industrially processed Arizona Test Dust. This study highlights the importance of considering size-resolved compositional data when interpreting the cloud-nucleation activity of natural mineral and soil dusts.

The important roles of surface tension and growth rate in the contribution of new particle formation (NPF) to cloud condensation nuclei (CCN) number concentration: evidence from field measurements in southern China

Abstract. The contribution of new particle formation (NPF) to cloud condensation nuclei (CCN) number concentration (NCCN) varies largely under different environments and depends on several key factors such as formation rate (J), growth rate (GR), distribution of preexisting particles, and properties of new particles during NPF events. This study investigates the contribution of NPF to the NCCN and its controlling factors based on measurements conducted at the Heshan supersite, in the Pearl River Delta (PRD) region of China during fall 2019. The size-resolved cloud condensation nuclei activity and size-resolved particle hygroscopicity were measured by a cloud condensation nuclei counter (CCNc) and a hygroscopic tandem differential mobility analyzer (HTDMA), respectively, along with a scanning mobility particle sizer (SMPS) and a diethylene glycol scanning mobility particle sizer (DEG-SMPS) for particle number size distribution (PNSD). A typical NPF event on 29 October was chosen to investigate the contribution of the NPF to NCCN under several supersaturation (SS) ratios. Two particle properties (hygroscopicity and surface tension) affect CCN activation with the latter being more important in terms of the CCN concentration (NCCN). A lower value of surface tension (i.e., 0.06 N m−1) than the pure-water assumption (0.073 N m−1) could increase the NCCN at SS = 1.0 % by about 20 % during the nonevent period and by about 40 % during the event. In addition, an earlier peak time corresponding to a lower critical diameter (D50) was also observed. The results show that high formation rate, growth rate, and low background particle concentration lead to high number concentrations of newly formed particles. The high growth rate was found to have the most significant impact on the NCCN, which can be attributed to the fact that a higher growth rate can grow particles to the CCN size in a shorter time before they are scavenged by preexisting particles. Two other NPF events (an event on 18 October in this campaign and an event on 12 December 2014 in Panyu) were chosen to perform sensitivity tests under different scenarios (growth rate, formation rate, and background particle concentration). The calculated NCCN at SS = 1.0 % on 12 December 2014 was significantly lower than that from the other two events. The event on 12 December was re-simulated using the growth rate taken from the event on 18 October which resulted in similar CCN concentrations between the two events (12 December and 18 October), implying that the growth rate is the major impact factor for CCN activation. Our results highlight the importance of growth rate and surface tension when evaluating the contribution of NPF to the NCCN.

Phosphorus recovery from wastewater by struvite in response to initial nutrients concentration and nitrogen/phosphorus molar ratio

Nutrients recovery from wastewater using struvite crystallization has received significant attention because the recovered nutrients can be used as a fertilizer in agriculture. However, the wastewater with different composition of nutrients might exert distinct struvite characteristics. The objective of this study is to explore the influence of nitrogen/phosphorus (N/P) molar ratio and initial nutrient concentrations on the phosphorus (P) recovery from wastewater and the crystallographic properties of struvite through batch experiments. Both the higher nutrients concentrations and N/P molar ratio in the wastewater resulted in higher recovery of P. However, initial nutrients concentration in the wastewater posed a larger effect on the formation of struvite than that of initial N/P ratio. The ratio of N to P consumed during the process varied with varying the N/P ratio or the initial nutrients concentration, indicating the existence of different crystallization mechanisms under different elemental compositions in the wastewater. The decline in solution pH was negatively correlated with the N/P ratio, whereas it was positively correlated with the nutrient concentration. The crystals produced were mainly rough (dendritic) under the N/P ratio of 2, while the morphology evolved from a regular coffin-like to irregular columnar with the increase in N/P ratio from 4 to 10. Meanwhile, the shape of the irregular cylinder gradually changed from elongated needle shape to the thick rods appearance with the increase in the nutrients concentration. Higher N/P ratio increased the nucleation rate, resulting in finer particles and an uneven crystal size distribution, but purer struvite crystals. The purity of struvite was also positively correlated with the initial nutrients concentration. The Visual MINTEQ modelling analysis demonstrated that the supersaturation ratio of struvite gradually increased with the increase in the N/P ratio or nutrients concentration, which led to a positive effect on struvite crystallization.

Physiologically-based pharmacokinetics modeling to investigate formulation factors influencing the generic substitution of dabigatran etexilate.

The exposure‐response relationship of direct acting oral anti‐coagulants (DOACs) for bleeding risk is steep relative to ischemic stroke reduction. As a result, small changes in exposure may lead to bleeding events. The overall goal of this project was to determine the effect of critical formulation parameters on the pharmacokinetics (PKs) and thus safety and efficacy of generic DOACs. In this first installment of our overall finding, we developed and verified a physiologically‐based PK (PBPK) model for dabigatran etexilate (DABE) and its metabolites. The model was developed following a middle out approach leveraging available in vitro and in vivo data. External validity of the model was confirmed by overlapping predicted and observed PK profiles for DABE as well as free and total dabigatran for a dataset not used during model development. The verified model was applied to interrogate the impact of modulating the microenvironment pH on DABE systemic exposure. The PBPK exploratory analyses highlighted the high sensitivity of DABE exposure to supersaturation ratio and precipitation kinetics.

Determination of chlorzoxazone crystal growth kinetics and size distribution under controlled supersaturation at 293.15 K

Background: Chlorzoxazone (CHZ) is a water-insoluble drug having bioavailability problems. The absorption rate of such drugs can be improved by reducing their particle size. In this work, the crystal growth kinetics of CHZ–ethanol for different degrees of supersaturation (SS) has been studied. Method: The equilibrium solubility data of CHZ in ethanol is determined by the shake-flask method within the 283.15–313.15 K temperature range. The mole fraction solubility of CHZ is calculated and correlated with the modified Apelblat equation, λh equation, van’t Hoff equation, Wilson, and non-random two liquid (NRTL) equation. Batch crystallization experiments are performed on three different degrees of SS-1.16, 1.18, and 1.20 at 293.15 K as a function of time. Results: The maximum root mean square difference (RMSD) and relative average deviation (RAD) values of 169.24 x10-6 and 0.699 x10-2, respectively, are observed in the NRTL equation model. The dissolution properties such as standard enthalpy, standard entropy, and Gibbs free energy are predicted using van’t Hoff equation. Using a simple integral technique, the average crystal growth rate constant KG is calculated as 1.58 (μm/min) (mg/ml)-1 and the order n=1 for CHZ–ethanol at 293.15 K. Conclusion: The obtained result concludes that the crystals growth size is found to be varied at different SS ratio in batch crystallization. The particle size control in batch crystallization can be achieved by optimizing the operating conditions to get the desired size crystals.

A turbidity titration procedure for the nucleation mechanism determination of sodium sulfate decahydrate (Glauber salt) in unseeded aqueous solution

As a noteworthy salt hydrate, sodium sulfate decahydrate or Glauber salt can be used as a phase change thermal energy storage material. Kinetic parameters of sodium sulfate decahydrate salt solution are evaluated experimentally. Instead of the traditional polythermal and isothermal methods, a novel constant temperature experimental method (based on the turbidity titration) was adopted to experimentally illustrate the induction time and metastable zone width, in unseeded batch crystallization for sodium sulfate decahydrate salt solution at different temperatures (7, 9, 10, 13, 16, 19, 22 °C) and supersaturation ratio (1.01–1.43). We determined crystallization thermodynamics parameters, solubility, and supersolubility, of sodium sulfate decahydrate salt solution under atmospheric pressure and at different temperatures. The solubility data could be well fitted by the solubility carve of sodium sulfate decahydrate in the phase diagram of sodium sulfate. Statistical analysis shows that there was consistency in the result data of solubility. Two models, classical nucleation theory (primary homogeneous) and secondary nucleation, were employed to analyze the experimental data. The secondary nucleation model helped determine the order of nucleation and nucleation kinetic constants.

Determination of nucleation kinetics from the induction time of 1,1-diamino-2,2-dinitroethylene (FOX-7) in DMSO/Water

Elucidation of the crystal nucleation process can provide guidance for controlling crystal size and quality. To understand the nucleation process of 1,1-diamino-2,2-dinitroethylene (FOX-7), the induction time and nucleation kinetics of FOX-7 were studied using a turbidity method in a binary solvent system (DMSO ​+ ​water, xDMSO ​= ​0.3364) under cooling crystallization conditions. Using the CrystalSCAN system, the induction time was determined at a range of temperatures (325.05, 335.25, 343.15, 348.15, and 354.65 ​K) and supersaturations (S) (1.20, 1.22, 1.24, 1.27, 1.30, 1.32, 1.35, 1.37), and it was found that induction time decreases as supersaturation increases. The system displayed a homogeneous nucleation mechanism at high supersaturation ratios (≥1.27) and heterogeneous nucleation at low supersaturation ratios, below 1.25. The FOX-7 crystal exhibited a continuous growth mechanism, as inferred from the value of the surface entropy factor (f). The induction time data were analyzed using the classical nucleation theory to calculate the interfacial energy (γ) and various nucleation parameters, including the radius of the critical nucleus (r∗), critical free energy of the nucleus (ΔG∗), molecular number of the critical nucleus (i∗), and the nucleation rate (J). The morphology of FOX-7 crystals changed negligibly with varying temperature and supersaturation, while the average particle size decreased with an increase in supersaturation and a decrease in temperature.

The Variation of Factor of Enhancement in Nucleation Rate with Electric Field for Water Vapour and Ice

the nucleation rate is the parameter to judge the effect of electric field on nucleation of water vapour and ice glaciation. In the presence of electric field the total nucleation is the sum of nucleation due to electric field and nucleation due to diffusion of water molecules. Thus we can say the nucleation rate is enhanced by the factor of RE. This is known as factor of enhancement in nucleation rate. In the present work we will calculate the factor of enhancement in nucleation rate for water vapour and ice on temperature 268 K at different electric fields as a function of super saturation ratio.

Numerical investigation of barite scaling kinetics in fractures

Barite stands out as one of the most ubiquitous scaling agents in deep geothermal systems, responsible for irreversible efficiency loss. Due to complex parameter interplay, it is imperative to utilise numerical simulations to investigate temporal and spatial precipitation effects. A one-dimensional reactive transport model is set up with heterogeneous nucleation and crystal growth kinetics. In line with geothermal systems in the North German Basin, the following parameters are considered in a sensitivity analysis: temperature (25 to 150 °C), pore pressure (10 to 50 MPa), fracture aperture (10−4 to 10−2 m), flow velocity (10−3 to 100 m s−1), molar volume (50.3 to 55.6 cm3 mol−1), contact angle for heterogeneous nucleation (0° to 180°), interfacial tension (0.07 to 0.134 J m−2), salinity (0.1 to 1.5 mol kgw−1 NaCl), pH (5 to 7), and supersaturation ratio (1 to 30). Nucleation and consequently crystal growth can only begin if the threshold supersaturation is exceeded, therefore contact angle and interfacial tension are the most sensitive in terms of precipitation kinetics. If nucleation has occurred, crystal growth becomes the dominant process, which is mainly controlled by fracture aperture. Results show that fracture sealing takes place within months (median 33 days) and the affected range can be on the order of tens of metres (median 10 m). The presented models suggest that barite scaling must be recognised as a serious threat if the supersaturation threshold is exceeded, in which case, large fracture apertures could help to minimise kinetic rates. The models further are of use for adjusting the fluid injection temperature.

Analytical expression for isolated pore shape in solid

Algebraic expressions for the pore shape after a bubble completely entrapped in solid are provided in this study. Properties of functional materials in micro-or nano-technologies strongly depend on pore shapes in solid. The model is based on a previous work by accounting for transient gas pressure in the pore affected by solute transfer for different cases, and balance of gas, capillary and hydrostatic pressures, and physico-chemical equilibrium at the bubble cap. The results find that algebraic prediction of the pore shapes with exact expressions of the maximum pore radii in different cases can be accomplished by dividing the pore length into three segments with inclination angles greater than initial contact angle, between initial contact angle and 90 degrees, and less than 90 degrees. The shape of an isolated pore is thus delineated by the bottom spherical cap, radius and length at the initial contact angle and maximum pore radius and length at inclination angle of 90 degrees, and top spherical cap. Dimensionless independent parameters controlling the pore length include initial contact angle, mass transfer coefficient, supersaturation ratio, product of Bond number with initial solute concentration in liquid, Henry's law constant (in Cases 1-3), and partition coefficient (in Cases 3 and 4). The predicted lengths in three segments and shapes of the isolated pore agree with numerical computations confirmed by experimental data.

Determination of the metastable zone and induction time of thiourea for cooling crystallization

Abstract The solubility, metastable zone width (MSZW), and induction time of thiourea for cooling crystallization were experimentally determined in the temperature range of 283–323 K. The solubility data could be well described by the Apelblat equation model as lnx = −99.55 + 1071.66/T + 16.27lnT. The determinations of the effects of various stirring and cooling rates indicated that the MSZW increased with increasing and decreasing cooling and stirring rates, respectively. Furthermore, the induction times at various temperatures and supersaturation ratios were also measured. The results indicated that homogeneous nucleation could occur at high supersaturation, whereas heterogeneous nucleation was more likely to occur at low supersaturation. Based on the classical nucleation theory and induction period data, the calculated solid–liquid interfacial tensions of thiourea in deionized water at 302.46 and 312.58 K were 2.86 and 2.94 mJ⋅m−2, respectively.

ALÜMİNYUM HİDROKSİT KRİSTALİZASYONU ÜZERİNE LİTYUM SAFSIZLIĞININ ETKİSİ

Bu çalışmada, farklı modülb değerlerine (1,35; 1,41; 1,45; 1,49; 1,8; 2,0; 2,25; 2,50) sahip sodyum alüminat çözeltilerinin nükleasyon davranışları incelenmiştir. Bu amaçla, çözeltiye verilen farklı aşırı doygunluk değeri (1,321-1,785) ve farklı derişimde (5-20 ppm) lityum (Li) varlığı için bekleme zamanı ölçümleri yapılmıştır. Deneysel çalışmalar sonucu, kritik serbest enerji değişimi, kritik nüklei yarıçapı, kritik nükleide yer alan molekül sayısı ve nükleasyon hızı hesaplanmıştır. Katkısız sodyum alüminat çözeltisi için bekleme zamanının, farklı aşırı doygunluk değerlerine bağlı olarak 100-400 dk. aralığında değiştiği belirlenmiştir. Lityum varlığında ise, en yüksek bekleme zamanı 10 ppm lityum derişimi için 20 dk. olarak tespit edilmiştir. Klasik nükleasyon teorisine göre yapılan hesaplamalar sonucu, lityum varlığında, katkısız ortama kıyasla, kritik nüklei yarıçapının düştüğü, kritik nükleideki molekül sayısının azaldığı ve nükleasyon hızının arttığı belirlenmiştir. 5 ppm lityum katkısı için, katkısız ortama kıyasla, nükleasyon hızındaki artışın yaklaşık 100 kat, 20 ppm lityum katkısı için ise yaklaşık olarak 39 kat olduğu belirlenmiştir. Lityum varlığında, farklı modülb değerlerindeki sodyum alüminat çözeltilerinin bekleme zamanlarının düşük ve yüksek modülb değerine sahip çözeltiler için 6 – 7 dk. aralığında değiştiği tespit edilmiştir. Modülb 1,49 ve 1,8 için ise maksimum 10 dk’lık bekleme süreleri elde edilmiştir.

CFD-calculation of influence of impurities on the characteristics of a helium turboexpander

The process of expanding of two-component gaseous mixture was studied in a stage of a turboexpander unit in three-dimensional unsteady setting with use of methods of computer fluid dynamics. The calculation method used in this work made it possible to study the turboexpander unit in a single calculation model but not in parts due to the use of sliding interfaces. Based on the distribution of the supersaturation ratio, assumption was made about the possible localization of phase transitions in the flow part of the stage of the turboexpander unit, confirmed by the characteristic impeller damage.

Incipient membrane scaling in the presence of polysaccharides during reverse osmosis desalination in spacer-filled channels

This study aims to shed light into the complicated phenomena occurring during the early stages of RO-membrane scaling when organic-foulants are present. Experiments were performed, using spacer-filled channel in once-through flow-mode, closely simulating conditions prevailing at tail elements of pressure-vessels. The effect was studied of a typical foulant (polysaccharide, sodium-alginate, SA), at small concentrations (~2 mg/L and ~10 mg/L), on incipient crystallization/deposition of calcium sulfate (CaSO4·2H2O, gypsum) during RO-desalination of synthetic brackish-water at small super-saturation ratio S (1.0 to 1.5). Scanning Electron Microscopy and membrane-scale/foulants dissolution techniques were employed. At small SA concentration (~2 mg/L) incipient-scaling inhibition is observed (likely due to crystallite-growth retardation by adsorbed organic molecules); however, at higher SA concentration (~10 mg/L), significant enhancement of incipient scaling occurs, attributed to formation of coherent organic-gel fouling-layer, favoring concentration increase of inorganic-scalants at the membrane-surface and consequent increase of supersaturation. Under such conditions, although the fouling-layer thickness remains roughly constant (due to constant deposited organic-matter), the specific fouling resistance α tends to significantly increase with increasing supersaturation, likely due to physico-chemical structural changes within the alginate gel-layer. The techniques employed allow determination and correlation of key fouling/scaling parameter-values (i.e. scale-mass deposition-rate and resistance α), that are necessary for developing reliable process modeling/simulation tools.

Impact of Supersaturation Ratio on the Kinetics of Gas Evolution at Elevated Pressures

The kinetics of gas evolution in supersaturated solutions is a critical uncertainty in the design and operation of gas/liquid separators. Incorrectly predicting the amount of gas that evolves in a ...

On the particle formation of leucine in spray drying of inhalable microparticles

The particle formation of L-leucine, a dispersibility-enhancing amino acid used in the spray drying of inhalable pharmaceutical aerosols, was extensively studied using three experimental methods, and the results were interpreted with the aid of theory. A comparative-kinetics electrodynamic balance was used to study the shell formation behavior in single evaporating microdroplets containing leucine and trehalose. Different concentration thresholds of solidification and shell formation were determined for trehalose and leucine, which were then used in the particle formation model to predict the properties of spray-dried particles. Furthermore, a droplet chain instrument was used to study the particle morphologies and particle densities that were not accessible in the single particle experiments. Lab-scale spray drying was also used to produce powders typical for actual pharmaceutical applications. Raman spectroscopy confirmed that a glass former, such as trehalose, can inhibit the crystallization of leucine. The surface compositions of these spray-dried powders were analyzed via time-of-flight secondary ion mass spectrometry. The leucine surface coverage in a polydisperse powder was determined to be a function of the particle size or the initial droplet diameter of each respective particle. This observation confirms the important role of leucine crystallization kinetics in its shell-forming capabilities. A critical supersaturation ratio of 3.5 was also calculated for leucine, at which it is assumed to instantaneously nucleate out of solution. This ratio was used as the threshold for the initiation of crystallization. Crystallinity predictions for the leucine-trehalose particles based on this supersaturation ratio were in good agreement with the solid-state characterizations obtained by Raman spectroscopy. This study improves the fundamental understanding of the particle formation process of leucine-containing formulations, which can apply to other crystallizing systems and potentially facilitate the rational design of such formulations with reduced experimental effort.