A study of the drying of single droplets in free-flight

The literature relating to evaporation from single droplets of pure liquids and the drying of solution and slurry droplets, and of droplet sprays has been reviewed. The heat and mass transfer rates for individual droplets suspended in free-flight, were investigated using a specially-designed vertical wind tunnel, to simulate conditions in a spray drier. The technique represented a unique alternative method for investigating evaporation from unrestrained single droplets with variable residence times. The experiments covered droplets of pure liquid allowbreak (water, isopropanol) allowbreak and of significantly different solutions (sucrose, potassium sulphate) over a range of temperatures of 37oC to 97oC, initial concentrations of 5 to 40wt/wt% , and initial drop sizes of 2.8 to 4.6mm. Drop behaviour was recorded photographically and dried particles were examined by Scanning Electron Microscopy. Correlations were developed for mass transfer coefficients for pure water droplets in free-flight; (i) experiencing oscillations, rotation and deformation, Sh = -105 + 3.9 [Ta - Td/Tamb]0.18Re0.5Sc033 for Re approx. > 1380 (ii) when these movements had ceased or diminished, Sh = 2.0 + 0.71 [Ta - Td/Tamb]0.18Re0.5Sc033 for Re approx. < 1060. Data for isopropanol drops were correlated resonably well by these equations. The heat transfer data showed a similar transition range. The drying rate curves for drops of sucrose and potassium sulphate solution exhibited three distinct stages; an initial increase in the drying rate as drop temperature reduced to the wet-bulb temperature, a short constant-rate period and a falling-rate period characterised by formation of a crust which controlled the mass transfer rate. Due to drop perturbation the rates in the high Re number region were up to 5 times greater than predicted from theory for spherical droplets. In the case of sucrose solution a `skin' formed over the drop surface prior to crust formation. This provided an additional resistance to mass transfer and resulted in extended drying times and a smooth crust of low porosity. The relevance of the results to practical spray drying operations is discussed.

Dielectric studies of molecules and intramolecular relaxation processes

A new bridge technique for the measurement of the dielectric absorption of liquids and solutions at microwave frequencies has been described and its accuracy assessed. 'l'he dielectric data of the systems studied is discussed in terms of the relaxation processes contributing to the dielectric absorption and the apparent dipole moments. Pyridine, thiophen and furan in solution have a distribution of relaxation times which may be attributed to the small size of the solute molecules relative to the solvent. Larger rigid molecules in solution were characterized by a single relaxation time as would be anticipated from theory. The dielectric data of toluene, ethyl-, isopropyl- and t-butylbenzene as pure liquids and in solution were described by two relaxation times, one identified with molecular re-orientation and a shorter relaxation time.· The subsequent work was investigation of the possible explanations of this short relaxation process. Comparable short relaxation times were obtained from the analysis of the dielectric data of solutions of p-chloro- and p-bromotoluene below 40°C, o- and m-xylene at 25°C and 1-methyl- and 2 methylnaphthalene at 50 C. Rigid molecules of similar shapes and sizes were characterized by a single relaxation time identified with molecular re-orientation. Contributions from a long relaxation process attributed to dipolar origins were reported for solutions of nitrobenzene, benzonitrile and p-nitrotoluene. A short relaxation process of possible dipolar origins contributed to the dielectric absorption of 4-methyl- and 4-t-butylpyridine in cyclohexane at 25°C. It was concluded that the most plausible explanation of the short relaxation process of the alkyl-aryl hydrocarbons studied appears to be intramolecular relaxation about the alkyl-aryl bond. Finally the mean relaxation times of some phenylsubstituted compounds were investigated to evaluate any shortening due to contributions from the process of relaxation about the phenyl-central atom bond. The relaxation times of triphenylsilane and phenyltrimethylsilane were significantly short.

Swelling properties of alkali-metal doped polymeric anion-exchange membranes in alcohol media for application in fuel cells

Swelling properties of four commercial anion-exchange membranes with different structure have been analyzed in several hydro-organic media. With this target, the liquid uptake and the surface expansion of the membranes in contact with different pure liquids, water and alcohols (methanol, ethanol and 1-propanol), and with water alcohol mixtures with different concentrations have been experimentally determined in presence and in absence of an alkaline medium (LiOH, NaOH and KOH of different concentrations). The alkali-metal doping effect on the membrane water uptake has also been investigated, analyzing the influence of the hydroxide concentration and the presence of an alcohol in the doping solution. The results show that the membrane structure plays an essential role in the influence that alcohol nature and alkaline media has on the selective properties of the membrane. The heterogeneous membranes, with lower density, show higher liquid uptakes and dimensional changes than the homogeneous membranes, regardless of the doping conditions. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

A molecular theory of collective orientational relaxation in pure and binary dipolar liquids

A molecular theory of collective orientational relaxation of dipolar molecules in a dense liquid is presented. Our work is based on a generalized, nonlinear, Smoluchowski equation (GSE) that includes the effects of intermolecular interactions through a mean‐field force term. The effects of translational motion of the liquid molecules on the orientational relaxation is also included self‐consistently in the GSE. Analytic expressions for the wave‐vector‐dependent orientational correlation functions are obtained for one component, pure liquid and also for binary mixtures. We find that for a dipolar liquid of spherical molecules, the correlation function ϕ(k,t) for l=1, where l is the rank of the spherical harmonics, is biexponential. At zero wave‐vector, one time constant becomes identical with the dielectric relaxation time of the polar liquid. The second time constant is the longitudinal relaxation time, but the contribution of this second component is small. We find that polar forces do not affect the higher order correlation functions (l>1) of spherical dipolar molecules in a linearized theory. The expression of ϕ(k,t) for a binary liquid is a sum of four exponential terms. We also find that the wave‐vector‐dependent relaxation times depend strongly on the microscopic structure of the dense liquid. At intermediate wave vectors, the translational diffusion greatly accelerates the rate of orientational relaxation. The present study indicates that one must pay proper attention to the microscopic structure of the liquid while treating the translational effects. An analysis of the nonlinear terms of the GSE is also presented. An interesting coupling between the number density fluctuation and the orientational fluctuation is uncovered.

Transport properties of protic ionic liquids, pure and in aqueous solutions: Effects of the anion and cation structure

Ionic conductivities of twelve protic ionic liquids (PILs) and their mixtures with water over the whole composition range are reported at 298.15 K and atmospheric pressure. The selected PILs are the pyrrolidinium-based PILs containing nitrate, acetate or formate anions; the formate-based PILs containing diisopropylethylammonium, amilaminium, quinolinium, lutidinium or collidinium cations; and the pyrrolidinium alkylcarboxylates, [Pyrr][CnH2n+1COO] with n = 5–8. This study was performed in order to investigate the influence of molecular structures of the ions on the ionic conductivities in aqueous solutions. The ionic conductivities of the aqueous solutions are 2–30 times higher than the conductivities of pure PILs. The maximum in conductivity varies from ww=0.41???to???0.74 and is related to the nature of cations and anions. The molar conductance and the molar conductance at infinite dilution for (PIL + water) solutions are then determined. Self-diffusion coefficients of the twelve protic ionic liquids in water at infinite dilution and at 298.15 K are calculated by using the Nernst–Haskell, the original and the modified Wilke–Chang equations. These calculations show that similar values are obtained using the modified Wilke–Chang and the Nernst–Haskell equations. Finally, the effective hydrodynamic (or Stokes) radius of the PILs was determined by using the Stokes–Einstein equation. A linear relationship was established in order to predict this radius as a function of the anion alkyl chain length in the case of the pyrrolidinium alkylcarboxylates PILs.

Density and viscosity of several pure and water-saturated ionic liquids

Densities and viscosities were measured as a function of temperature for six ionic liquids (1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium ethylsulfate and butyltrimethylammonium bis(trifluoromethylsulfonyl)imide. The density and the viscosity were obtained using a vibrating tube densimeter from Anton Paar and a rheometer from Rheometrics Scientific at temperatures up to 393 K and 388 K with an accuracy of 10-3 g cm-3 and 1%, respectively. The effect of the presence of water on the measured values was also examined by studying both dried and water-saturated samples. A qualitative analysis of the evolution of density and viscosity with cation and anion chemical structures was performed. © The Royal Society of Chemistry 2006.

New Method for the Estimation of Viscosity of Pure and Mixtures of Ionic Liquids Based on the UNIFAC–VISCO Model

A modified UNIFAC–VISCO group contribution method was developed for the correlation and prediction of viscosity of ionic liquids as a function of temperature at 0.1 MPa. In this original approach, cations and anions were regarded as peculiar molecular groups. The significance of this approach comes from the ability to calculate the viscosity of mixtures of ionic liquids as well as pure ionic liquids. Binary interaction parameters for selected cations and anions were determined by fitting the experimental viscosity data available in literature for selected ionic liquids. The temperature dependence on the viscosity of the cations and anions were fitted to a Vogel–Fulcher–Tamman behavior. Binary interaction parameters and VFT type fitting parameters were then used to determine the viscosity of pure and mixtures of ionic liquids with different combinations of cations and anions to ensure the validity of the prediction method. Consequently, the viscosities of binary ionic liquid mixtures were then calculated by using this prediction method. In this work, the viscosity data of pure ionic liquids and of binary mixtures of ionic liquids are successfully calculated from 293.15 K to 363.15 K at 0.1 MPa. All calculated viscosity data showed excellent agreement with experimental data with a relative absolute average deviation lower than 1.7%.

Solvation dynamics of a quadrupolar solute in dipolar liquids

A microscopic calculation of solvation dynamics of dipolar and quadrupolar solutes in liquid water and acetonitrile is presented. The solvation is found to he biphasic. The calculated solvation time correlation function of ionic quadrupolar solute (K+) in water is in good agreement with re cent computer simulation results. Present study reveals some interesting aspects of quadrupolar solvation dynamics which differ significantly from that of ionic and dipolar solvation.

Self-similar breakup of near-inviscid liquids

The final stages of pinchoff and breakup of dripping droplets of near-inviscid Newtonian fluids are studied experimentally for pure water and ethanol. High-speed imaging and image analysis are used to determine the angle and the minimum neck size of the cone-shaped extrema of the ligaments attached to dripping droplets in the final microseconds before pinchoff. The angle is shown to steadily approach the value of 18.0 ±0.4, independently of the initial flow conditions or the type of breakup. The filament thins and necks following a τ2 /3 law in terms of the time remaining until pinchoff, regardless of the initial conditions. The observed behavior confirms theoretical predictions. © 2012 American Physical Society.

Self-similar breakup of near-inviscid liquids.

The final stages of pinchoff and breakup of dripping droplets of near-inviscid Newtonian fluids are studied experimentally for pure water and ethanol. High-speed imaging and image analysis are used to determine the angle and the minimum neck size of the cone-shaped extrema of the ligaments attached to dripping droplets in the final microseconds before pinchoff. The angle is shown to steadily approach the value of 18.0 ± 0.4°, independently of the initial flow conditions or the type of breakup. The filament thins and necks following a τ(2/3) law in terms of the time remaining until pinchoff, regardless of the initial conditions. The observed behavior confirms theoretical predictions.

The separation of Cerium(IV) from nitric acid solutions containing Thorium(IV) and Lanthanides(III) using pure [C(8)mim]PF6 as extracting phase

The extraction behavior of Ce(IV) along with Th(IV) and Ln(III) (Ln = Ce, Gd, Yb) nitrate by pure ionic liquid, [C(8)mim]PF6, was investigated. [C(8)mim]PF6 alone showed good extraction ability for Ce(IV), while it was slight for Th(IV) and negligible for Ln(III). The extraction behavior of Ce(IV) by [C(8)mim]PF6 was particularly studied, and the most probable extraction mechanism proposed was the anion exchange mechanism. Moreover, the stripping of Ce(IV) from IL phase was also investigated. The Ce(IV) in IL phase can be quantitatively recovered by water.

Preparation of colorless ionic liquids "on water" for spectroscopy

Although colorless ionic liquids (ILs) are most desirable, as synthesized they frequently bear color, despite appearing pure by most analytical techniques. It leads to some uncertainties and limits for the fundamental research and applications of ILs, such as spectroscopy. Using 1-butyl-3-methylimidazolium bromide (BMIMBr), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) and 1-hexyl-3-methylimidazolium bromide (HMIMBr) as models, we demonstrated that following classic preparing method except that the water was added as solvent, colorless ILs could be facilely prepared. Neither critical pre-treatment of starting materials and pre-cautions during the reaction nor time-consuming and costly post-decolor-purification was needed, The effects of "on water" reaction conditions on preparing colorless IL and the reason why using water as solvent could produce colorless ILs were also preliminary investigated.

Inorganic glasses, glass-forming liquids and amorphizing solids

Greaves, George; Sen, S., (2007) 'Inorganic glasses, glass-forming liquids and amorphizing solids', Advances in Physics 56(1) pp.1-166 RAE2008

Polyamorphism in aluminate liquids

McMillan, P. F., Wilson, M., Wilding, M. C. (2003). Polyamorphism in aluminate liquids. Journal of Physics: Condensed Matter, 15 (36), 6105-6121 RAE2008