Phase transfer and freezing processes investigated on acoustically levitated aqueous droplets

An acoustic trap was designed and constructed to investigate, on a microscale, physicochemical processes relevant to the troposphere, mainly focusing on the temperature range below 0 degrees C. Droplets ranging from 0.5 nL to 4 microliter (0.1 to 2 mm in diameter) were introduced into the cooled reaction chamber by means of a piezo-driven micro pump with a reproducibility better than 5%. Up-take of H2O2 from the gas phase by the levitated droplet was measured and calibrated by in-situ chemiluminescence. Freezing of stably positioned droplets was observed and documented by means of a microscope and a video camera; this demonstrated the usefulness of the technique for simulation and investigation of cloud processes. Ex-situ microanalysis of sub-microliter droplets by use of a fiber optic luminometer was also shown to be a suitable means of investigating relevant physicochemical processes on a micro scale.     

Investigations of the hygroscopic properties of ammonium sulfate and mixed ammonium sulfate and glutaric acid micro droplets by means of optical levitation and Raman spectroscopy

In the presented work an optical levitation technique performed by means of a focused laser beam, Mie and Raman spectroscopy have been utilized for measuring hygroscopic growth curves and composition of laboratory generated single ammonium sulfate (AS) and internally mixed ammonium sulfate-glutaric acid (GA) droplets in the micrometer range. The generated particles have been found to immediately supersaturate (above 45wt% for AS) at 297 K after capturing in the laser beam. Further increase of the relative humidity (RH) up to 85% does not dilute the droplets under the saturation point. A spontaneous hygroscopic growth takes place at 73.5-78% RH for pure AS. The particle grows with an average factor of 1.62 at the deliquescence relative humidity (DRH). Efflorescence of AS occurs at 43% RH with a corresponding concentration of more than 85wt%. Independent of the mixing ratios in ranges 25/75, 50/50, 75/25% AS/GA mixed particles don't exist as a metastable supersaturated solution droplets in the 35-85% RH range. Instead of growing with increasing relative humidity internally mixed particles build up a solid crystalline layer on the surface. This crystalline phase is not further influenced by ambient relative humidities.     

Equilibrium phase diagrams of aqueous mixtures of malonic acid and sulfate/ammonium salts

Tropospheric aerosols are usually complex mixtures of inorganic and organic components. Although the thermodynamic properties of inorganic aerosols have been widely studied, the effect of organics on such properties is still under discussion. In this study, solubility in water, water activity (a(w)) of aqueous solutions, deliquescence relative humidity (DRH), eutonic composition, and eutonic DRH were determined for bulk mixtures of malonic acid (MA) with ammonium sulfate (AS) and ammonium bisulfate (ABS) at 25 degrees C over the full range of composition (from 0 wt % to the solubility limit of the mixture components). The data were used to construct equilibrium phase diagrams, which show the phase of the mixtures as a function of total composition, dry mixture composition, water content, and ambient relative humidity (RH). This work complements previous reports on the thermodynamic properties of AS/MA mixtures because the range of concentrations investigated is larger than in any other published single study. On the other hand, this is the first report on the a(w), deliquescence, and water absorption of ABS/MA mixtures. The eutonic composition for AS/MA mixtures was found to be 66.8 MA dry wt % (MA dry wt % = MA mass x 100/(AS mass + MA mass) with a DRH of 0.437. The eutonic composition for the ABS/MA mixtures was lower than for the AS/MA mixtures: 20.9 MA dry wt % with a DRH of 0.327. Measured a(w) of liquid AS/MA and ABS/MA solutions is compared with an extended Zdanovskii-Stokes-Robinson expression, obtaining a good agreement (error < 5-6%). The expression was used to predict water uptake of mixtures and might be useful to interpret particle hygroscopic growth experiments. Comparison of the AS/MA and ABS/MA systems indicates that ABS reduces the DRH and enhances water uptake, relative to mixtures with AS. The results confirm that ambient particles containing sulfate and water-soluble organic compounds can remain liquid or partially liquid at very low ambient RH conditions, especially if the sulfate is not completely neutralized.     

聚乙二醇-硫酸铵双水相萃取次甲基蓝的研究

利用分光光度法研究了次甲基蓝在聚乙二醇-硫酸铵双水相体系的萃取行为,探索了质量配比(mPEc/m(NH4)2SO4)、温度和次甲基蓝的浓度对双水相及次甲基蓝萃取率(Y)的影响.实验表明:(1)在一定的温度和浓度下,随着mPEC/m(NH4)2SO4的减小,分配系数K( cup/clow)增加,萃取率Y略有减小;(2)在一定的质量配比和浓度下,分配系数K(cup/clow)随温度的升高而增大,但萃取率Y却基本保持不变;(3)在一定的质量配比和温度下,随着次甲基蓝浓度的增加,分配系数K(cup/clow)增大;萃取率Y略有增加.在mPEG/m( NH4) 2SO4为1.50∶1,c次甲基蓝=8.915×10-5mol/L、t=30℃的实验条件下,K(cup/clow)=22.14,萃取率(y)可达95.43％.     

Condensation and freezing of droplets on superhydrophobic surfaces

Superhydrophobic coatings are reported as promising candidates for anti-icing applications. Various studies have shown that as well as having ultra water repellency the surfaces have reduced ice adhesion and can delay water freezing. However, the structure or texture (roughness) of the superhydrophobic surface is subject to degradation during the thermocycling or wetting process. This degradation can impair the superhydrophobicity and the icephobicity of those coatings. In this review, a brief overview of the process of droplet freezing on superhydrophobic coatings is presented with respect to their potential in anti-icing applications. To support this discussion, new data is presented about the condensation of water onto physically decorated substrates, and the associated freezing process which impacts on the freezing of macroscopic droplets on the surface.     

Air-liquid interfaces of aqueous solutions containing ammonium and sulfate: spectroscopic and molecular dynamics studies

Investigations of the air-liquid interface of aqueous salt solutions containing ammonium (NH(4)(+)) and sulfate (SO(4)(2-)) ions were carried out using molecular dynamics simulations and vibrational sum frequency generation spectroscopy. The molecular dynamics simulations show that the predominant effect of SO(4)(2-) ions, which are strongly repelled from the surface, is to increase the thickness of the interfacial region. The vibrational spectra reported are in the O-H stretching region of liquid water. Isotropic Raman and ATR-FTIR (attenuated total reflection Fourier transform infrared) spectroscopies were used to study the effect of ammonium and sulfate ions on the bulk structure of water, whereas surface sum frequency generation spectroscopy was used to study the effect of these ions on the interfacial structure of water. Analysis of the interfacial and bulk vibrational spectra reveal that aqueous solutions containing SO(4)(2-) perturb the interfacial water structure differently than the bulk and, consistent with the molecular dynamics simulations, reveal an increase in the thickness of the interfacial region.     

醇-盐双水相技术去除废水中的酚类物质

A novel method for treatment of phenolic compounds in cokery wastewater by propyl-alcohol ammonium sulfate aqueous two-phase system was investigted.The effects of the amount of ammonium sulfate used,the amount of propyl-alcohol used,pH value on extractield was studied.Extraction was optimized using a L9(34)orthogonal test.The results indicated optimum extraction conditions were the amount of ammonium sulfate used of 18.0 g,the amount of propyl-alcohol used of 16 mL,and pH value of 3.0.A extraction yield of 99.37% was achived under optimum extraction conditions and via secondary extraction.     

硫酸铵的热分解

目前 ,关于各种无机酸铵盐的热分解情况都研究得比较清楚 ,但关于硫酸铵热分解情况的报道结果则不一致[1 - 7] 。本文对硫酸铵在各种温度下的常量热分解进行了研究 ,探讨其热分解机理 ,以利于对磷石膏 (主要成分为ＣａＳＯ4)的开发利用提供新的思路和方法[8] 。1　实验坩锅炉中热分解　约 1 0ｇ(ＮＨ4) 2 ＳＯ4置于恒重坩埚中 ,再放入坩埚炉中升温至设定温度 ,恒温0 5ｈ ,取出冷却 ,称重。并将坩埚中残余物用水溶解 ,测定水溶液中的Ｈ+、ＮＨ+4、ＳＯ2 -4 等离子的含量。其中ＮＨ+4含量采用甲醛法测定 ,ＳＯ2 -4 含量采用硫酸钡重量法测定…     

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.     

Precipitation of zinc ammonium phosphate from homogeneous solution

Urea hydrolysis has been employed to raise the pH for homogeneous precipitation of zinc ammonium phosphate. From 30 to 100 mg of zinc can conveniently be determined by this technique (relative standard deviation 0.2% for 89 mg). The interference of nickel was minimized by using ammonium tartrate as masking agent, but copper could not be effectively masked with the same tartrate. Ammonium tartrate obtained from a different source was found to mask the copper more effectively. Investigations showed that the latter tartrate contained an appreciable amount of ammonium oxalate.     

Precipitation of manganese ammonium phosphate from homogeneous solution

Precipitation of manganese, zinc and cadmium ammonium phosphates from homogeneous solution by decomposition of metal EDTA complexes by boiling with hydrogen peroxide in presence of phosphate has been investigated. Precipitation of Cd is not quantitative, but of Mn is complete in 2 hr, and of Zn in 6 hr.     

Experimental and theoretical investigation of the micellar-assisted solubilization of ibuprofen in aqueous media

Surfactants can be used to increase the solubility of poorly soluble drugs in water and to increase drug bioavailability. In this article, the aqueous solubilization of the nonsteroidal, antiinflammatory drug ibuprofen is studied experimentally and theoretically in micellar solutions of anionic (sodium dodecyl sulfate, SDS), cationic (dodecyltrimethylammonium bromide, DTAB), and nonionic (dodecyl octa(ethylene oxide), C12E8) surfactants possessing the same hydrocarbon "tail" length but differing in their hydrophilic headgroups. We find that, for these three surfactants, the aqueous solubility of ibuprofen increases linearly with increasing surfactant concentration. In particular, we observed a 16-fold increase in the solubility of ibuprofen relative to that in the aqueous buffer upon the addition of 80 mM DTAB and 80 mM C12E8 but only a 5.5-fold solubility increase upon the addition of 80 mM SDS. The highest value of the molar solubilization capacity (chi) was obtained for DTAB (chi = 0.97), followed by C12E8 (chi = 0.72) and finally by SDS (chi = 0.23). A recently developed computer simulation/molecular-thermodynamic modeling approach was extended to predict theoretically the solubilization behavior of the three ibuprofen/surfactant mixtures considered. In this modeling approach, molecular-dynamics (MD) simulations were used to identify which portions of ibuprofen are exposed to water (hydrated) in a micellar environment by simulating a single ibuprofen molecule at an oil/water interface (modeling the micelle core/water interface). On the basis of this input, molecular-thermodynamic modeling was then implemented to predict (i) the micellar composition as a function of surfactant concentration, (ii) the aqueous solubility of ibuprofen as a function of surfactant concentration, and (iii) the molar solubilization capacity (chi). Our theoretical results on the solubility of ibuprofen in aqueous SDS and C12E8 surfactant solutions are in good agreement with the experimental data. The ibuprofen solubility in aqueous DTAB solutions was somewhat overpredicted because of challenges associated with accurately modeling the strong electrostatic interactions between the anionic ibuprofen and the cationic DTAB. Our results indicate that computer simulations of ibuprofen at a flat oil/water interface can be used to obtain accurate information about the hydrated and the unhydrated portions of ibuprofen in a micellar environment. This information can then be used as input to a molecular-thermodynamic model of self-assembly to successfully predict the aqueous solubilization behavior of ibuprofen in the three surfactant systems studied.     

Thermodynamics of aqueous sodium sulfate

The activity coefficient of saturated aqueous Na₂SO₄ is calculated from the properties of the solid and the infinitely dilute solution as well as the solubility. These values are compared with those given by the equation of Rogers and Pitzer which is based on the measured dependence of heat capacity upon molality together with other solution properties at low temperature. Excellent agreement is found from 30 to 280°C. Consequently the equation of Rogers and Pitzer is given an extended range of validity to saturated molality and to 280°C. The trend of solubility with temperature is discussed in relation to the C_p of solution.     

Treatment of ferric sulfate waste solutions for the production of ammonium ferric sulfate dodecahydrate

The process of precipitation of ammonium ferric sulfate dodecahydrate (NH₄Fe(SO₄)₂·12H₂O) from waste solutions, obtained during autoclave oxidation of pyrite concentrate has been studied. A special feature of these solutions is the high concentration of Fe(III) ions (>60 g L^–1) and sulfuric acid (> 61 g L^–1). Based on comprehensive laboratory tests, the study determined the optimal conditions for the precipitation process of ammonium ferric sulfate dodecahydrate (AFS) by salting out with ammonium sulfate: reagent excess (100% over stoichiometric, temperature 276 K, time 1 h). The process should be conducted under continuous slow stirring which would not allow forming of large crystals that are difficult to remove from the reactor. The test work confirmed that high quality crystals can be produced by prior oxidation of Fe(II) to Fe(III) ions using hydrogen peroxide and copper removal from the solution.     

Heterogeneous reactivity of chlorine atoms with ammonium sulfate and ammonium nitrate particles

In this laboratory study, model particles of ammonium sulfate (AS) and ammonium nitrate (AN) were exposed to chlorine atoms and uptake experiments were performed in a coated wall flow tube reactor coupled to a molecular beam mass spectrometer. The reactive surfaces were prepared by coating the inner surface of the reactor using two different methods: either by depositing size-selected particles on the halocarbon wax or by spray depositing thin films using a constant output atomizer. The observed uptake coefficients vary for (NH(4))(2)SO(4), ranging from γ(Cl)(AS)≈ 1 × 10(-3) for size-selected particles to γ(Cl)(AS)≈ 6 × 10(-2) for thin films prepared by spray. An uptake coefficient of γ(Cl)(AN)≈ 2.5 × 10(-3) of Cl˙ on size-selected NH(4)NO(3) particles was measured. A heterogeneous recombination of Cl atoms to from Cl(2) molecules was observed for the two surfaces. Furthermore, an ageing process was observed for AS particles, this phenomenon leading to the formation of new chlorine species on the solid substrate.     

Raman and infrared spectroscopic investigation of contact ion pair formation in aqueous cadmium sulfate solutions

Raman and IR data for aqueous CdSO₄ and (NH₄)₂SO₄ solutions have been recorded over broad concentration and temperature ranges. Whereas the v₁-SO ₄ ^2– band profile is symmetrical in (NH₄)₂SO₄ solutions, in CdSO₄ solutions a shoulder appears on the high frequency side which increases in intensity with increasing concentration and temperature. The molar scattering coefficient of the v₁-SO ₄ ^2– band is the same for all forms of sulfate in (NH₄)₂SO₄ and CdSO₄ solutions and is independent of temperature up to 99°C. The high frequency shoulder is attributed to the formation of a contact ion pair [Cd²⁺OSO ₃ ^2– ] (11 associate). Also the v₃-SO ₄ ^2– antisymmetric stretching mode shows a splitting in the CdSO₄ solution. Further spectroscopic evidence for contact ion pair formation is provided by IR spectroscopy. No higher associates or anionic complexes are required to interpret the spectroscopic data. The degree of association has been measured as a function of concentration and temperature. The thermodynamic association constant, K_A=0.15±0.05 kg-mol^–1 at 25°C is estimated from the Raman data by an extrapolation procedure by taking account of the activity coefficients. Values are reported for the activity coefficient of the ion pair. From the Raman temperature dependence studies, the enthalpy of formation for the contact ion pair is estimated to be 10±1 kJ-mol^–1.