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Equation agrees with measurements over wide concentration range. Plot of calculated values from equation and measured values show close match except at extremely low concentrations of electrolyte. Other equations do not match data as well and limited to dilute solutions.
The theories of diffusion-controlled dendritic crystallization will be reviewed briefly, along with recently published critical experiments on the kinetics and morphology of dendritic growth in pure substances. The influence of the gravitational body force on dendrite growth kinetics will be shown to be highly dependent on the growth orientation with respect to the gravity vector and on the level of the thermal supercooling. In fact, an abrupt transition occurs at a critical supercooling, above which diffusional transport dominates the growth process and below which convective transport dominates. Our most recent work on binary mixtures shows that dilute solute additions influence the crystallization process indirectly, by altering the interfacial stability, rather than by directly affecting the transport mode. Directions for future studies in this field will also be discussed.
A quantitative calculation of growth rates and tip radii is presented for dendrites growing in undercooled dilute solutions. Included in the calculations are the capillary corrections to the steady-state Ivantsov needle-crystal solutions. The results show good agreement with available experimental data and support the validity of the marginal-stability theory of dendritic growth.
The absorbing species responsible for the UV cloud features and pale yellow hue of the Venus clouds is presently suggested to be the carbon monoxide-polymer croconic acid, which strongly absorbs in the blue and near-UV. Laboratory absorption-coefficient measurements of a dilute solution of croconic acid in sulfuric acid are used as the bases of cloud-scattering models; the Venus planetary albedo's observed behavior in the blue and near-UV are noted to be qualitatively reproduced. Attention is given to a plausible croconic acid-production mechanism for the Venus cloudtop region.
A preliminary research program was conducted to demonstrate a new concept for additives to liquid lubricants. It was demonstrated that suspensions of o-phthalonitrile and a substituted 1,2-maleonitrile in mineral oil and dilute solutions of o-phthalonitrile and tetrafluoro-o-phthalonitrile extended the lifetime of bearings under boundary lubricating conditions. The solutions exhibited coefficients of friction under high loads of 0.02-0.03. These results were consistent with the hypothesis that these compounds react with the hot metal surface to form a planar lubricating film by means of a metal or metal oxide template reaction. Also, the adherence was very strong due to the chelating action of the planar macrocycles postulated to form under the experimental conditions.
Two types of emission behavior for Pt(II) complexes containing alpha-diimine ligands have been observed in dilute solution. If the complex also has weak field ligands such as chloride, ligand field (d-d) excited states become the lowest energy excited states. If only strong field ligands are present, a diimine 3(pi-pi/asterisk/) state becomes the lowest. In none of the cases studied did metal-to-ligand charge transfer excited state lie lowest.
Wet chemical techniques are described for treatment of YBa2Cu3O(7-x) surfaces, which result in the formation of native compounds known to have little or no reactivity to water. Suitable native compounds include CuI, BaSO4, CuS, Cu2S, YF3, and the oxalates. Formation of surface layers in which these nonreactive native compounds are major constituents is verified with X-ray photoelectron spectroscopy (XPS) measurements on YBa2Cu3O(7-x) films treated with dilute solutions of HI, H2SO4, Na2S, HF, or H2C2O4. No significant changes are observed in the XPS spectra when the sulfide, sulfate, or oxalate films are dipped in water, while the iodide and fluoride films show evidence of reaction with water. X-ray diffraction measurements show that the superconducting phase is absent in the sulfide film, but is unaffected by the oxalate and sulfate treatments.
Free shear flows, like those of mixing layers, are encountered in aerodynamics, in the atmosphere, and in the ocean as well as in many industrial applications such as flow reactors or combustion chambers. It is, therefore, crucial to understand the mechanisms governing the process of transition to turbulence in order to predict and control the evolution of the flow. Delaying transition to turbulence as far downstream as possible allows a gain in energy expenditure while accelerating the transition can be of interest in processes where high mixing is desired. Various methods, including the use of polymer additives, can be effective in controlling fluid flows. The drag reduction obtained by the addition of small amounts of high polymers has been an active area of research for the last three decades. It is now widely believed that polymer additives can affect the stability of a large variety of flows and that dilute solutions of these polymers have been shown to produce drag reductions of over 80 percent in internal flows and over 60 percent in external flows under a wide range of conditions. The major thrust of this work is to study the effects of polymer additives on the stability of the incompressible mixing layer through large scale numerical simulations. In particular, we focus on the two dimensional flow and examine how the presence of viscoelasticity may affect the typical structures of the flow, namely roll-up and pairing of vortices.
Fourier transform-infrared (FTIR) spectroscopy was used to examine films representative of stratospheric sulfuric acid aerosols. Thin films of sulfuric acid were formed in situ by the condensed phase reaction of SO3 with H2O. FTIR spectra show that the sulfuric acid films absorb water while cooling in the presence of water vapor. Using stratospheric water pressures, the most dilute solutions observed were greater than 40 wt % before simultaneous ice formation and sulfuric acid freezing occurred. FTIR spectra also revealed that the sulfuric acid films crystallized mainly as sulfuric acid tetrahydrate (SAT). Crystallization occurred either when the composition was about 60 wt% H2SO4 or after ice formed on the films at temperatures 1-4 K below the ice frost point. Finally, we determined that the melting point for SAT depended on the background water pressure and was 216-219 K in the presence of 4 x 10(exp -4) Torr H2O. Our results suggest that once frozen, sulfuric acid aerosols in the stratosphere are likely to melt at these temperatures, 30 K colder than previously thought.
The destruction of organic contaminants in waste water for closed systems, such as that of Space Station, is crucial due to the need for recycling the waste water. A co-current upflow bubble column using oxygen as the gas phase oxidant and packed with catalyst particles consisting of a noble metal on an alumina substrate is being developed for this process. The objective of this study is to develop a plug-flow model that will predict the performance of this three phase reactor system in destroying a multicomponent mixture of organic contaminants in water. Mass balances on a series of contaminants and oxygen in both the liquid and gas phases are used to develop this model. These mass balances incorporate the gas-to-liquid and liquid-to-particle mass transfer coefficients, the catalyst effectiveness factor, and intrinsic reaction rate. To validate this model, a bench scale reactor has been tested at Michigan Technological University at elevated pressures (50-83 psig,) and a temperature range of 200 to 290 F. Feeds consisting of five dilute solutions of ethanol (approx. 10 ppm), chlorobenzene (approx. 20 ppb), formaldehyde (approx. 100 ppb), dimethyl sulfoxide (DMSO approx. 300 ppb), and urea (approx. 20 ppm) in water were tested individually with an oxygen mass flow rate of 0.009 lb/h. The results from these individual tests were used to develop the kinetic parameter inputs necessary for the computer model. The computer simulated results are compared to the experimental data obtained for all 5 components run in a mixture on the differential test column for a range of reactor contact times.
Polymeric precursors to Si-C-O, SI-B-N and Si-C were evaluated for use as ceramic interfaces in ceramic matrix composites. Use of the preceramic polymers allows for easy dip coating of fibers from dilute solutions of a polymer, which are then pyrolyzed to obtain the ceramic. SCS-0 fibers (Textron Specialty Materials, Lowell, MA) were coated with polymers from three systems: polysilsesquioxanes, polyborosilazanes and polycarbosilanes. The polysilsesquioxane systems were shown to produce either silicon oxycarbide or silicon oxynitride, depending on the pyrolysis conditions, and demonstrated some promise in an RBSN (reaction-bonded silicon nitride) matrix model system. Polyborosilazanes were shown, in studies of bulk polymers, to give rise to oxidation resistant Si-B-N ceramics which remain amorphous to temperatures of 1600 C, and should therefore provide a low modulus interface. Polycarbosilanes produce amorphous carbon-rich Si-C materials which have demonstrated oxidation resistance.
The reaction of guanidine hydrochloride with cyanoacetaldehyde gives high yields (40-85%) of 2,4-diaminopyrimidine under the concentrated conditions of a drying lagoon model of prebiotic synthesis, in contrast to the low yields previously obtained under more dilute conditions. The prebiotic source of cyanoacetaldehyde, cyanoacetylene, is produced from electric discharges under reducing conditions. The effect of pH and concentration of guanidine hydrochloride on the rate of synthesis and yield of diaminopyrimidine were investigated, as well as the hydrolysis of diaminopyrimidine to cytosine, isocytosine, and uracil. Thiourea also reacts with cyanoacetaldehyde to give 2-thiocytosine, but the pyrimidine yields are much lower than with guanidine hydrochloride or urea. Thiocytosine hydrolyzes to thiouracil and cytosine and then to uracil. This synthesis would have been a significant prebiotic source of 2-thiopyrimidines and 5-substituted derivatives of thiouracil, many of which occur in tRNA. The applicability of these results to the drying lagoon model of prebiotic synthesis was tested by dry-down experiments where dilute solutions of cyanoacetaldehyde, guanidine hydrochloride, and 0.5 M NaCl were evaporated over varying periods of time. The yields of diaminopyrimidine varied from 1 to 7%. These results show that drying lagoons and beaches may have been major sites of prebiotic syntheses.
In order to simulate prebiotic synthetic processes on Europa and other ice-covered planets and satellites. we have investigated the prebiotic synthesis of organic compounds from dilute solutions of NH4CN frozen for 25 year at -20 and -78 C. In addition the aqueous products of spark discharge reactions from a reducing atmosphere were frozen for 5 years at -20%. We find that both adenine and guanine, as well as a simple set of amino acids dominated by glycine, are produced in substantial yields under these conditions. These results indicate that some of the key components necessary for the origin of life may have been available on Europa throughout its history and suggest that the circumstellar zone where life might arise may be m der than previously thought.
Doctinary overlays on the definition of life can effectively be avoided by focusing discussion on microorganisms, their vital processes, and their genetic pedigree. To reach beyond these present and highly advanced forms of life and to inquire about its origin it is necessary to consider the requirements imposed by the environment. These requirements include geophysically and geochemically acceptable conjectures for the generation of source compounds, their concentration from dilute solution, and their selective combination into functional biomolecules. For vital function these macromolecules require programming in the form of specific sequence motifs. This critical programming constitutes the scientifically least understood process in the origin of life. Once this stage has been surpassed the laws of Darwinian evolution can operate in ways that are understood and experimentally demonstrated.
Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.
In order to simulate prebiotic synthetic processes on Europa and other ice-covered planets and satellites, we have investigated the prebiotic synthesis of organic compounds from dilute solutions of NH4CN frozen for 25 years at -20 and -78 degrees C. In addition, the aqueous products of spark discharge reactions from a reducing atmosphere were frozen for 5 years at -20 degrees C. We find that both adenine and guanine, as well as a simple set of amino acids dominated by glycine, are produced in substantial yields under these conditions. These results indicate that some of the key components necessary for the origin of life may have been available on Europa throughout its history and suggest that the circumstellar zone where life might arise may be wider than previously thought.
Mucus plays an exceptionally wide range of important biological roles. It operates as a protective, exchange, and transport medium in the digestive, respiratory, and reproductive systems of humans and other vertebrates. Mucus is a polymer hydrogel. It is secreted as discrete packages (secretory granules) by specialized secretory cells. Mucus hydrogel is stored in a condensed state inside the secretory granules. Depending upon the architecture of their constituent macromolecules and on the composition of the solvent, polymer gels can form liquid crystalline microstructures, with orientational order being exhibited over optically resolvable distances. Individual mucin molecules consist of alternating rigid segments (heavily glycosylated; hydrophilic) and flexible segments (nonglycosylated; hydrophobic). Polymer molecules consisting of rigid units linked by flexible spacers are frequently associated with liquid crystalline behavior, which again raises the possibility that mucus could form anisotropic fluid phases. Suggestions that mucins may be self-associating in dilute solution have previously been challenged on the basis of sedimentation-equilibrium studies performed on mucus in which potential sites of association were competitively blocked with inhibitors. However, the formation of stable liquid crystalline phases does not depend on the existence of inter- or intramolecular associations; these phases can form on the basis of steric considerations alone.
We report the formation of a three-dimensionally ordered array of air bubbles of monodisperse pore size in a polymer film through a templating mechanism based on thermocapillary convection. Dilute solutions of a simple, coil-like polymer in a volatile solvent are cast on a glass slide in the presence of moist air flowing across the surface. Evaporative cooling and the generation of an ordered array of breath figures leads to the formation of multilayers of hexagonally packed water droplets that are preserved in the final, solid polymer film as spherical air bubbles. The dimensions of these bubbles can be controlled simply by changing the velocity of the airflow across the surface. When these three-dimensionally ordered macroporous materials have pore dimensions comparable to the wavelength of visible light, they are of interest as photonic band gaps and optical stop-bands.