Geochemistry and resonance ionization of platinum-group elements

Experimental studies were conducted with the goals of 1) determining the origin of Pt- group element (PGE) alloys and associated mineral assemblages in refractory inclusions from meteorites and 2) developing a new ultrasensitive method for the in situ chemical and isotopic analysis of PGE. A general review of the geochemistry and cosmochemistry of the PGE is given, and specific research contributions are presented within the context of this broad framework.

An important step toward understanding the cosmochemistry of the PGE is the determination of the origin of POE-rich metallic phases (most commonly εRu-Fe) that are found in Ca, AJ-rich refractory inclusions (CAI) in C3V meteorites. These metals occur along with γNi-Fe metals, Ni-Fe sulfides and Fe oxides in multiphase opaque assemblages. Laboratory experiments were used to show that the mineral assemblages and textures observed in opaque assemblages could be produced by sulfidation and oxidation of once homogeneous Ni-Fe-PGE metals. Phase equilibria, partitioning and diffusion kinetics were studied in the Ni-Fe-Ru system in order to quantify the conditions of opaque assemblage formation. Phase boundaries and tie lines in the Ni-Fe-Ru system were determined at 1273, 1073 and 873K using an experimental technique that allowed the investigation of a large portion of the Ni-Fe-Ru system with a single experiment at each temperature by establishing a concentration gradient within which local equilibrium between coexisting phases was maintained. A wide miscibility gap was found to be present at each temperature, separating a hexagonal close-packed εRu-Fe phase from a face-centered cubic γNi-Fe phase. Phase equilibria determined here for the Ni-Fe-Ru system, and phase equilibria from the literature for the Ni-Fe-S and Ni-Fe-O systems, were compared with analyses of minerals from opaque assemblages to estimate the temperature and chemical conditions of opaque assemblage formation. It was determined that opaque assemblages equilibrated at a temperature of ~770K, a sulfur fugacity 10 times higher than an equilibrium solar gas, and an oxygen fugacity 10⁶ times higher than an equilibrium solar gas.

Diffusion rates between -γNi-Fe and εRu-Fe metal play a critical role in determining the time (with respect to CAI petrogenesis) and duration of the opaque assemblage equilibration process. The diffusion coefficient for Ru in Ni (D^Ru_Ni) was determined as an analog for the Ni-Fe-Ru system by the thin-film diffusion method in the temperature range of 1073 to 1673K and is given by the expression:

D^Ru_Ni (cm² sec^-1) = 5.0(±0.7) x 10^-3 exp(-2.3(±0.1) x 10¹² erg mole^-1/RT) where R is the gas constant and T is the temperature in K. Based on the rates of dissolution and exsolution of metallic phases in the Ni-Fe-Ru system it is suggested that opaque assemblages equilibrated after the melting and crystallization of host CAI during a metamorphic event of ≥ 10³ years duration. It is inferred that opaque assemblages originated as immiscible metallic liquid droplets in the CAI silicate liquid. The bulk compositions of PGE in these precursor alloys reflects an early stage of condensation from the solar nebula and the partitioning of V between the precursor alloys and CAI silicate liquid reflects the reducing nebular conditions under which CAI were melted. The individual mineral phases now observed in opaque assemblages do not preserve an independent history prior to CAI melting and crystallization, but instead provide important information on the post-accretionary history of C3V meteorites and allow the quantification of the temperature, sulfur fugacity and oxygen fugacity of cooling planetary environments. This contrasts with previous models that called upon the formation of opaque assemblages by aggregation of phases that formed independently under highly variable conditions in the solar nebula prior to the crystallization of CAI.

Analytical studies were carried out on PGE-rich phases from meteorites and the products of synthetic experiments using traditional electron microprobe x-ray analytical techniques. The concentrations of PGE in common minerals from meteorites and terrestrial rocks are far below the ~100 ppm detection limit of the electron microprobe. This has limited the scope of analytical studies to the very few cases where PGE are unusually enriched. To study the distribution of PGE in common minerals will require an in situ analytical technique with much lower detection limits than any methods currently in use. To overcome this limitation, resonance ionization of sputtered atoms was investigated for use as an ultrasensitive in situ analytical technique for the analysis of PGE. The mass spectrometric analysis of Os and Re was investigated using a pulsed primary Ar⁺ ion beam to provide sputtered atoms for resonance ionization mass spectrometry. An ionization scheme for Os that utilizes three resonant energy levels (including an autoionizing energy level) was investigated and found to have superior sensitivity and selectivity compared to nonresonant and one and two energy level resonant ionization schemes. An elemental selectivity for Os over Re of ≥ 10³ was demonstrated. It was found that detuning the ionizing laser from the autoionizing energy level to an arbitrary region in the ionization continuum resulted in a five-fold decrease in signal intensity and a ten-fold decrease in elemental selectivity. Osmium concentrations in synthetic metals and iron meteorites were measured to demonstrate the analytical capabilities of the technique. A linear correlation between Os⁺ signal intensity and the known Os concentration was observed over a range of nearly 10⁴ in Os concentration with an accuracy of ~ ±10%, a millimum detection limit of 7 parts per billion atomic, and a useful yield of 1%. Resonance ionization of sputtered atoms samples the dominant neutral-fraction of sputtered atoms and utilizes multiphoton resonance ionization to achieve high sensitivity and to eliminate atomic and molecular interferences. Matrix effects should be small compared to secondary ion mass spectrometry because ionization occurs in the gas phase and is largely independent of the physical properties of the matrix material. Resonance ionization of sputtered atoms can be applied to in situ chemical analysis of most high ionization potential elements (including all of the PGE) in a wide range of natural and synthetic materials. The high useful yield and elemental selectivity of this method should eventually allow the in situ measurement of Os isotope ratios in some natural samples and in sample extracts enriched in PGE by fire assay fusion.

Phase equilibria and diffusion experiments have provided the basis for a reinterpretation of the origin of opaque assemblages in CAI and have yielded quantitative information on conditions in the primitive solar nebula and cooling planetary environments. Development of the method of resonance ionization of sputtered atoms for the analysis of Os has shown that this technique has wide applications in geochemistry and will for the first time allow in situ studies of the distribution of PGE at the low concentration levels at which they occur in common minerals.

Part I. Kinetics of coarsening of the gamma-prime precipitate in nickel-silicon alloys. Part II. Rate of crystallization of an amorphous Fe-P-C alloy

The coarsening kinetics of Ni₃ Si(γ') precipitate in a binary Ni-Si alloy containing 6.5 wt. % silicon was studied by magnetic techniques and transmission electronmicroscopy. A calibration curve was established to determine the concentration of silicon in the matrix. The variation of the Si content of the Ni-rich matrix as a function of time follows Lifshitz and Wagner theory for diffusion controlled coarsening phenomena. The estimated values of equilibrium solubility of silicon in the matrix represent the true coherent equilibrium solubilities.

The experimental particle-size distributions and average particle size were determined from dark field electron micrographs. The average particle size varies linearly with t^-1/3 as suggested by Lifshitz and Wagner. The experimental distributions of particle sizes differ slightly from the theoretical curve at the early stages of aging, but the agreement is satisfactory at the later stages. The values of diffusion coefficient of silicon, interfacial free energy and activation energy were calculated from the results of coarsening kinetics. The experimental value of effective diffusion coefficient is in satisfactory agreement with the value predicted by the application of irreversible the rmodynamics to the process of volume constrained growth of coherent precipitate during coarsening. The coherent γ' particles in Ni-Sialloy unlike those in Ni-Al and Ni-Ti seem to lose coherency at high temperature. A mechanism for the formation of semi-coherent precipitate is suggested.

Development of Asymmetric Protonation Reactions for the Synthesis of Indoline Alkaloids

Nitrogen-containing heterocycles, such as indolines and pyrroloindolines, are prevalent in a variety of diverse natural products, many of which exhibit remarkable biological activities. These frameworks have inspired innovative research aimed at discovering novel methods for their stereoselective preparation.

We have developed an enantioselective synthesis of pyrroloindolines based on a formal (3 + 2) cycloaddition of indoles and 2-amidoacrylates. This reaction is promoted by (R)-BINOL•SnCl₄; this complex is a Lewis acid-assisted Brønsted acid that effects a highly face-selective catalyst-controlled protonation of an enolate. Mechanistic studies also determined that the initial product of this reaction is an indolinium ion, which upon aqueous workup undergoes cyclization to the pyrroloindoline.

Based on this result, we investigated alternative nucleophiles to trap the indolinium ion. First, addition of sodium borohydride to the optimized reaction conditions yields indoline-containing amino acid derivatives.

Next, carbon nucleophiles were explored. Indole substrates incorporating a tethered alkene were exposed to the conditions for the formal (3 + 2) cycloaddition, resulting in a conjugate addition/asymmetric protonation/Prins cyclization cascade. In this transformation, the indolinium ion is attacked by the olefin, and the resulting carbocation is quenched by a chloride ion. Zirconium tetrachloride was found to be the optimal Lewis acid. Stoichiometric proton and chloride sources were also found to be crucial for reactivity.

A quantitative investigation of the solar modulation of cosmic-ray protons and helium nuclei

The differential energy spectra of cosmic-ray protons and He nuclei have been measured at energies up to 315 MeV/nucleon using balloon- and satellite-borne instruments. These spectra are presented for solar quiet times for the years 1966 through 1970. The data analysis is verified by extensive accelerator calibrations of the detector systems and by calculations and measurements of the production of secondary protons in the atmosphere.

The spectra of protons and He nuclei in this energy range are dominated by the solar modulation of the local interstellar spectra. The transport equation governing this process includes as parameters the solar-wind velocity, V, and a diffusion coefficient, K(r,R), which is assumed to be a scalar function of heliocentric radius, r, and magnetic rigidity, R. The interstellar spectra, j_D, enter as boundary conditions on the solutions to the transport equation. Solutions to the transport equation have been calculated for a broad range of assumed values for K(r,R) and j_D and have been compared with the measured spectra.

It is found that the solutions may be characterized in terms of a dimensionless parameter, ψ(r,R) = ^∞∫_r V dr'/(K(r',R). The amount of modulation is roughly proportional to ψ. At high energies or far from the Sun, where the modulation is weak, the solution is determined primarily by the value of ψ (and the interstellar spectrum) and is not sensitive to the radial dependence of the diffusion coefficient. At low energies and for small r, where the effects of adiabatic deceleration are found to be large, the spectra are largely determined by the radial dependence of the diffusion coefficient and are not very sensitive to the magnitude of ψ or to the interstellar spectra. This lack of sensitivity to j_D implies that the shape of the spectra at Earth cannot be used to determine the interstellar intensities at low energies.

Values of ψ determined from electron data were used to calculate the spectra of protons and He nuclei near Earth. Interstellar spectra of the form j_D α (W - 0.25m)^-2.65 for both protons and He nuclei were found to yield the best fits to the measured spectra for these values of ψ, where W is the total energy and m is the rest energy. A simple model for the diffusion coefficient was used in which the radial and rigidity dependence are separable and K is independent of radius inside a modulation region which has a boundary at a distance D. Good agreement was found between the measured and calculated spectra for the years 1965 through 1968, using typical boundary distances of 2.7 and 6.1 A.U. The proton spectra observed in 1969 and 1970 were flatter than in previous years. This flattening could be explained in part by an increase in D, but also seemed to require that a noticeable fraction of the observed protons at energies as high at 50 to 100 MeV be attributed to quiet-time solar emission. The turnup in the spectra at low energies observed in all years was also attributed to solar emission. The diffusion coefficient used to fit the 1965 spectra is in reasonable agreement with that determined from the power spectra of the interplanetary magnetic field (Jokipii and Coleman, 1968). We find a factor of roughly 3 increase in ψ from 1965 to 1970, corresponding to the roughly order of magnitude decrease in the proton intensity at 250 MeV. The change in ψ might be attributed to a decrease in the diffusion coefficient, or, if the diffusion coefficient is essentially unchanged over that period (Mathews et al., 1971), might be attributed to an increase in the boundary distance, D.

Kinetics and mechanisms of adsorption of Escherichia coli bacteriophage T_4 to activated carbon

A study was conducted on the adsorption of Escherichia coli bacteriophage T₄ to activated carbon. Preliminary adsorption experiments were also made with poliovirus Type III. The effectiveness of such adsorbents as diatomaceous earth, Ottawa sand, and coconut charcoal was also tested for virus adsorption.

The kinetics of adsorption were studied in an agitated solution containing virus and carbon. The mechanism of attachment and site characteristics were investigated by varying pH and ionic strength and using site-blocking reagents.

Plaque assay procedures were developed for bacteriophage T₄ on Escherichia coli cells and poliovirus Type III on monkey kidney cells. Factors influencing the efficiency of plaque formation were investigated.

The kinetics of bacteriophage T₄ adsorption to activated carbon can be described by a reversible second-order equation. The reaction order was first order with respect to both virus and carbon concentration. This kinetic representation, however, is probably incorrect at optimum adsorption conditions, which occurred at a pH of 7.0 and ionic strength of 0.08. At optimum conditions the adsorption rate was satisfactorily described by a diffusion-limited process. Interpretation of adsorption data by a development of the diffusion equation for Langmuir adsorption yielded a diffusion coefficient of 12 X 10^-8 cm²/sec for bacteriophage T₄. This diffusion coefficient is in excellent agreement with the accepted value of 8 X 10^-8 cm²/sec. A diffusion-limited theory may also represent adsorption at conditions other than the maximal. A clear conclusion on the limiting process cannot be made.

Adsorption of bacteriophage T₄ to activated carbon obeys the Langmuir isotherm and is thermodynamically reversible. Thus virus is not inactivated by adsorption. Adsorption is unimolecular with very inefficient use of the available carbon surface area. The virus is probably completely excluded from pores due to its size.

Adsorption is of a physical nature and independent of temperature. Attraction is due to electrostatic forces between the virus and carbon. Effects of pH and ionic strength indicated that carboxyl groups, amino groups, and the virus's tail fibers are involved in the attachment of virus to carbon. The active sites on activated carbon for adsorption of bacteriophage T₄ are carboxyl groups. Adsorption can be completely blocked by esterifying these groups.

Polaron hopping in olivine phosphates studied by nuclear resonant scattering

Valence fluctuations of Fe²⁺ and Fe³⁺ were studied in a solid solution of Li_xFePO₄ by nuclear resonant forward scattering of synchrotron x rays while the sample was heated in a diamond-anvil pressure cell. The spectra acquired at different temperatures and pressures were analyzed for the frequencies of valence changes using the Blume-Tjon model of a system with a fluctuating Hamil- tonian. These frequencies were analyzed to obtain activation energies and an activation volume for polaron hopping. There was a large suppression of hopping frequency with pressure, giving an anomalously large activation volume. This large, positive value is typical of ion diffusion, which indicates correlated motions of polarons, and Li⁺ ions that alter the dynamics of both.

In a parallel study of Na_xFePO₄, the interplay between sodium ordering and electron mobility was investigated using a combination of synchrotron x-ray diffraction and nuclear resonant scattering. Conventional Mossbauer spectra were collected while the sample was heated in a resistive furnace. An analysis of the temperature evolution of the spectral shapes was used to identify the onset of fast electron hopping and determine the polaron hopping rate. Synchrotron x-ray diffraction measurements were carried out in the same temperature range. Reitveld analysis of the diffraction patterns was used to determine the temperature of sodium redistribution on the lattice. The diffraction analysis also provides new information about the phase stability of the system. The temperature evolution of the iron site occupancies from the Mossbauer measurements, combined with the synchrotron diffraction results give strong evidence for a relationship between the onset of fast electron dynamics and the redistribution of sodium in the lattice.

Measurements of activation barriers for polaron hopping gave fundamental insights about the correlation between electronic carriers and mobile ions. This work established that polaron-ion interactions can alter the local dynamics of electron and ion transport. These types of coupled processes may be common in many materials used for battery electrodes, and new details concerning the influence of polaron-ion interactions on the charge dynamics are relevant to optimizing their electrochemical performance.

On the transport properties of fluid-particle flow

The hydrodynamic forces acting on a solid particle in a viscous, incompressible fluid medium at low Reynolds number flow is investigated mathematically as a prerequisite to the understanding of transport processes in two-phase flow involving solid particles and fluid. Viscous interaction between a small number of spherical particles and continuous solid boundaries as well as fluid interface are analyzed under a “point-force” approximation. Non-spherical and elastic spherical particles in a simple shear flow area are then considered. Non-steady motion of a spherical particle is briefly touched upon to illustrate the transient effect of particle motion.

A macroscopic continuum description of particle-fluid flow is formulated in terms of spatial averages yielding a set of particle continuum and bulk fluid equations. Phenomenological formulas describing the transport processes in a fluid medium are extended to cases where the volume concentration of solid particles is sufficiently high to exert an important influence. Hydrodynamic forces acting on a spherical solid particle in such a system, e.g. drag, torque, rotational coupling force, and viscous collision force between streams of different sized particles moving relative to each other are obtained. Phenomenological constants, such as the shear viscosity coefficient, and the diffusion coefficient of the bulk fluid, are found as a function of the material properties of the constituents of the two-phase system and the volume concentration of solid. For transient heat conduction phenomena, it is found that the introduction of a complex conductivity for the bulk fluid permits a simple mathematical description of this otherwise complicated process. The rate of heat transfer between particle continuum and bulk fluid is also investigated by means of an Oseen-type approximation to the energy equation.

Solar flare particle propagation--comparison of a new analytic solution with spacecraft measurements

A new analytic solution has been obtained to the complete Fokker-Planck equation for solar flare particle propagation including the effects of convection, energy-change, corotation, and diffusion with ĸ_r = constant and ĸ_Ɵ ∝ r². It is assumed that the particles are injected impulsively at a single point in space, and that a boundary exists beyond which the particles are free to escape. Several solar flare particle events have been observed with the Caltech Solar and Galactic Cosmic Ray Experiment aboard OGO-6. Detailed comparisons of the predictions of the new solution with these observations of 1-70 MeV protons show that the model adequately describes both the rise and decay times, indicating that ĸ_r = constant is a better description of conditions inside 1 AU than is ĸ_r ∝ r. With an outer boundary at 2.7 AU, a solar wind velocity of 400 km/sec, and a radial diffusion coefficient ĸ_r ≈ 2-8 x 10²⁰ cm²/sec, the model gives reasonable fits to the time-profile of 1-10 MeV protons from "classical" flare-associated events. It is not necessary to invoke a scatter-free region near the sun in order to reproduce the fast rise times observed for directly-connected events. The new solution also yields a time-evolution for the vector anisotropy which agrees well with previously reported observations.

In addition, the new solution predicts that, during the decay phase, a typical convex spectral feature initially at energy T_o will move to lower energies at an exponential rate given by T_KINK = T_oexp(-t/Ƭ_KINK). Assuming adiabatic deceleration and a boundary at 2.7 AU, the solution yields Ƭ_KINK ≈ 100h, which is faster than the measured ~200h time constant and slower than the adiabatic rate of ~78h at 1 AU. Two possible explanations are that the boundary is at ~5 AU or that some other energy-change process is operative.

Path-integral and Coarse-graining Strategies for Complex Molecular Phenomena

Molecular simulation provides a powerful tool for connecting molecular-level processes to physical observables. However, the facility to make those connections relies upon the application and development of theoretical methods that permit appropriate descriptions of the systems or processes to be studied. In this thesis, we utilize molecular simulation to study and predict two phenomena with very different theoretical challenges, beginning with (1) lithium-ion transport behavior in polymers and following with (2) equilibrium isotope effects with relevance to position-specific and clumped isotope studies. In the case of ion transport in polymers, there is motivation to use molecular simulation to provide guidance in polymer electrolyte design, but the length and timescales relevant for ion diffusion in polymers preclude the use of direct molecular dynamics simulation to compute ion diffusivities in more than a handful of candidate systems. In the case of equilibrium isotope effects, the thermodynamic driving forces for isotopic fractionation are often fundamentally quantum mechanical in nature, and the high precision of experimental instruments demands correspondingly accurate theoretical approaches. Herein, we describe respectively coarse-graining and path-integral strategies to address outstanding questions in these two subject areas.

Temperature effects on the activity coefficient of the bicarbonate ion

Natural waters may be chemically studied as mixed electrolyte solutions. Some important equilibrium properties of natural waters are intimately related to the activity-concentration ratios (i.e., activity coefficients) of the ions in solution. An Ion Interaction Model, which is based on Pitzer's (1973) thermodynamic model, is proposed in this dissertation. The proposed model is capable of describing the activity coefficient of ions in mixed electrolyte solutions. The effects of temperature on the equilibrium conditions of natural waters and on the activity coefficients of the ions in solution, may be predicted by means of the Ion Interaction Model presented in this work.

The bicarbonate ion, HCO₃^-, is commonly found in natural waters. This anion plays an important role in the chemical and thermodynamic properties of water bodies. Such properties are usually directly related to the activity coefficient of HCO₃^- in solution. The Ion Interaction Model, as proposed in this dissertation, is used to describe indirectly measured activity coefficients of HCO₃^- in mixed electrolyte solutions.

Experimental pH measurements of MCl-MHCO₃ and MCl-H₂CO₃ solutions at 25°C (where M = K⁺, Na⁺, NH₄⁺, Ca²⁺ or Mg²⁺) are used in this dissertation to evaluate indirectly the MHCO₃ virial coefficients. Such coefficients permit the prediction of the activity coefficient of HCO₃^- in mixed electrolyte solutions. The Ion Interaction Model is found to be an accurate method for predicting the activity coefficient of HCO₃^- within the experimental ionic strengths (0.2 to 3.0 m). The virial coefficients of KHCO₃ and NaHCO₃ and their respective temperature variations are obtained from similar experimental measurements at 10° and 40°C. The temperature effects on the NH₄HCO₃, Ca(HCO₃)₂, and Mg(HCO₃)₂ virial coefficients are estimated based on these results and the temperature variations of the virial coefficients of 40 other electrolytes.

Finally, the Ion Interaction Model is utilized to solve various problems of water chemistry where bicarbonate is present in solution.

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

Enhanced Thermoelectric Performance at the Superionic Phase Transitions of Mixed Ion-Electron Conducting Materials

The quality of a thermoelectric material is judged by the size of its temperature de- pendent thermoeletric-figure-of-merit (zT ). Superionic materials, particularly Zn₄Sb₃ and Cu₂Se, are of current interest for the high zT and low thermal conductivity of their disordered, superionic phase. In this work it is reported that the super-ionic materials Ag₂Se, Cu₂Se and Cu_1.97Ag_0.03Se show enhanced zT in their ordered, normal ion-conducting phases. The zT of Ag₂Se is increased by 30% in its ordered phase as compared to its disordered phase, as measured just below and above its first order phase transition. The zT ’s of Cu₂Se and Cu_1.97Ag_0.03Se both increase by more than 100% over a 30 K temperatures range just below their super-ionic phase transitions. The peak zT of Cu₂Se is 0.7 at 406 K and of Cu_1.97Ag_0.03Se is 1.0 at 400 K. In all three materials these enhancements are due to anomalous increases in their Seebeck coefficients, beyond that predicted by carrier concentration measurements and band structure modeling. As the Seebeck coefficient is the entropy transported per carrier, this suggests that there is an additional quantity of entropy co-transported with charge carriers. Such co-transport has been previously observed via co-transport of vibrational entropy in bipolaron conductors and spin-state entropy in Na_xCo₂O₄. The correlation of the temperature profile of the increases in each material with the nature of their phase transitions indicates that the entropy is associated with the thermodynamcis of ion-ordering. This suggests a new mechanism by which high thermoelectric performance may be understood and engineered.