Salicylaldehyde hydrazones: buttressing of outer sphere hydrogen-bonding and copper-extraction properties

Salicylaldehyde hydrazones are weaker copper extractants than their oxime derivatives, which are used in hydrometallurgical processes to recover ~20 % of the world’s copper. Their strength, based on the extraction equilibrium constant Ke, can be increased by nearly three orders of magnitude by incorporating electron-withdrawing or hydrogen-bond acceptor groups (X) ortho to the phenolic OH group of the salicylaldehyde unit. Density functional theory calculations suggest that the effects of the 3-X substituents arise from a combination of their influence on the acidity of the phenol in the pH-dependent equilibrium, Cu2+ + 2Lorg ⇌ [Cu(L–H)2]org + 2H+, and on their ability to ‘buttress’ interligand hydrogen bonding by interacting with the hydrazone N–H donor group. X-ray crystal structure determination and computed structures indicate that in both the solid state and the gas phase, coordinated hydrazone groups are less planar than coordinated oximes and this has an adverse effect on intramolecular hydrogen-bond formation to the neighbouring phenolate oxygen atoms

Fast and Accurate Coarsening Simulation with an Unconditionally Stable Time Step

We present Cahn-Hilliard and Allen-Cahn numerical integration algorithms that are unconditionally stable and so provide significantly faster accuracy-controlled simulation. Our stability analysis is based on Eyre's theorem and unconditional von Neumann stability analysis, both of which we present. Numerical tests confirm the accuracy of the von Neumann approach, which is straightforward and should be widely applicable in phase-field modeling. We show that accuracy can be controlled with an unbounded time step Delta-t that grows with time t as Delta-t ~ t^alpha. We develop a classification scheme for the step exponent alpha and demonstrate that a class of simple linear algorithms gives alpha=1/3. For this class the speed up relative to a fixed time step grows with the linear size of the system as N/log N, and we estimate conservatively that an 8192^2 lattice can be integrated 300 times faster than with the Euler method.Comment: 14 pages, 6 figure

The California-Kepler Survey. II. Precise Physical Properties of 2025 Kepler Planets and Their Host Stars

We present stellar and planetary properties for 1305 Kepler Objects of Interest (KOIs) hosting 2025 planet candidates observed as part of the California-Kepler Survey. We combine spectroscopic constraints, presented in Paper I, with stellar interior modeling to estimate stellar masses, radii, and ages. Stellar radii are typically constrained to 11%, compared to 40% when only photometric constraints are used. Stellar masses are constrained to 4%, and ages are constrained to 30%. We verify the integrity of the stellar parameters through comparisons with asteroseismic studies and Gaia parallaxes. We also recompute planetary radii for 2025 planet candidates. Because knowledge of planetary radii is often limited by uncertainties in stellar size, we improve the uncertainties in planet radii from typically 42% to 12%. We also leverage improved knowledge of stellar effective temperature to recompute incident stellar fluxes for the planets, now precise to 21%, compared to a factor of two when derived from photometry.Comment: 13 pages, 4 figures, 4 tables, accepted for publication in AJ; full versions of tables 3 and 4 are include

Chemical History with a Nuclear Microprobe

A nuclear microprobe cannot give direct information on the chemical state of an element, but the spatial distribution of elements in a specimen is often determined by the chemical history of the sample. Fuel cells and minerals are examples of complex systems whose elemental distributions are determined by past chemical history. The distribution of catalyst in used fuel cell electrodes provides direct information on the chemical stability of dispersed catalysts under operating conditions. We have used spatially resolved Rutherford backscattering to measure the migration of platinum and vanadium from intermetallic catalysts and to determine their suitability for use under the extreme operating conditions found in phosphoric acid fuel cells. Geologic materials are complex, heterogeneous samples with small mineral grains. The trace element distribution within the individual mineral grains and between different mineral phases is sensitive to the details of the mineral formation and history. The spatial resolution and sub-100-ppm sensitivity available with a nuclear microprobe open up several new classes of experiments to the geochemist. Geochemistry and electrochemistry are two areas proving particularly fruitful for application of the nuclear microprobe

A journey to client and therapist mutuality in person-centered psychotherapy: a case study

This aim of this case study was to build theory on the development of client–therapist mutuality in person-centered psychotherapy. A case study focusing on a 42-year-old female client who had presented for therapy following trauma within interpersonal relationships has been used. A reflective, theory-building, case study method was adopted that used data gathered from verbatim session notes and research interviews between the therapist (first author) and research supervisor (second author). Three primary therapeutic processes that contributed to the development of mutuality are discussed. First, the development of mutual empathy in the relationship; second, strategies for disconnection and staying out of relationship are identified. Third, client agency and mutuality is explored. In conclusion the study proposes that mutuality is a key construct within person-centered psychotherapy and develops as a natural consequence of the presence of Rogers’ therapeutic conditions

Formation of Super-Earths

Super-Earths are the most abundant planets known to date and are characterized by having sizes between that of Earth and Neptune, typical orbital periods of less than 100 days and gaseous envelopes that are often massive enough to significantly contribute to the planet's overall radius. Furthermore, super-Earths regularly appear in tightly-packed multiple-planet systems, but resonant configurations in such systems are rare. This chapters summarizes current super-Earth formation theories. It starts from the formation of rocky cores and subsequent accretion of gaseous envelopes. We follow the thermal evolution of newly formed super-Earths and discuss their atmospheric mass loss due to disk dispersal, photoevaporation, core-cooling and collisions. We conclude with a comparison of observations and theoretical predictions, highlighting that even super-Earths that appear as barren rocky cores today likely formed with primordial hydrogen and helium envelopes and discuss some paths forward for the future.Comment: Invited review accepted for publication in the 'Handbook of Exoplanets,' Planet Formation section, Springer Reference Works, Juan Antonio Belmonte and Hans Deeg, Ed

The RMS Survey: Resolving kinematic distance ambiguities towards a sample of compact HII regions using HI absorption

We present high-resolution HI data obtained using the Australia Telescope Compact Array to resolve the near/far distance ambiguities towards a sample of compact HII regions from the Red MSX Source (RMS) survey. The high resolution data are complemented with lower resolution archival HI data extracted from the Southern and VLA Galactic Plane surveys. We resolve the distance ambiguity for nearly all of the 105 sources where the continuum was strong enough to allow analysis of the HI absorption line structure. This represents another step in the determination of distances to the total RMS sample, which with over 1,000 massive young stellar objects and compact HII regions, is the largest and most complete sample of its kind. The full sample will allow the distribution of massive star formation in the Galaxy to be examined.Comment: Accepted by MNRAS. This paper consists of 15 pages and contains 10 figures and 5 table

The California-Kepler Survey. I. High Resolution Spectroscopy of 1305 Stars Hosting Kepler Transiting Planets

The California-Kepler Survey (CKS) is an observational program to improve our knowledge of the properties of stars found to host transiting planets by NASA's Kepler Mission. The improvement stems from new high-resolution optical spectra obtained using HIRES at the W. M. Keck Observatory. The CKS stellar sample comprises 1305 stars classified as Kepler Objects of Interest, hosting a total of 2075 transiting planets. The primary sample is magnitude-limited (Kp < 14.2) and contains 960 stars with 1385 planets. The sample was extended to include some fainter stars that host multiple planets, ultra short period planets, or habitable zone planets. The spectroscopic parameters were determined with two different codes, one based on template matching and the other on direct spectral synthesis using radiative transfer. We demonstrate a precision of 60 K in effective temperature, 0.10 dex in surface gravity, 0.04 dex in [Fe/H], and 1.0 km/s in projected rotational velocity. In this paper we describe the CKS project and present a uniform catalog of spectroscopic parameters. Subsequent papers in this series present catalogs of derived stellar properties such as mass, radius and age; revised planet properties; and statistical explorations of the ensemble. CKS is the largest survey to determine the properties of Kepler stars using a uniform set of high-resolution, high signal-to-noise ratio spectra. The HIRES spectra are available to the community for independent analyses.Comment: 20 pages, 19 figures, accepted for publication in AJ; a full version of Table 5 is included as tab_cks.csv and tab_cks.te

Perpendicular Ion Heating by Low-Frequency Alfven-Wave Turbulence in the Solar Wind

We consider ion heating by turbulent Alfven waves (AWs) and kinetic Alfven waves (KAWs) with perpendicular wavelengths comparable to the ion gyroradius and frequencies smaller than the ion cyclotron frequency. When the turbulence amplitude exceeds a certain threshold, an ion's orbit becomes chaotic. The ion then interacts stochastically with the time-varying electrostatic potential, and the ion's energy undergoes a random walk. Using phenomenological arguments, we derive an analytic expression for the rates at which different ion species are heated, which we test by simulating test particles interacting with a spectrum of randomly phased AWs and KAWs. We find that the stochastic heating rate depends sensitively on the quantity epsilon = dv/vperp, where vperp is the component of the ion velocity perpendicular to the background magnetic field B0, and dv (dB) is the rms amplitude of the velocity (magnetic-field) fluctuations at the gyroradius scale. In the case of thermal protons, when epsilon << eps1, where eps1 is a constant, a proton's magnetic moment is nearly conserved and stochastic heating is extremely weak. However, when epsilon > eps1, the proton heating rate exceeds the cascade power that would be present in strong balanced KAW turbulence with the same value of dv, and magnetic-moment conservation is violated. For the random-phase waves in our test-particle simulations, eps1 is approximately 0.2. For protons in low-beta plasmas, epsilon is approximately dB/B0 divided by the square root of beta, and epsilon can exceed eps1 even when dB/B0 << eps1. At comparable temperatures, alpha particles and minor ions have larger values of epsilon than protons and are heated more efficiently as a result. We discuss the implications of our results for ion heating in coronal holes and the solar wind.Comment: 14 pages, 5 figures, submitted to Ap