Heat capacities of aqueous sodium hydroxide/aluminate mixtures and prediction of the solubility constant of boehmite up to 300 °C

A modified commercial (Setaram C80) calorimeter has been used to measure the isobaric volumetric heat capacities of concentrated alkaline sodium aluminate solutions at ionic strengths from 1 to 6 mol kg-1, with up to 40 mol.% substitution of hydroxide by aluminate, at temperatures from 50 to 300 °C and a pressure of 10 MPa. Apparent molar heat capacities for the mixtures, Cpφ{symbol}, derived from these data were found to depend linearly on the aluminate substitution level, i.e., they followed Young's rule. These quantities were used to estimate the apparent molar heat capacities of pure, hypothetical sodium aluminate solutions, Cpφ{symbol} ('NaAl(OH)4'(aq)). Slopes of the Young's rule plots were invariant with ionic strength at a given temperature but depended linearly on temperature. The heat capacities of ternary aqueous sodium hydroxide/aluminate mixtures could therefore be modelled using only two parameters in addition to those needed for the correlation of Cpφ{symbol} (NaOH(aq)) reported previously from these laboratories. An assessment of the standard thermodynamic quantities for boehmite, gibbsite and the aluminate ion yielded a set of recommended values that, together with the present heat capacity data, accurately predicts the solubility of gibbsite and boehmite at temperatures up to 300 °C

Soil sustainability in organic agricultural production

Traditionally, the assessment of soil sustainability and the potential impact of cultivation are based upon the application of chemical procedures. In the absence of a biological context, these measurements offer little in understanding longterm changes in soil husbandry. Detailed microcosm investigations were applied as a predictive tool for management change. The microcosms were designed with homogenised soils treated with organic amendments. Key soil functional relationships were quantified using stable isotope techniques, biochemical measurements and traditional approaches

Zintl Chemistry for Designing High Efficiency Thermoelectric Materials

Zintl phases and related compounds are promising thermoelectric materials; for instance, high zT has been found in Yb_(14)MnSb_(11), clathrates, and the filled skutterudites. The rich solid-state chemistry of Zintl phases enables numerous possibilities for chemical substitutions and structural modifications that allow the fundamental transport parameters (carrier concentration, mobility, effective mass, and lattice thermal conductivity) to be modified for improved thermoelectric performance. For example, free carrier concentration is determined by the valence imbalance using Zintl chemistry, thereby enabling the rational optimization of zT. The low thermal conductivity values obtained in Zintl thermoelectrics arise from a diverse range of sources, including point defect scattering and the low velocity of optical phonon modes. Despite their complex structures and chemistry, the transport properties of many modern thermoelectrics can be understood using traditional models for heavily doped semiconductors

Transport properties of the layered Zintl compound SrZnSb_2

Transport properties of the layered Zintl compound SrZnSb_2 have been characterized from room temperature to 725 K on polycrystalline samples. SrZnSb_2 samples were found to be p-type with a Hall carrier concentration of 5×10^(20) cm^(−3) at room temperature, and a small Seebeck coefficient and electrical resistivity are observed. A single band model predicts that, even with optimal doping, significant thermoelectric performance will not be achieved in SrZnSb_2. A relatively low lattice thermal conductivity is observed, κ_L~1.2 W m^(−1) K^(−1), at room temperature. The thermal transport of SrZnSb_2 is compared to that of the layered Zintl compounds AZn2Sb_2 (A=Ca,Yb,Sr,Eu), which have smaller unit cells and larger lattice thermal conductivity, κ_L~2 W m^(−1) K^(−1), at 300K. Ultrasonic measurements, in combination with kinetic theory and the estimated κ_L values, suggest that the lower κ_L of SrZnSb_2 is primarily the result of a reduction in the volumetric specific heat of the acoustic phonons due to the increased number of atoms per unit cell. Therefore, this work recommends that unit cell size should be considered when selecting Zintl compounds for potential thermoelectric application

Secondary literacy across the curriculum: Challenges and possibilities

This paper discusses the challenges and possibilities attendant upon successfully implementing literacy across the curriculum initiatives – or ‘school language policies’ as they have come to be known - particularly at the secondary or high school level. It provides a theoretical background to these issues, exploring previous academic discussions of school language policies, and highlights key areas of concern as well as opportunity with respect to school implementation of such policies. As such, it provides a necessary conceptual background to the subsequent papers in this special issue, which focus upon the Secondary Schools’ Literacy Initiative (SSLI) – a New Zealand funded programme that aims to establish cross-curricular language and literacy policies in secondary schools

Thermoelectric properties of p-type LiZnSb: Assessment of ab initio calculations

In response to theoretical calculations on the thermoelectric performance of LiZnSb, we report the pertinent transport properties between room temperature and 523 K. Nominal LiZnSb samples are found to be p-type, with a carrier concentration in the range (4–7)×10^(20) cm^(−3). The thermoelectric figure of merit (zT) is found to be 0.02–0.08 at 523 K. Analysis of material transport parameters and previously reported ab initio calculations demonstrates that even with optimal doping, p-type LiZnSb is unlikely to achieve zT>0.2 at 523 K. The accuracy of the high zT estimate (zT>2) for n-type compositions from ab initio calculations is discussed within the current synthetic limits

Eigenvalue Separation in Some Random Matrix Models

The eigenvalue density for members of the Gaussian orthogonal and unitary ensembles follows the Wigner semi-circle law. If the Gaussian entries are all shifted by a constant amount c/Sqrt(2N), where N is the size of the matrix, in the large N limit a single eigenvalue will separate from the support of the Wigner semi-circle provided c > 1. In this study, using an asymptotic analysis of the secular equation for the eigenvalue condition, we compare this effect to analogous effects occurring in general variance Wishart matrices and matrices from the shifted mean chiral ensemble. We undertake an analogous comparative study of eigenvalue separation properties when the size of the matrices are fixed and c goes to infinity, and higher rank analogues of this setting. This is done using exact expressions for eigenvalue probability densities in terms of generalized hypergeometric functions, and using the interpretation of the latter as a Green function in the Dyson Brownian motion model. For the shifted mean Gaussian unitary ensemble and its analogues an alternative approach is to use exact expressions for the correlation functions in terms of classical orthogonal polynomials and associated multiple generalizations. By using these exact expressions to compute and plot the eigenvalue density, illustrations of the various eigenvalue separation effects are obtained.Comment: 25 pages, 9 figures include

Overcoming the barriers to implementing urban road user charging schemes

Urban road user charging offers the potential to achieve significant improvements in urban transport, but is notoriously difficult to implement. Cities need guidance on the range of factors to be considered in planning and implementing such schemes. This paper summarises the results of a 3 year programme which has collated evidence on the issues of most concern to cities. A state of the art report has provided evidence on 14 themes, ranging from objectives and design to implementation and evaluation. A set of 16 case studies has reviewed experience in design and implementation across Europe. The paper summarises their findings, provides references to more detailed information, presents the resulting policy recommendations to European, national and local government, and outlines the areas in which further research is needed

Optimization of protein extraction from Aspergillus nidulans for gel electrophoresis

Efficient extraction of proteins from filamentous fungi is difficult both as a result of high endogenous protease activity, the existence of a hard cell wall, and the tendency of hyphae to clump. We have had difficulty using published protocols in extracting high molecular weight proteins (\u3e150 kDa), and in extraction from germlings grown on minimal media with a poor carbon source such as glycerol. In order to address these problems, we have compared several different extraction protocols and found the protocol utilizing 9M Urea-sample buffer to be the fastest and most efficient with sample variation being kept to a minimum