Physicochemical properties of nickel and cobalt sulphate solutions of hydrometallurgical relevance

Producing nickel and cobalt metal by high pressure acid leaching (HPAL) of nickel laterites is becoming one of Australia's largest mineral processing industries. However, the background chemical information for this process, including the fundamental physicochemical properties of acidic metal sulphate leachate solutions, is not well known. In order to improve the efficiency of current and future HPAL plants, high quality physicochemical and thermodynamic data will be necessary. This thesis reports measurements on the densities and heat capacities of nickel and cobalt sulphate solutions and their mixtures along with detailed studies of the nature of the species present and the thermodynamics of their interconversions. Densities and heat capacities of nickel and cobalt sulphate and perchlorate solutions and their ternary mixtures were measured using a vibrating tube densimeter and a flow microcalorimeter respectively. These data were used to calculate the apparent molal volumes and heat capacities of these solutions. Standard partial molal quantities were then obtained by appropriate extrapolation procedures, along with the volume and heat capacity changes of ion pair formation. A comparison has been made between experimental densities and heat capacities with those predicted by Young's rule. Good agreement was obtained except when the degree of complexation varied significantly in the mixtures. The various ion pair species in nickel and cobalt sulphate solutions, along with those of magnesium sulphate (which is a major impurity in HPAL leachates), were reinvestigated by dielectric relaxation spectroscopy. Doubly solvent separated ion pairs, solvent shared ion pairs and contact ion pairs were shown to exist simultaneously in solution and their concentrations were determined from dilute to near-saturated concentrations. Evidence for the possible existence of a triple ion, M2SO4 2+, was also obtained in highly concentrated solutions. The equilibrium constants of the stepwise reactions and the effective hydration numbers of ions and ion pairs were also calculated. The heats of complexation of nickel(II) and cobalt(II) sulphate were determined at different ionic strengths in sodium perchlorate media by titration calorimetry. These data were fitted to a specific ion interaction model to obtain the standard state values. The corresponding entropies of complexation were calculated and were found to be the major contributor to the stability of the complexes

Sharp benefit-to-cost rules for the evolution of cooperation on regular graphs

We study two of the simple rules on finite graphs under the death-birth updating and the imitation updating discovered by Ohtsuki, Hauert, Lieberman and Nowak [Nature 441 (2006) 502-505]. Each rule specifies a payoff-ratio cutoff point for the magnitude of fixation probabilities of the underlying evolutionary game between cooperators and defectors. We view the Markov chains associated with the two updating mechanisms as voter model perturbations. Then we present a first-order approximation for fixation probabilities of general voter model perturbations on finite graphs subject to small perturbation in terms of the voter model fixation probabilities. In the context of regular graphs, we obtain algebraically explicit first-order approximations for the fixation probabilities of cooperators distributed as certain uniform distributions. These approximations lead to a rigorous proof that both of the rules of Ohtsuki et al. are valid and are sharp.Comment: Published in at http://dx.doi.org/10.1214/12-AAP849 the Annals of Applied Probability (http://www.imstat.org/aap/) by the Institute of Mathematical Statistics (http://www.imstat.org

Couldn't or Wouldn't? the Influence of Privacy Concerns and Self-Efficacy in Privacy Management on Privacy Protection

Sampling 515 college students, this study investigates how privacy protection, including profile visibility, self-disclosure, and friending, are influenced by privacy concerns and efficacy regarding one's own ability to manage privacy settings, a factor that researchers have yet to give a great deal of attention to in the context of social networking sites (SNSs). The results of this study indicate an inconsistency in adopting strategies to protect privacy, a disconnect from limiting profile visibility and friending to self-disclosure. More specifically, privacy concerns lead SNS users to limit their profile visibility and discourage them from expanding their network. However, they do not constrain self-disclosure. Similarly, while self-efficacy in privacy management encourages SNS users to limit their profile visibility, it facilitates self-disclosure. This suggests that if users are limiting their profile visibility and constraining their friending behaviors, it does not necessarily mean they will reduce self-disclosure on SNSs because these behaviors are predicted by different factors. In addition, the study finds an interaction effect between privacy concerns and self-efficacy in privacy management on friending. It points to the potential problem of increased risk-taking behaviors resulting from high self-efficacy in privacy management and low privacy concerns.Radio-Television-Fil