title: Anodically polarized nickel electrodes in DMSO or DMF solutions of pseudohalide ions: IR spectroelectrochemical studies

authors: Alwis, L. K. H. K.

subjects: chemistry

abstract: A novel subtractively normalized interfacial Fourier transform infrared spectroscopic (SNIFTIRS) investigation of anodically polarized nickel electrodes in pseudohalide-containing DMF or DMSO solutions (i.e. OCN⁻, SCN⁻, SeCN⁻), in supporting electrolyte, tetrabutylammonium perchlorate (TBAP), is presented. In general, the data showed that nickel demonstrated irreversible anodic dissolution in all solutions studied at very high values of the applied potential, > +500 mV (AgCl/Ag). The predominant speciation of nickel in these systems was as complex ions consisting of Ni²⁺ ion complexed to pseudohalide ions and solvent molecules. Insoluble films and dissolved CO₂ were also detected, though mostly in the Ni/OCN⁻ systems studied. Ni(II)/pseudohalide complex ion species detected were modeled using solutions containing Ni²⁺ ion mixed with pseudohalide ion in different mole ratios. In general, the Ni/OCN⁻ electrochemical system behaved differently relative to those of Ni/SCN⁻ and Ni/SeCN⁻ due to the difference in colors observed in cell solutions after SNIFTIRS experiments which was mirrored in the model solutions. Ni(II)-cyanate species had a different, coordination geometry and gave a characteristic bright blue color due possibly to Ni(NCO)₄²⁻ ion while Ni(II) thiocyanate and selenocyanate complex ion species had octahedral coordination geometries containing solvent and one coordinated pseudohalide ion and formed greeny yellow solutions.

text: Anodically polarized nickel electrodes in DMSO or DMF solutions of pseudohalide ions: IR spectroelectrochemical studies A novel subtractively normalized interfacial Fourier transform infrared spectroscopic (SNIFTIRS) investigation of anodically polarized nickel electrodes in pseudohalide-containing DMF or DMSO solutions (i.e. OCN⁻, SCN⁻, SeCN⁻), in supporting electrolyte, tetrabutylammonium perchlorate (TBAP), is presented. In general, the data showed that nickel demonstrated irreversible anodic dissolution in all solutions studied at very high values of the applied potential, > +500 mV (AgCl/Ag). The predominant speciation of nickel in these systems was as complex ions consisting of Ni²⁺ ion complexed to pseudohalide ions and solvent molecules. Insoluble films and dissolved CO₂ were also detected, though mostly in the Ni/OCN⁻ systems studied. Ni(II)/pseudohalide complex ion species detected were modeled using solutions containing Ni²⁺ ion mixed with pseudohalide ion in different mole ratios. In general, the Ni/OCN⁻ electrochemical system behaved differently relative to those of Ni/SCN⁻ and Ni/SeCN⁻ due to the difference in colors observed in cell solutions after SNIFTIRS experiments which was mirrored in the model solutions. Ni(II)-cyanate species had a different, coordination geometry and gave a characteristic bright blue color due possibly to Ni(NCO)₄²⁻ ion while Ni(II) thiocyanate and selenocyanate complex ion species had octahedral coordination geometries containing solvent and one coordinated pseudohalide ion and formed greeny yellow solutions.

year: 2013

title: Doctorates in the dark: Threshold concepts and the improvement of doctoral supervision

authors: Johnson, E. Marcia

subjects: threshold concepts

abstract: The overall goal of this qualitative research case study into doctoral writing was to determine if there were knowable threshold concepts and, if so, to develop effective strategies for helping students overcome them. In addition, it was understood that such strategies could have change implications for supervisory practice. Interview and survey data were collected from students and supervisors. From the student data two threshold concepts had emerged: “Talking to think”—a strategy for developing clarity in writing; and self-efficacy—the belief in one's ability to overcome writing barriers and become an independent academic researcher. In this paper, those two threshold concepts provide an organising framework for the presentation of supervisor findings and for discussion of supervisor professional development needs. The paper concludes with insights into how supervisor professional development could be improved and extended beyond its current focus on regulations and compliance issues.

text: Doctorates in the dark: Threshold concepts and the improvement of doctoral supervision The overall goal of this qualitative research case study into doctoral writing was to determine if there were knowable threshold concepts and, if so, to develop effective strategies for helping students overcome them. In addition, it was understood that such strategies could have change implications for supervisory practice. Interview and survey data were collected from students and supervisors. From the student data two threshold concepts had emerged: “Talking to think”—a strategy for developing clarity in writing; and self-efficacy—the belief in one's ability to overcome writing barriers and become an independent academic researcher. In this paper, those two threshold concepts provide an organising framework for the presentation of supervisor findings and for discussion of supervisor professional development needs. The paper concludes with insights into how supervisor professional development could be improved and extended beyond its current focus on regulations and compliance issues.

year: 2014

title: Improving prediction of potential for treatment completion at Tai Aroha

authors: Astridge Clarke,  Abigail Darcy

subjects: Treatment

abstract: Participant non-completion can be a major problem for treatment programmes. Staff may try to minimise non-completion by deciding who to select for treatment using professional intuition and referral information. It can be difficult for treatment staff to make these decisions regarding the potential for programme completion due to a lack of clear guidelines about what information to consider. This lack of clear guidelines can increase susceptibility to biases, and lead to unreliable and potentially inaccurate decisions. Research has identified ‘simple rules’ that are tools to aid decision-making quickly, effectively, and consistently. Therefore, using past treatment data, we1 aimed to identify predictors of programme completion vs. non-completion at Tai Aroha—a residential treatment programme based in Hamilton—to explore whether a “simple rule” can be developed from information readily available at the time of referral, to support staff decision-making when selecting offenders to attend treatment, with the potential to increase programme completion. We were successful in the development of a simple rule to aid Tai Aroha staff selection decisions. The implications, and limitations of our rule and our study are discussed, and future research relating to simple rules are identified.

text: Improving prediction of potential for treatment completion at Tai Aroha Participant non-completion can be a major problem for treatment programmes. Staff may try to minimise non-completion by deciding who to select for treatment using professional intuition and referral information. It can be difficult for treatment staff to make these decisions regarding the potential for programme completion due to a lack of clear guidelines about what information to consider. This lack of clear guidelines can increase susceptibility to biases, and lead to unreliable and potentially inaccurate decisions. Research has identified ‘simple rules’ that are tools to aid decision-making quickly, effectively, and consistently. Therefore, using past treatment data, we1 aimed to identify predictors of programme completion vs. non-completion at Tai Aroha—a residential treatment programme based in Hamilton—to explore whether a “simple rule” can be developed from information readily available at the time of referral, to support staff decision-making when selecting offenders to attend treatment, with the potential to increase programme completion. We were successful in the development of a simple rule to aid Tai Aroha staff selection decisions. The implications, and limitations of our rule and our study are discussed, and future research relating to simple rules are identified.

year: 2023