Effects of instructional changes on student learning of electrochemistry in an IB chemistry course

This study investigated the effectiveness of incorporating several new instructional strategies into an International Baccalaureate (IB) chemistry course in terms of how they supported high school seniors’ understanding of electrochemistry. The three new methods used were (a) providing opportunities for visualization of particle movement by student manipulation of physical models and interactive computer simulations, (b) explicitly addressing common misconceptions identified in the literature, and (c) teaching an algorithmic, step-wise approach for determining the products of an aqueous solution electrolysis. Changes in student understanding were assessed through test scores on both internally and externally administered exams over a two-year period. It was found that visualization practice and explicit misconception instruction improved student understanding, but the effect was more apparent in the short-term. The data suggested that instruction time spent on algorithm practice was insufficient to cause significant test score improvement. There was, however, a substantial increase in the percentage of the experimental group students who chose to answer an optional electrochemistry-related external exam question, indicating an increase in student confidence. Implications for future instruction are discussed.

Sulfoxides as an intramolecular sulfenylating agent for indoles and diverse applications of the sulfide-sulfoxide redox cycle in organic chemistry

This dissertation involves study of various aspects of sulfoxide chemistry. Specifically designed t-butyl and propanenitrile sulfoxides tethered to indole-2-carboxamide were used as a source of intramolecular sulfenylating agents to synthesize novel indolo[3,2-b]-1-5-benzothiazepinones which are structurally analogous to the other biologically active benzothiazepinones. This study reveals that the intramolecular cyclization of sulfoxide follows an electrophilic sulfenylation (Sulfoxide Electrophilic Sulfenylation, SES) reaction pathway. Evidence of the absence of sulfenic acid as a transient reactive intermediate in such intramolecular cyclization is also provided. In another study, sulfoxide was used as a “protecting group” of thioether to synthesize 8-membered, indole substituted, thiazocine-2-acetic acid derivative via Ring Closing Metathesis (RCM). Protection (oxidation) of inert (to RCM) sulfide to sulfoxide followed by RCM produced cyclized product in good yields. Deprotection (reduction) of sulfoxide was achieved using Lawessons Reagent (L.R.). Application of the sulfide-sulfoxide redox cycle to solve the existing difficulties in using RCM methodology to thioethers is illustrated. A new design of a “molecular brake”, based on the sulfide-sulfoxide redox cycle is described. N-Ar rotation in simple isoindolines is controlled by the oxidation state of the proximate sulfur atom. Sulfide [S(II)] shows “free” [brake OFF] N-Ar rotation whereas sulfoxide displayed hindered [brake ON] N-Ar rotation. The semi-empirical molecular orbital (PM3) calculations revealed concerted pyramidalization of amidic nitrogen with N-Ar rotation.

Improving learning by connecting chemistry curriculum to students' experiences

The purpose of the study was to design, implement, and assess the effects of a teaching unit about fuel sources and chemical energy on students’ learning. The unit was designed to incorporate students’ experiences in a way that was aligned with the Michigan High School Content Expectations. The study was completed with all of the students taking General Chemistry in a rural Michigan high school in the 2010-11 school year. There were 138 participants total. The participants were mostly Caucasian and the majority were in the 11th grade. Of these, 77 constituted the experimental group and were taught the unit. The additional 61 participants in the control group were given the posttest only. Data was derived from the results of pre/post tests, final assessment projects, and the researcher’s observations. A pretest that contained questions about the fuel sources was administered at the beginning of the unit. An identical posttest was administered at the completion of the unit. A final assessment project required students to choose the best fuel source for the area, and support their opinion with facts and data from their research or the learning activities and labs performed in class. The results of the study revealed that the teaching unit did produce significant learning gains in the experimental group. The results also indicated that the teaching unit added value to the current General Chemistry curriculum by expanding what students were learning. The instructional goals of the unit were aligned with the Michigan High School Content Expectations. The results also revealed that the students were able to learn to support their thinking and decisions with explanations based on the data and labs. These are essential science literacy skills. The study supported the view that connecting the required curriculum with students’ experiences and interests was effective, and that students can learn important science literacy skills, such as providing support for arguments and communicating scientific explanations, when given adequate teacher support.

The Role of Water Chemistry in the Concentration of Hematite Ore

Selective flocculation and dispersion processes rely on differences in the surface chemistry of fine mineral particles (<25 >ìm) to allow for the concentration of specific minerals from an ore body. The effectiveness of selective flocculation and dispersion processes for the concentration of hematite (Fe2O3) ore are strongly dependent on the ionic content of the process water. The goal of this research was to analyze the ionic content of an operating selective flocculation and dispersion type hematite ore concentrator and determine how carbon dioxide affects the filtration of the final product. A detailed water chemistry analysis of the entire process was determined to show concentration profiles throughout the process. This information was used to explain process phenomena and promote future research into this subject. A subsequent laboratory study was conducted to show how carbon dioxide affects filtration rate and relate this effect to the zeta potential of the constituents of the concentrated hematite ore.

COORDINATION CHEMISTRY OF BIS(BENZYL)PHOSPHINATE

The work presented in this dissertation deals with the coordination chemistry of the bis(benzyl)phosphinate ligand with vanadium, tungsten and cobalt. The long term goal of this project was to produce and physically characterize high oxidation state transition metal oxide phosphinate compounds with potential catalytic applications. The reaction of bis(benzyl)phosphinic acid with VO(acac)2 in the presence of water or pyridine leads to the synthesis of trimeric vanadium(IV) clusters (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(H2O) and (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(py). In contrast, when diphenylphosphinic acid or 2-hydroxyisophosphindoline-2-oxide were reacted with VO(acac)2, insoluble polymeric compounds were produced. The trimeric clusters were characterized using FTIR, elemental analysis, single crystal diffraction, room temperature magnetic susceptibility, thermogravimetric analysis and differential scanning calorimetry. The variable-temperature, solid-state magnetic susceptibility was measured on (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(py). The polymeric compounds were characterized using FTIR, powder diffraction and elemental analysis. Two different cubane clusters made of tungsten(V) and vanadium(V) were stabilized using bis(benzyl)phosphinate. The oxidation of (V3(µ3-O)O2)(µ2-O2P(CH2C6H5)2)6(H2O) with tBuOOH led to the formation of V4(µ3-O)4(µ2-O2P(Bn)2)4(O4). W4(µ3-O)4(µ2-O2P(Bn)2)4(O4) was produced by heating W(CO)6 in a 1:1 mixture of EtOH/THF at 120 ˚C. Both compounds were characterized using single crystal diffraction, FTIR, 31P-NMR, 1H-NMR and elemental analysis. W4(µ3-O)4(µ2-O2P(Bn)2)4(O4) was also characterized using UV-vis. Cobalt(II) reacted with bis(benzyl)phosphinate to produce three different dinuclear complexes. [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4], (py)3Co(µ2-O2P(Bn)2)3Co(Cl) and (py)(µ2-NO3)Co(µ2-O2P(Bn)2)3Co(py) were all characterized using single crystal diffraction, elemental analysis and FTIR. Room temperature magnetic susceptibility measurements were performed on [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4] and (py)3Co(µ2-O2P(Bn)2)3Co(Cl). The variable-temperature, solid-state magnetic susceptibility was also measured on [(py)3Co(µ2-O2P(Bn)2)3Co(py)][ClO4].

Looking at Chemistry in Hard to See Places: Understanding Energy Conversion at 1400° Celsius

Solid oxide fuel cells (SOFCs) are promising devices for stationary and portable power and heat generation, because they can use complex fuels such as hydro-carbons, CO, and alcohols. Extreme, non-equilibrium conditions and high tem-peratures (≥ 700 ˚C) required for SOFC operation hamper efforts to understand the mechanisms of component degradation in SOFCs. This talk focuses on new insights into SOFC chemistry and the conversion of carbon-containing fuels (both hydrocarbons and oxygenated) into electricity, carbon dioxide and water, gleaned from a combination of techniques including electrochemical impedance spectroscopy, voltammetry, and vibrational Raman scattering.

Integrated data acquisition and processing to determine metabolite contents, relaxation times, and macromolecule baseline in single examinations of individual subjects

Absolute quantitation of clinical (1)H-MR spectra is virtually always incomplete for single subjects because the separate determination of spectrum, baseline, and transverse and longitudinal relaxation times in single subjects is prohibitively long. Integrated Processing and Acquisition of Data (IPAD) based on a combined 2-dimensional experimental and fitting strategy is suggested to substantially improve the information content from a given measurement time. A series of localized saturation-recovery spectra was recorded and combined with 2-dimensional prior-knowledge fitting to simultaneously determine metabolite T(1) (from analysis of the saturation-recovery time course), metabolite T(2) (from lineshape analysis based on metabolite and water peak shapes), macromolecular baseline (based on T(1) differences and analysis of the saturation-recovery time course), and metabolite concentrations (using prior knowledge fitting and conventional procedures of absolute standardization). The procedure was tested on metabolite solutions and applied in 25 subjects (15-78 years old). Metabolite content was comparable to previously found values. Interindividual variation was larger than intraindividual variation in repeated spectra for metabolite content as well as for some relaxation times. Relaxation times were different for various metabolite groups. Parts of the interindividual variation could be explained by significant age dependence of relaxation times.

Convenient synthesis of substituted α-methylene--valerolactones in aqueous medium using Baylis-Hillman chemistry

A mild and convenient synthesis of substituted α-methylene--valerolactones was achieved by SN2 nucleophilic substitution of the acetates of the Baylis-Hillman adducts with acetyl acetone followed by one-pot saponification of the ester, reduction of the keto group and subsequent intramolecular ring closure in aqueous medium.