High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Investigation of Mantle Dynamics from Platinum Group Elements and Rhenium-Osmium Isotope Systematics of Mantle Xenoliths from Oahu, Hawaii

Intraplate volcanism that has created the Hawaiian-Emperor seamount chain is generally thought to be formed by a deep-seated mantle plume. While the idea of a Hawaiian plume has not met with substantial opposition, whether or not the Hawaiian plume shows any geochemical signal of receiving materials from the Earth’s Outer Core and how the plume may or may not be reacting with the overriding lithosphere remain debatable issues. In an effort to understand how the Hawaiian plume works I report on the first in-situ sulfides and bulk rock Platinum Group Element (PGE) concentrations, together with Os isotope ratios on well-characterized garnet pyroxenite xenoliths from the island of Oahu in Hawaii. The sulfides are Fe-Ni Monosulfide Solid Solution and show fractionated PGE patterns. Based on the major elements, Platinum Group Elements and experimental data I interpret the Hawaiian sulfides as an immiscible melt that separated from a melt similar to the Honolulu Volcanics (HV) alkali lavas at a pressure-temperature condition of 1530 ± 100OC and 3.1±0.6 GPa., i.e. near the base or slightly below the Pacific lithosphere. The 187Os/188Os ratios of the bulk rock vary from subchondritic to suprachondritic (0.123-0.164); and the 187Os/188Os ratio strongly correlates with major element, High Field Strength Element (HFSE), Rare Earth Element (REE) and PGE abundances. These correlations strongly suggest that PGE concentrations and Os isotope ratios reflect primary mantle processes. I interpret these correlations as the result of melt-mantle reaction at the base of the lithosphere: I suggest that the parental melt that crystallized the pyroxenites selectively picked up radiogenic Os from the grain boundary sulfides, while percolating through the Pacific lithosphere. Thus the sampled pyroxenites essentially represent crystallized melts from different stages of this melt-mantle reaction process at the base of the lithosphere. I further show that the relatively low Pt/Re ratios of the Hawaiian sulfides and the bulk rock pyroxenites suggest that, upon ageing, such pyroxenites plus their sulfides cannot generate the coupled 186Os- 187Os isotope enrichments observed in Hawaiian lavas. Therefore, recycling of mantle sulfides of pyroxenitic parentage is unlikely to explain the enriched Pt-Re-Os isotope systematics of plume-derived lavas.

GRE as a predictor of graduate student success at a Hispanic serving institution of higher education

Accurately predicting the success of graduate students is an important aspect of determining which students should be admitted into graduate programs. The GRE is a pivotal factor to examine since it is one of the most widely used criteria for graduate school admission. Even though the GRE is advertised as an accurate tool for predicting first year graduate GPA, there is a lack of research on long term success factors such as time to degree and graduate rate (Luthy, 1996; Powers, 2004). Furthermore, since most studies have low minority sample sizes, the validity of the GRE may not be the same across all groups (ETS, 2008b; Kuncel, Hezlett, & Ones, 2001). Another gap in GRE studies is that few researchers analyze student characteristics, which may alter or moderate the prediction validity of the GRE. Thus, student characteristics such as degree of academic involvement, mentorship interactions, and other academic and social experiences have not been widely examined in this context. These gaps in the analysis of GRE validity are especially relevant given the high attrition rates within of some graduate programs (e.g., an estimated 68% of doctoral student never complete their programs in urban universities; Lovitts, 2001). A sequential mixed methods design was used to answer the research questions in two phases. The quantitative phase used student data files to analyze the relationship of two success variables (graduation rate and graduate GPA) to the GRE scores as well as other academic and demographic graduate student characteristics. The qualitative phase served to complement the first phase by describing a wider range of characteristics from the 11 graduate students who were interviewed. Both proximal and distal moderators influence student behaviors and success in graduate school. In the first phase of the study, the GRE was the distal facilitator under analysis. Findings suggested that both the GRE Quantitative and the GRE Verbal were predictors of success for master’s students, but the GRE Quantitative was not predictive of success for doctoral students. Other student characteristics such as demographic variables and disciplinary area were also predictors of success for the population of students studied. In the second phase of the study, it was inconclusive whether the GRE was predictive of graduate student success; though it did influence access to graduate programs. Furthermore, proximal moderators such as student involvement, faculty/peer interactions, motivational factors, and program structure were perceived to be facilitators and/or detractors for success.

Development of an instrument to measure high school students' global awareness and attitudes: Looking through the lens of social sciences

The purpose of this study was to develop an instrument to measure high school students’ perspectives on global awareness and attitudes toward social issues. The research questions that guided this study were: (a) Can acceptable validity and reliability estimates be established for an instrument developed to measure high schools students' global awareness? (b) Can acceptable validity and reliability estimates be established for an instrument developed to measure high schools students' attitudes towards global social issues? (c) What is the relationship between high school students’ GPA, race/ethnicity, gender, socio-economic status, parents’ education, getting the news, reading and listening habits, the number of classes taken in the social sciences, whether they speak a second language, and have experienced living in or visiting other countries, and their perception of global awareness and attitudes toward global social issues. ^ An ex post facto research design was used and the data were collected using a 4-part Likert-type survey. It was administered to 14 schools in the Miami-Dade County, Florida area to 704 students. A factor analysis with an orthogonal varimax rotation was vii used to select the factors that best represented the three constructs – global education, global citizenship, and global workforce. This was done to establish construct validity. Cronbach’s alpha was used to determine the reliability of the instrument. Descriptive statistics and a hierarchical multiple regression were used for the demographics to establish their relationship, if any, to the findings. ^ Key findings of the study were that reliable and valid estimates can be developed for the instrument. The multiple regression analysis for model 1 and 2 accounted for a variance of 3% and 5% for self-perceptions of global awareness (factor 1). The regression model also accounted for a 5% and 13% variance in the two models for attitudes toward global social issues (factor 2). The demographics that were statistically significant were: ethnicity, gender, SES, parents’ education, listening to music, getting the news, speaking a second language, GPA, classes taken in the social sciences, and visiting other countries. An important finding for the study was those attending public schools (as opposed to private schools) had more positive attitudes towards global social issues (factor 2) The statistics indicated that these students had taken history, economics, and social studies – a curriculum infused with global perspectives.^

The relationship between a retention program and the persistence and graduation rates of first-generation low-income students at an urban, public university

The purpose of this study was to examine the relationship between participation in a retention program designed to promote academic and social integration and the persistence rates of first generation, low-income college students at an urban, public multiethnic university. Archival data were collected from the university’s Office of Institutional Research and the retention program office and included SAT/ACT scores, GPA, gender, ethnicity, and program participation data. A total of 292 first-generation, low-income students who were admitted to the university in the summer of 1999 were identified for the study. A group of 166 students were selected for the comparison group because they had not participated in the retention program; 126 students had participated in the retention program. ^ Three major research questions guided this study: (a) Are there differences in persistence rates and other academic characteristics of underprepared, low-income, first generation college students who participate and do not participate in the retention program?; (b) Does involvement in the retention program predict student persistence of first generation low-income, underprepared students?, and (c) Can predictors of GPA be identified for students in the retention program using program and descriptive variables? ^ A series of logistic regression analyses were conducted to assess the relationship between various retention services and the persistence and graduation rates of participants. The results showed that there were statistically significant relationships between participation and non-participation in the retention program and having higher GPAs and higher graduation and persistence rates. Of the four program features, participation in tutoring, workshops, and social events were found to be predictors of graduation. College GPA was also found to be a predictor of graduation for all students. The results also showed that women were more likely to graduate than men.^

The role of emotional intelligence in college students' success

The purpose of this study was to determine if higher academic performance was positively correlated to higher emotional intelligence among traditional age male and female college students enrolled in an Introduction to Business course at a large multi-campus state college in Florida. The Bar-On 2004 (Emotional Quotient Inventory) EQ-i 133-item inventory was used to assess students’ emotional intelligence. Within the scope of this ex-post facto study, a quasi-experimental design was included to further determine if emotional intelligence could be increased through the inclusion of a curricular component on emotional intelligence. Four groups of students (N=111) participated in the three-phase study over two semesters. The first phase (pre-intervention) was limited to students with an established GPA and an attempted-to-completed credit hour ratio within the institution (N=82). Results showed a slight positive correlation between the two factors and the students’ emotional intelligence pretest assessment scores. The second phase of the study involved establishing a control and an experimental group in each of two semesters to compare the attainment of overall emotional intelligence scores as measured by the EQ-i. The third phase of the study examined four measures of academic success (GPA, the attempted-to-completed credit hour ratio, grade in the business course, and persistence in college) to determine if these factors were positively correlated with the students’ posttest EQ-i scores. The study also included a research question to determine if significant differences in overall EQ-i scores existed between male and female students during the three phases. Findings from the study indicated that (a) there was a slight positive correlation in the pre-intervention stage between emotional intelligence and traditional measures of academic success specifically, GPA and the attempted-to-completed credit hour ratio; (b) curricular intervention made a significant difference at the p <.05 level, with an .5 effect size, in one semester but failed to meet that threshold in the following semester with the second pair of groups; (c) at the post-intervention phase, the four measures of traditional academic success yielded a low positive correlation with the students’ emotional intelligence assessment scores, and (d) female students showed significant gains in their overall EQ-i scores.

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Predictors of success: Medical Laboratory Associate in Science Degree Program

Hospitals and healthcare facilities in the United States are facing serious shortages of medical laboratory personnel, which, if not addressed, stand to negatively impact patient care. The problem is compounded by a reduction in the numbers of academic programs and resulting decrease in the number of graduates to keep up with the increase in industry demands. Given these challenges, the purpose of this study was to identify predictors of success for students in a selected 2-year Medical Laboratory Technology Associate in Science Degree Program. ^ This study examined five academic factors (College Placement Test Math and Reading scores, Cumulative GPA, Science GPA, and Professional [first semester laboratory courses] GPA) and, demographic data to see if any of these factors could predict program completion. The researcher examined academic records for a 10-year period (N =158). Using a retrospective model, the correlational analysis between the variables and completion revealed a significant relationship (p < .05) for CGPA, SGPA, CPT Math, and PGPA indicating that students with higher CGPA, SGPA, CPT Math, and PGPA were more likely to complete their degree in 2 years. Binary logistic regression analysis with the same academic variables revealed PGPA was the best predictor of program completion (p < .001). ^ Additionally, the findings in this study are consistent with the academic part of the Bean and Metzner Conceptual Model of Nontraditional Student Attrition which points to academic outcome variables such as GPA as affecting attrition. Thus, the findings in this study are important to students and educators in the field of Medical Laboratory Technology since PGPA is a predictor that can be used to provide early in-program intervention to the at-risk student, thus increasing the chances of successful timely completion.^

Profiling The Campus Recruiter At A Four-Year Hospitality Program

Profiling the Campus Recruiter At a Four-Year Hospitality Program, is a written profile, supported by anecdotal rather than stridently empirical evidence, by Al lzzolo, Assistant Professor, College of Hotel Administration, University of Nevada, Las Vegas. “Each year major chain corporations as well as single unit companies interview hospitality students throughout the country. A study conducted at the University of Nevada, Las Vegas, was designed to profile the hospitality industry campus recruiter and to provide meaningful data to college students who would be interviewing with these recruiters,” the author initially proffers. “Recruiting at the four-year hospitality program, by its nature, is not a science, nor is it highly quantifiable. The interviewing and selection processes are highly subjective and vary from company to company,” says Izzolo to preface his essay. “Data were collected via a questionnaire specifically designed to answer questions about the recruiters and/or the companies that sent interviewers to the placement office of the university's hospitality program,” our author says to explain the process used to gather information for the piece. Findings of the study indicate that the typical recruiter is male, college educated – but not necessarily in a Hospitality’ curriculum – and almost 80 percent of respondents said they had the authority to hire management trainees. Few campuses are visited by hospitality industry recruitment staff as evidenced by Izzolo’s observations/data. Table 3 analyzes the desirable traits a recruiter deems appropriate for the potential employee candidate. Personal appearance, work experience, grade point average, and verbal communication rank high on the list of distinguishable attributes. The most striking finding in this portion of the study is that a student’s GPA is virtually ignored. “Recruiting for the hospitality industry appears to be very subjective,” Izzolo says. “Recruiters are basing decisions to hire not on knowledge levels as determined by an academic grade point average but rather on criteria much less definitive, such as verbal skills and personal appearance,” our author opines. In closing, Izzolo concedes this is not a definitive study, but is merely a launching pad to a more comprehensive investigation on the recruitment subject.

The impact of a Classroom Performance System on learning gains in a biology course for science majors

This study was conducted to determine if the use of the technology known as Classroom Performance System (CPS), specifically referred to as "Clickers", improves the learning gains of students enrolled in a biology course for science majors. CPS is one of a group of developing technologies adapted for providing feedback in the classroom using a learner-centered approach. It supports and facilitates discussion among students and between them and teachers, and provides for participation by passive students. Advocates, influenced by constructivist theories, claim increased academic achievement. In science teaching, the results have been mixed, but there is some evidence of improvements in conceptual understanding. The study employed a pretest-posttest, non-equivalent groups experimental design. The sample consisted of 226 participants in six sections of a college biology course at a large community college in South Florida with two instructors trained in the use of clickers. Each instructor randomly selected their sections into CPS (treatment) and non-CPS (control) groups. All participants filled out a survey that included demographic data at the beginning of the semester. The treatment group used clicker questions throughout, with discussions as necessary, whereas the control groups answered the same questions as quizzes, similarly engaging in discussion where necessary. The learning gains were assessed on a pre/post-test basis. The average learning gains, defined as the actual gain divided by the possible gain, were slightly better in the treatment group than in the control group, but the difference was statistically non-significant. An Analysis of Covariance (ANCOVA) statistic with pretest scores as the covariate was conducted to test for significant differences between the treatment and control groups on the posttest. A second ANCOVA was used to determine the significance of differences between the treatment and control groups on the posttest scores, after controlling for sex, GPA, academic status, experience with clickers, and instructional style. The results indicated a small increase in learning gains but these were not statistically significant. The data did not support an increase in learning based on the use of the CPS technology. This study adds to the body of research that questions whether CPS technology merits classroom adaptation.

Achievement of generic baccalaureate student nurses using computer -assisted instruction simulations during a nursing review course

The use of computer assisted instruction (CAI) simulations as an instructional strategy provides nursing students with a critical thinking approach for evaluating risks and benefits and choosing correct alternatives in "safe" patient care situations. It was hypothesized that using CAI simulations during an upper level nursing review course would have a positive effect on the students' posttest scores. Subjects (n = 36) were senior nursing students enrolled in a nursing review course in an undergraduate baccalaureate program. A limitation of the study was the small sample size. The study employed a modified group experimental design using the t test for independent samples. The group who received the CAI simulations during the physiological system review demonstrated a significant increase (p $<$.01) in the posttest score mean when compared to the lecture-discussion group score mean. There was no significant difference between high and low clinical grade point average (GPA) students in the CAI and lecture-discussion groups and their score means on the posttest. However, score mean differences of the low clinical GPA students showed a greater increase for the CAI group than the lecture-discussion group. There was no significant difference between the groups in their system content subscore means on the exit examination completed three weeks later. It was concluded that CAI simulations are as effective as lecture-discussion in assisting upper level students to process information for clinical decision making. CAI simulations can be considered as an instructional strategy to supplement or replace lecture content during a review course, allowing more efficient use of faculty time. It is recommended that the study be repeated using a larger sample size. Further investigations are recommended in comparing the effectiveness of computer software formats and various instructional strategies for other learning situations and student populations. ^

Ethnic identity, self-esteem and academic factors in second -generation post-1970 Jamaican immigrants

Immigrants from Jamaica represent the largest number of migrants to the United States from the English speaking Caribbean. Research indicates that of all Caribbean immigrants they are most likely to retain the ethnic identity of their home country for the longest period of time. This dissertation explored the nature of ethnic identity and sought to determine its impact upon the additional variables of self-esteem and academic factors. A secondary analysis was carried out using data collected in the Spring of 1992 by Portes and Rumbaut on the children of immigrants attending the eighth and ninth grades in local schools in San Diego and southern Florida. A sample of 151 second-generation Jamaican immigrants was selected from the data set. ^ Six hypotheses yielded mixed results. Both parents who have a Jamaican ethnic identity present in the household are the best predictor Jamaican youth who retain a Jamaican ethnic identity. It was expected that ethnic identity would be a predictor of positive academic factors. The study showed that ethnic identity was not associated with one of the academic factors which were examined: help given with homework. ^ Neither family economic status nor parents' level of education played a significant role in the retention of Jamaican identity. Other findings were that there was no mean difference in the self-esteem scores of respondents who had similar ethnic identities to their parents and those who did not. There was also no difference found in the academic factors of either group. The study also showed that there was a small correlation between parent-child conflict and self-esteem. Specifically, the study found that the higher the conflict between youth and their parents, the lower the self-esteem of the youth. Finally it found that time lived in the U.S. was the best predictor of a higher GPA and it was also related to lower self-esteem. ^ Surprisingly, the study found that the relationship between ethnic identity and SES was the opposite of what was expected in that it found that SES was higher when there was no Jamaican identity. ^