Analytical Chemistry Commons^™

Kinetics And Activation Energy Parameters For Hydrolysis Of Acetic Anhydride In A Water-Acetone Cosolvent System, Samson Olowoyo

Electronic Theses and Dissertations

The hydrolysis of acetic anhydride is a widely-studied liquid phase reaction studied since 1906. Different approaches have been used to study the kinetics of this reaction. Approaches used by researchers have involved the use of sophisticated experimental set-ups. In this work, the pH technique has been adopted which involves the use of a pH meter to monitor the hydrolysis reaction. Analysis of the hydrolysis reaction has been performed for water/acetone cosolvent systems over a range of temperatures and mole fractions. Eyring analysis was performed under isomole fraction conditions and activation enthalpy, entropy, and Gibbs free energy for hydrolysis of acetic …

Eyring Activation Energy Analysis Of Acetic Anhydride Hydrolysis In Acetonitrile Cosolvent Systems, Nathan Mitchell

Electronic Theses and Dissertations

Acetic anhydride hydrolysis in water is considered a standard reaction for investigating activation energy parameters using cosolvents. Hydrolysis in water/acetonitrile cosolvent is monitored by measuring pH vs. time at temperatures from 15.0 to 40.0 °C and mole fraction of water from 1 to 0.750. This work utilizes a temperature controlled water bath and a Vernier glass-body pH probe with Vernier Logger Pro 3.10.1 software for automated data collection. Data analysis is used to determine observed kinetic rate constants under the assumption that hydrolysis is a pseudo-first-order reaction. Eyring plots were used to compare activation energy parameters under iso-mole fraction conditions. …

Phosphomolybdic Acid Catalysis Of Cellulose Hydrolysis, Troy R. Dolmetsch

Undergraduate Honors Theses

Renewable sources such as cellulose derived biofuels are sought after in order to replace fossil fuel sources that are currently used to meet energy demands. Cellulose is a biological polymer composed of a chain of glucose molecules. Hydrolysis of cellulosic materials then has potential to serve as a source of renewable energy in the form of biofuels. The crystalline structure of cellulose is very stable, and current methods of catalyzed hydrolysis are inefficient for industrial application. This project explores the use of phosphomolybdic acid (PMA) in water to catalyze hydrolysis of microcrystalline cellulose. Temperature of hydrolysis was varied from 40 …

Hydrogen Molybdenum Bronze Catalyzed Hydrolysis Of Cellulose, Claire O. Baker

Undergraduate Honors Theses

In recent years, there has been increasing concern with respect to the large dependence across the globe on nonrenewable energy sources, such as fossil fuels. Ethanol has been explored, however, in alleviating this problem; cellulose, a polymer of glucose molecules, is a precursor to this potentially useful biofuel. However, the strength and rigidity of the cellulose structure has proven to be a difficult obstacle to overcome in this multistep synthesis. Harsh conditions are required, often including concentrated sulfuric acid and extremely high temperatures, to complete hydrolysis to a useful extent. In this work, the hydrolysis of cellulose was performed with …

Functionalized Silica Gel For Adsorption Of Cesium From Solution, Kenneth Marshall Seaton Iii

Electronic Theses and Dissertations

Mesoporous silica gel containing embedded phosphotungstic acid (PTA) was synthesized by sol-gel co-condensation of tetraethyl orthosilicate with PTA in acidic media. The obtained material had high Brunauer-Emmett-Teller Theory (BET) surface area and pore volume. A characteristic band of the Keggin structure of PTA was present in its FT-IR spectrum while its X-ray diffraction patterns were absent. This proved the embedding of PTA on a sub-molecular level and not as a second phase. Acidic sites were determined by neutralization with base in aprotic solvent, followed by titration of the remaining base with an acid. The material demonstrated high adsorption capacity of …

Extracting (1,3/1,6)-Β-Glucans From Saccharomyces Cerevisiae: A Fungal Immunotherapeutic, James C. Elliott

Undergraduate Honors Theses

The goal of this research was the development of a method to extract pure (1,3/1,6)-β-glucans from Saccharomyces cerevisiae. These β-glucans are of pharmaceutical importance because an animal’s immune system can recognize glucan molecules, and these molecules can act as immunomodulators, essentially turning on the immune system. The problem in the past has been that previously published methods produce β-glucans with low side chain lengths and few branching occurrences. This issue was tackled by a multivariable approach that reduced extraction steps, initial sample size, and concentrations of reagents used. This method has been shown to produce greater yields of β-glucans while …

Immobilization Of Heteropolyacids In Silica Gel, Opeyemi Adetola

Electronic Theses and Dissertations

Silica gels containing incorporated heteropolyacids (HPAs) were synthesized in acidic media by co-condensation of tetraethoxysilane (TEOS) with phosphotungstic or phosphomolybdic acids using sol-gel technique. Effect of the synthesis conditions on their structure and morphology was studied. Yields of modified materials were some lower as compared to non-modified silica gels. All materials were mesoporous but contained micropores in their structures. Presence of bands of Keggin’s structures in FT-IR spectra along with absence of XRD patterns of crystalline HPAs confirmed their fine incorporation into silica network. Particle sizes of modified materials were 800-1100 nm excepting for W-containing sample obtained with trimethylstearylammonium chloride. …

Facilitating Conceptual Learning In Quantitative Chemistry, Sarah R. Johnson

Electronic Theses and Dissertations

Traditional chemistry laboratory courses have a manual consisting of “step-by-step” experiments; instructions are given to complete experiments, requiring minimal information/concepts processing to be successful. This experience leaves students unprepared for the real-world, where critical thinking skills are needed to conduct research. This study focused on building analytical techniques, conceptual knowledge, and critical thinking skills used to solve research problems. A new quantitative chemistry laboratory manual was developed to transition students from traditional to inquiry-based experiments, requiring analytical method development. Data showed students having less difficulty using the new manual (0.8281 average difficulty) on method development exam questions and experiments, compared …

Linkage Analysis And Compositional Studies Of Β-Glucan From Saccharomyces Cerevisiae And Compositional Studies Of Mannan From Candida Albicans, Clara Arthur

Electronic Theses and Dissertations

The efficacy of a novel carbohydrate extraction procedure was investigated with methylation analysis and alditol acetate method by Gas Chromatography-Mass Spectrometry. A published extraction procedure for β-glucans was compared to one developed in house. Both procedures gave a dominant glucose peak in the Gas chromatogram indicative of successful β-glucan isolation. Further linkage studies showed four linkage positions for β-glucans isolated with the published method; terminal, 1,3-linkage, 1,6-linkage and 1,3,6-linkage, while β-glucans isolated using the new method showed six linkage positions; terminal, 1,3-linkage, 1,6-linkage, 1,4-linkage, 1,2,3-linkage and 1,3,6-linkage. Diminishing β-glucan linkage peaks in the chromatogram for the published method indicated structure …

Optimized Acid/Base Extraction And Structural Characterization Of Β-Glucan From Saccharomyces Cerevisiae, Shardrack O. Asare

Electronic Theses and Dissertations

β-glucan is a major component of the fungal cell wall consisting of (1→3)-β linked glucose polymers with (1→6)-β linked side chains. The published classical isolation procedure of β-glucan from Saccharomyces cerevisiae is expensive and time-consuming. Thus, the aim of this research was to develop an effective procedure for the extraction of glucans. We have developed a new method for glucan extraction that will be cost effective and will maintain the native structure of the glucan. The method that we developed is 80% faster and utilizes ¹/₃ of the reagents compared to the published classical method. Further, the method …

The Analysis Of The Decomposition Of Hydrogen Peroxide Using A Schiff Base Copper Complex By Cyclic Voltammetry, Gavin James Rustin Mr.

Undergraduate Honors Theses

Copper(II) complexes of Schiff bases can be used in the catalysis of hydrogen peroxide to create water and oxygen. The mechanism and the kinetics of this disproportionation reaction by a dimeric copper(II) complex [CuSALAD]₂ are studied in this experiment, where SALAD refers to a Schiff Base ligand formed from salicyaldehyde and 1S,2S-D(+)-1-phenyl-2-amino-1,3-propanediol. By using cyclic voltammetry, the oxidation-reduction processes of a reaction may be monitored. The [CuSALAD]­₂ is initially reacted with a base such as imidazole to form the catalytic species, and the ratio of the copper(II) complex to the imidazole was found to be 1:4, consistent with …

Study Of Immobilizing Cadmium Selenide Quantum Dots In Selected Polymers For Application In Peroxyoxalate Chemiluminescence Flow Injection Analysis, Christopher S. Moore

Electronic Theses and Dissertations

Two batches of CdSe QDs with different sizes were synthesized for immobilizing in polyisoprene (PI), polymethylmethacrylate (PMMA), and low-density polyethylene (LDPE). The combinations of QDs and polymer substrates were evaluated for their analytical fit-for-use in applicable immunoassays. Hydrogen peroxide standards were injected into the flow injection analyzer (FIA) constructed to simulate enzyme-generated hydrogen peroxide reacting with bis-(2,4,6-trichlorophenyl) oxalate.

Linear correlations between hydrogen peroxide and chemilumenscent intensities yielded regression values greater than 0.9750 for hydrogen peroxide concentrations between 1.0 x 10^-4 M and 1.0 x 10^-1 M. The developed technique’s LOD was approximately 10 ppm. Variability of the prepared …

Survey Of Flavonoids And Their Distribution In Different Kinds Of Onions Using High Performance Liquid Chromatography And Gas Chromatography Mass Spectrometry., Archana Racharla

Electronic Theses and Dissertations

This research is done to determine the distribution of flavonoids in diverse varieties of onions (commercial and wild onions). Reflux extraction method was done on dried onions and the abstracts were analyzed subsequently by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GCMS). Statistical calculations were done to see if there are significant differences in the varieties of onions studied from the chromatographic profiles obtained. The chromatograms obtained were patterned using visual observations, scatter plot study, correlation co-efficient, and ANOVA to evaluate the significant difference of the distribution of flavonoids in varieties of onions. The organic white onions seem …

Determination Of Select Metal Ions In Commercially Available Conventional And Organic Baby Foods., Neva S. Winters

Electronic Theses and Dissertations

The goal of this study is to determine whether or not there is an appreciable difference between concentrations of various metal ions present in conventionally grown and processed and organically grown and processed baby foods. Two prominent, commercially available brands were chosen to undergo comparative studies between both their own conventional and organic varieties of second stage green beans and carrots. Samples were tested for cadmium, calcium, iron, lead, nickel, and zinc. Two containers of each variety of baby food were sampled in triplicate, with purchases of foods being made in separate areas to ensure that each set came from …

Computational Investigation Of Spin Traps Using Hybrid Solvation Models., Sai Sriharsha Manoj Konda

Electronic Theses and Dissertations

The cyclic nitrone 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), and the lesser known linear phenyl-N-tert-butylnitrone (PBN) and its phosphorylated analogues have been used as spin traps for the investigation of free radicals in biological systems. Theoretical work on these molecules suggests that there are important differences in their properties between biological systems and isolated molecules in the gas phase, most likely resulting from intra and intermolecular hydrogen bonding. Most dielectric solvation models such as the polarized continuum model and COSMO are incapable of direct determination of solvent-spin trap chemical interactions. To examine this, hybrid models incorporating COSMO for long range effects and discrete solvent …

Studies Of The Preparations And Use Of Sol-Gel For Enzyme Immobilization And Analytical Applications., Suzana Hamdan

Electronic Theses and Dissertations

Much attention has been paid to immobilization of enzymes to improve enzyme stability and permit its reuse. Glucose oxidase entrapment in different kinds of silica sol-gel matrices was investigated. The enzyme showed stable activity for 11 uses in the sol-gel with tetramethyl orthosilicate (TMOS) as precursor, and at least 7 uses in the sol-gel induced electrochemically with tetraethyl orthosilicate (TEOS) as precursor. The sol-gel made with TEOS as precursor and HCl as catalyst showed stability in enzyme activity for 11 uses but the activity decreases on the same sol-gel when modified with silica nanoparticles. Factors such as optimal incubation time …

Studies Of Capsaicinoids Contents Of Locally Grown And Commercial Chilies Using Reversed-Phase High Performance Liquid Chromatography., John Kailemia Muchena

Electronic Theses and Dissertations

Capsaicinoids are a class of compounds responsible for the "heat" of hot peppers. Capsaicin and dihydrocapsaicin have the highest burning effect. The aim of this work is to separate and quantify the two major capsaicinoids in fruits harvested at different stages of development and at different seasons. Simple and rapid HPLC method involves 73:27% methanol water mobile phase with C₁₈ stationary phase and UV-Vis detector set at 210 nm. The method showed good reproducibility with 1.74% - 4.72% relative standard deviations, a linear response within 0.65–45.5 and 0.25-17.5 μg/mL for capsaicin and dihydrocapsaicin, respectively. The method achieved average recovery …

Studies Of Surfactants Effect On Riboflavin Fluorescence And Its Determination In Commercial Food Products And Vitamin Tablets., William Emmanuel Ghann

Electronic Theses and Dissertations

A simple and economical fluorometer using blue LEDs excitation sources and simple PMT detection had been built, assembled, optimized, and employed for measurement of fluorescence from riboflavin (vitamin B₂). Surfactants have been known to enhance the intensity of fluorescence of fluorescent compounds. Fluorescence analysis of riboflavin in the presence of various anionic, cationic, and nonionic surfactants was also conducted to determine if they could improve analysis. However, the surfactants employed did not seem to have any meaningful enhancement; in fact, some actually diminished the fluorescence intensity of riboflavin. The procedure was linear for riboflavin from 0.01 to 2.5 …

Study On Methods Of Simultaneous Multi-Component Analysis., Jennifer Bernice Ashie

Electronic Theses and Dissertations

Many new instrumentation and different instrumental techniques have been developed to deal with increasing complexity of samples encountered. Many researchers also have coupled these instrumental techniques with chemometric algorithms to assist in the quantitative analysis of multi-component samples in the hope of alleviating the need of tedious separation and cleanup procedures. These newer chemometric procedures tend to be complex and difficult to understand and implement and are successful under different circumstances and conditions. In this study, we start from the very simple beginning and examine the factors that can present difficulties with obtaining the correct results and observe how the …

Monitoring Metal Containing Particulates Distribution On A College Campus Using Dandelion (Taraxacum Officinale) Leaves As Receptors., Suresh Chandra Regmi

Electronic Theses and Dissertations

This study aims to determine the distribution of particulates carrying heavy metals at selected sites on a college campus using dandelion leaves as collectors. As a comparison, sites far away from the campus surrounding Bristol Motor Speedway Car Racing Stadium were also monitored. To reduce the probability of memory effects from the long-term atmospheric deposition or absorption of metals from soil a seasonal plant, dandelion, was used to monitor the metal contents. The metals monitored are cadmium, calcium, copper, chromium, iron, lead, and zinc. Fourteen sites were monitored and samples were collected once a week initially (growing time of the …

Characterization Of Commercial Pectin Preparations By Spectroscopic And Chromatographic Techniques., Daniel Wayne Dixon

Electronic Theses and Dissertations

Pectin has a long history as a food additive. However, elucidation of its fine structural and property relationships remains elusive. Recent research has focused on pectin's ability to complex with divalent heavy metals to aid in characterizing it. Commercial pectins of unknown composition were obtained from local grocers. Purified pectin samples from orange peel, lemon peel, and apple pomace, each of low and high levels of methyl esterification and of unknown distribution pattern were also purchased. Instead of metal complexation, several highly absorbing dyes such as Ruthenium Red, Nile Blue, and Acridine Orange were used to complex with the pectins …

A Computational Chemistry Study Of Spin Traps., Jacob Fosso-Tande

Electronic Theses and Dissertations

Many defects in physiological processes are due to free radical damage: reactive oxygen species, nitric oxide, and hydroxyl radicals have been implicated in the parthenogenesis of cancer, diabetes mellitus, and rheumatoid arthritis. We herein characterize the phenyl-N-ter-butyl nitrone (PBN) type spin traps in conjunction with the most studied dimethyl-1-pyrroline-N-oxide (DMPO) type spin traps using the hydroxyl radical. In this study, theoretical calculations are carried out on the two main types of spin traps (DMPO and PBN) at the density functional theory level (DFT). The energies of the optimized structures, hyperfine calculations in gaseous and aqueous phases of the spin traps …

Reversed-Phase Hplc Determination Of Citral In Locally Grown Lemon Grass Harvested At Different Season., Mahmoud Al-Shaer

Electronic Theses and Dissertations

A simple HPLC procedure for the quantitative determination of citral, the major fragrant component in the lemon grass, has been developed. The procedure involves a C-8 stationary phase using a 90:10 methanol: water pH 5 mobile phase containing 0.25% 1-octanesulfonic acid and an UV detector (set at 233 nm). The lemon grass leaves were harvested fresh at different times of the year and were soaked in methanol for 48 hours without any mechanical assistance to extract the citral and other methanol soluble components. The method showed good reproducibility with relative standard deviation of 2.8% and 10.8% for two different sets …

Determination Of Cholesterol In Foods By Flow Injection Analysis With Perroxyoxalate Chemiluminescence., Abisake Feleke

Electronic Theses and Dissertations

Cholesterol is an important biological molecule with many important functions. However, high serum cholesterol is a health hazard. Thus analysis of cholesterol is important and many analytical techniques have been developed. The objectives of the proposed research are to develop an economical, rapid method for the determination of total cholesterol with good selectivity and enhanced sensitivity. For evaluation of proposed flow injection analysis with peroxyoxalate chemiluminescence (FIA-POCL) method, figures of merit such as accuracy, precision, and linear dynamic range will be assessed. The proposed procedure was then applied to the determination of total cholesterol in foods. The procedure was linear …

A Characterization Of Extractable, Hydroxylated Fatty Acid Bearing Components In Legionella Pneumophila, Jonathan R. Lane

Electronic Theses and Dissertations

Extraction of the lipids of Legionella pneumophila yields phases unlike those produced from other Gram-negative bacteria. A viscous interface forms between the aqueous (wash) and organic phases. More than half of the hydroxylated fatty acids were found distributed between the aqueous phase and the interfacial material, fractions in which such constituents have not been reported in other Gram-negative species. It was further observed that after the material from the aqueous/interfacial phase was dissolved in methanol or chloroform/methanol (2:1 (V/V)), the addition of acetone would create a white, flocculent precipitate. Analyses showed that the supernatant contained fatty acids that were nonhydroxylated …