Cavity-enhanced spectroscopies for applications of remote sensing, chemical kinetics and detection of radical species

This thesis describes applications of cavity enhanced spectroscopy towards applications of remote sensing, chemical kinetics and detection of transient radical molecular species. Both direct absorption spectroscopy and cavity ring-down spectroscopy are used in this work. Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was utilized for measurements of spectral lineshapes of O₂ and CO₂ for obtaining laboratory reference data in support of NASA’s OCO-2 mission. FS-CRDS is highly sensitive (> 10 km absorption path length) and precise (> 10000:1 SNR), making it ideal to study subtle non-Voigt lineshape effects. In addition, these advantages of FS-CRDS were further extended for measuring kinetic isotope effects: A dual-wavelength variation of FS-CRDS was used for measuring precise D/H and ¹³C/¹²C methane isotope ratios (sigma>0.026%) for the purpose of measuring the temperature dependent kinetic isotope effects of methane oxidation with O(¹D) and OH radicals. Finally, direct absorption spectroscopic detection of the trans-DOCO radical via a frequency combs spectrometer was conducted in collaboration with professor Jun Ye at JILA/University of Colorado.

Chemical and electrochemical investigations of cobalt cyanide and ruthenium ammine complexes

Part I.

The stoichiometry and kinetics of the reaction between Co(CN₅H^3- and HgX₂ (X = CN, OH) have been investigated. The products of the reaction are two new complexes, [(NC)₅Co-HgX]^3- and [(NC)₅Co-Hg-Co(CN)₅]^6-, whose spectra are reported. The kinetic measurements produced a value for the forward rate constant of the reaction Co(CN)₅H^3- + OH^- k₁/k_-1 Co(CN)₅^4- +H₂O, k1 = (9.7 ± 0.8) x 10^-2 M^-1 sec^-1 at 24°C, and an equilibrium constant for the reaction K = 10^-6 M^-1.

Part II.

Unusually large and sharp "adsorption waves" appear in cyclic voltammograms of Co(CN)₅^3- and several cobalt(III) pentacyano complexes at stationary mercury electrodes. The nature of the adsorbed species and the reasons for the absence of the adsorption waves in polarograms taken with a d.m.e. have been examined. The data are compatible with the adsorption, in all cases, of a coordinatively unsaturated cobalt(II) complex, Co(CN)₄^2-, by means of a cobalt-mercury bond. When the resulting adsorbed complex is reduced, a series of subsequent chemical and electrode reactions is initiated in which three faradays of charge are consumed for each mole of adsorbed complex. The adsorption of the anionic complex strongly retards the reduction of other negatively charged complexes.

Part III.

A number of formal redox potentials for Ru^III (NH₃)₅L + e = Ru^II (NH₃)₅L and Ru^III(NH₃)₄L₂ + e = Ru^II (NH₃)₄L₂ (where L is various ligands) has been measured by cyclic voltammetry, potentiometry, and polarography and are discussed in terms of the properties of the ligands, such as π-accepting capability. Reduction of coordinated pyrazine in the complexes, Ru(NH₃)₅ Pz²⁺, cis- and trans-Ru(NH₃)₄Pz₂²⁺, on a mercury electrode has been observed. The behavior of this reduction in various acidity of the solution as well as the reoxidation of the reduction products are discussed.

An investigation of the kinetics of CO2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO2 at temperatures of ca. 750 °C of a synthetic sorbent composed of 15 wt% mayenite (Ca12Al14O33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation–calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model – the size distribution of grains – was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation.

An investigation of the kinetics of CO 2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO 2 at temperatures of ca. 750°C of a synthetic sorbent composed of 15wt% mayenite (Ca 12Al 14O 33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation-calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model - the size distribution of grains - was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation. © 2011 Elsevier Ltd.

Topologically invariant reaction coordinates for simulating multistate chemical reactions.

Evaluating free energy profiles of chemical reactions in complex environments such as solvents and enzymes requires extensive sampling, which is usually performed by potential of mean force (PMF) techniques. The reliability of the sampling depends not only on the applied PMF method but also the reaction coordinate space within the dynamics is biased. In contrast to simple geometrical collective variables that depend only on the positions of the atomic coordinates of the reactants, the E(gap) reaction coordinate (the energy difference obtained by evaluating a suitable force field using reactant and product state topologies) has the unique property that it is able to take environmental effects into account leading to better convergence, a more faithful description of the transition state ensemble and therefore more accurate free energy profiles. However, E(gap) requires predefined topologies and is therefore inapplicable for multistate reactions, in which the barrier between the chemically equivalent topologies is comparable to the reaction activation barrier, because undesired "side reactions" occur. In this article, we introduce a new energy-based collective variable by generalizing the E(gap) reaction coordinate such that it becomes invariant to equivalent topologies and show that it yields more well behaved free energy profiles than simpler geometrical reaction coordinates.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

CO2-gasification of a lignite coal in the presence of an iron-based oxygen carrier for chemical-looping combustion

Chemical-looping combustion (CLC) has the inherent property of separating the product CO2 from flue gases. Instead of air, it uses an oxygen carrier, usually in the form of a metal oxide, to provide oxygen for combustion. All techniques so far proposed for chemical looping with solid fuels involve initially the gasification of the solid fuel in order for the gaseous products to react with the oxygen carrier. Here, the rates of gasification of coal were compared when gasification was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. This enabled an examination of the ability of chemical looping materials to enhance the rate of gasification of solid fuels. Batch gasification and chemical-looping combustion experiments with a German lignite and its char are reported, using an electrically-heated fluidised bed reactor at temperatures from 1073 to 1223 K. The fluidising gas was CO2 in nitrogen. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. A numerical model was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at about 20% conversion when (i) the surface area for reaction was at its maximum and (ii) because of the accompanying increase in porosity and pore size, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle. Excellent agreement was observed between the rates predicted by the numerical model and those observed experimentally. ©2013 Elsevier Ltd. All rights reserved.

Parasitic reaction and its effect on the growth rate of AlN by metalorganic chemical vapor deposition

The Al composition of metalorganic chemical vapor deposition (MOCVD)-grown AlGaN alloy layers is found to be greatly influenced by the parasitic reaction between ammonia (NH3) and trimethylaluminum (TMAI). The growth process of AlN is carefully investigated by monitoring the in situ optical reflection. The abnormal dependencies of growth rate on growth temperature, reactor pressure, and flux of NH3 are observed and can be well explained by the effect of parasitic reaction. The increase of growth rate with increasing flux of TMAI is found to depend on the growth temperature and reactor pressure due to the presence of parasitic effect. A relatively low growth temperature and a reduced reactor pressure are suggested for the effective decrease of parasitic reaction during the MOCVD growth of AlN and probably lead to a more effective incorporation of Al into the AlGaN layers. (c) 2005 Elsevier B.V. All rights reserved.

Kinetics and transport model for the chemical vapor epitaxy of GexSi1-x

A numerical model that combines mass transport and surface kinetics was applied, for the first time, to the chemical vapor epitaxy of GexSi1-x. The temperature, velocity and concentration fields were calculated from the conservation equations for energy, momentum and species coupled with the boundary conditions on the growth surface which were determined by surface kinetics. The deposition rates of Si and Ge were assumed to be limited, respectively, by surface kinetics and mass transport. A theoretical relation between the initial conditions and the Ge composition in the solid was established. The calculated growth rate as well as the Ge composition in the solid and its dependence on growth temperature agree well with experimental data.

Combined Effects of Hot Curing Conditions and Reaction Heat on Rubber Vulcanization Efficiency and Vulcanizate Uniformity

A mathematical model of the chemical kinetics of silicone rubber Vulcanization is developed, with the thermal effects being computed using the increment method, and the hot Vulcanization process estimated with the finite element method. The results show that the reaction heat of rubber vulcanization is important for energy saving, and that a proper curing medium temperature is important when considering both vulcanization efficiency and vulcanizate uniformity. The results also indicate that increases in the forced convective heat transfer coefficient have no significant effect above a certain level. The validity of the numerical model is indirectly proven by comparison with existing data.

A quantitative HPLC method for determining lactide content using hydrolytic kinetics

A new method for quantitative analysis of lactide has been developed by applying chemical kinetics to a HPLC system. The most important advance is its practical approach to the quantification of analytes that are unstable in the HPLC mobile phase. In HPLC analysis, anhydrous mobile phases cannot separate lactide from impurities, and only mixtures of water and organic solvent can achieve effective separation. By selecting conditions for testing and studying the kinetics of lactide hydrolysis, extensive experiments revealed that lactide degradation can be treated as a pseudo-first-order reaction under the given HPLC conditions, and lactide content or purity can be quantitatively determined. This method is practical for measuring the purity of the intermediate lactide in polylactic acid (PLA) production and the lactide content in PLA.

Extraction kinetics of Sc(III), Y(III), La(III) and Gd(III) from chloride medium by Cyanex 302 in heptane using the constant interfacial cell with laminar flow

The extraction kinetics of Sc, Y, La and Gd(III) from the hydrochloric acid medium using Cyanex 302 (hereafter HL) in heptane solution have been measured by the constant interfacial cell with laminar flow. Reaction regions are explored at liquid-liquid interface. Extraction regimes are deduced to be diffusion-controlled for Sc(Ill) and mixed controlled for Y, La and Gd(Ill). Extraction mechanisms are discussed according to the dimeric model of Cyanex 302 in non-polar solution. From the temperature dependence of rate measurement, the values of E-a, Delta H-+/-, Delta S-+/- and Delta G(300)(+/-) are calculated and it is found that the absolute values of these parameters keep crescent trend for Sc, Y, La and Gd(III). At the same time, it is found that it can easily achieve the mutual separation among the Sc, Y and La(III) with kinetics extraction methods.

Design of silicone rubber according to requirements based on the multi-objective optimization of chemical reactions

The explicit expression between composition and mechanical properties of silicone rubber was derived from the physics of polymer elasticity, the implicit expression among material composition, reaction conditions and reaction efficiency was obtained from chemical thermodynamics and kinetics, and then an implicit multi-objective optimization model was constructed. Genetic algorithm was applied to optimize material composition and reaction conditions, and the finite element method of cross-linking reaction processes was used to solve multi-objective functions, on the basis of which a new optimization methodology of crosslinking reaction processes was established. Using this methodology, rubber materials can be designed according to pre-specified requirements.