Line width parameters for a number of spectral lines in the pure rotational spectrum of formaldehyde (CH20) and formic acid (HCOOH) have been measured using a sourcemodulated microwave spectrograph. All transitions studied in this investigation were of the type ΔJ=O (i.e. Q-branch transitions), with ΔK-1=0 and ΔK+1 =+l. The center frequencies of the measured lines varied from 8662.0 MHz to 48612.70 MHz. The experimentally determined collision diameters for self broadening interactions involving HCOOH and CH2 Q molecules were found to be 2 - 27 per cent less than those calculated by the Murphy-Boggs theory of collision broadening. Much better agreement between a simplified broadening scheme for symmetric top molecules and the observed foreign-gas collision diameters is obtained by using Birnbaum's theory.

This dissertation thesis consists of six chapters. The main focus of this study is the need for understanding the reaction mechanism and intermediates formed on Pt-modified Au surface as anode catalysts in the formic acid fuel cells. Chapter 1 gives an introduction to formic acid and methanol fuel cells, an overview of the current catalysts employed at the anode of the fuel cells, specifically the Pt-modified Au electrodes as potential catalysts and the different deposition methods for preparing this catalytic surface. Information about different electrochemical methods used like cyclic voltammetry and potential step method along with other characterization methods and spectroscopic techniques has also been given. As one of the main methods to characterize the catalysts, Raman and surface enhanced Raman spectroscopy have been discussed in detail. The electrooxidation of formic acid and the nature of the intermediates at a platinum-modified gold surface prepared through spontaneous deposition were characterized using a combination of electrochemistry and in situ surface enhanced Raman spectroscopy (SERS). Spontaneously deposited platinum on gold showed unique high catalytic activity for formic acid electrooxidation. The oxidation current of formic acid is more than five times higher on the Pt-modified gold electrode surface than on a bare Pt surface and about 72 times higher than on a bare Au surface. SERS results reveal the involvement of a novel HCOO− adsorbate at 300 cm−1. Both electrochemical and spectroscopic results suggest that the formic acid electrooxidation takes place by the dehydrogenation pathway involving a low frequency formate intermediate on the Pt-modified gold electrode catalyst. Next, the effect of the deposition solution employed in the spontaneous deposition process was explored and demonstrated to play an important role in catalytic activity of these surfaces. Electrochemical studies show that Pt-modified Au surfaces prepared from bromoplatinate solution are most active in oxidizing formic acid. The second most active surface for formic acid electrooxidation was that from chloroplatinate followed by that from the iodoplatinate solutions. Also, the optimal condition to prepare the most active surface is different for various haloplatinate solutions. In situ surface enhanced Raman spectroscopy (SERS) with potential control revealed the presence of formate at 300 cm-1 as the reaction intermediate in the catalytic processes on all three Pt-modified Au surfaces, but with different potential-dependent behaviors. A clear and transparent bis ethylenedioxy tetrathiafulvalene iodine doped polymer films (BEDO-TTF) was successfully prepared by electrochemical method of cyclic voltammetry. The formation of the transparent films has been linked to the reduction of the iodine species in the film to iodide species giving rise to colorless films. Furthermore, Raman studies have revealed the presence of different iodide species like triodide, pentaiodide and iodine when anodic and cathodic potentials were applied to the films. Also, it was seen that the iodine was complexed with the BEDO-TTF polymer in a stoichiometry of 2.4: 3 [(BEDO-TTF) 2.4I3] at certain concentration in the doping technique. Raman studies were also conducted on single walled carbon nanotubes (SWCNTs) to study the defects introduced during the ball milling procedure and Ru doping. The Raman results reveal that both ball milling procedure and Ru doping leads to the formation of more defects and carbonaceous species in the SWCNTs. Thus, both electrochemical and Raman method were demonstrated to characterize the composition and properties of various materials including conducting polymer and carbon nanotubes

Includes bibliographical references (leaves 59-79) Examines the metabolism of volatile fatty acid and formic acid in fed sheep. Develops a method for analysing and qualifying volatile fatty acids with special reference to formic acid in biological fluids by High-Performance Liquid Chromatography.

A systematic study of formic acid electrooxidation on polycrystalline palladium is presented. The study begins with a discussion on the oxide growth process on platinum and palladium. CO electrooxidation under controlled mass transport is studied in order to elucidate the manner in which Pd interacts with CO, a proposed poisoning species in formic acid oxidation. The mechanism of formic acid oxidation is studied using various potentiodynamic techniques, including dynamic electrochemical impedance spectroscopy, which provides impedance measurements during a voltammogram. Through kinetic analysis, a model for the oxidation was developed. The impedance measurements support both the dc measurements as well as the results of the oxidation model. It was determined that CO formation was slow on Pd within the time scale of the experiments. The chief cause of surface deactivate was then determined to be the Pd surface interaction with the (bi)sulfate adsorption in the double layer region. / Graduate

Ritmos biológicos são regulados por mecanismos homeostáticos que asseguram a confiabilidade funcional do relógio fisiológico independentemente de mudanças de temperatura no ambiente. Compensação de temperatura, ou a independência do período oscilatório em relação à temperatura, é conhecida por exercer um papel central em muitos ritmos biológicos, mas um fenômeno raro em osciladores químicos. Estudou-se nessa dissertação a influência da temperatura na dinâmica oscilatória durante a oxidação catalítica de ácido fórmico sobre eletrodo de platina policristalina. Os experimentos foram conduzidos em cinco temperaturas diferentes de 5 à 25 ºC, e as oscilações foram estudadas sob controle galvanostático. Resultados experimentais foram comparados a um novo modelo proposto para a eletro-oxidação de ácido fórmico, considerando formato como intermediário ativo e a desidrogenação da água em altos potenciais. Sob condições oscilatórias apenas comportamento anti-Arrhenius foi observado. Sobre-compensação com coeficiente de temperatura (q10, definido como a razão entre a constante de velocidade à temperatura T + 10 ºC e em T) < 1 é achada para a maioria dos casos, exceto em altas correntes aplicadas onde compensação de temperatura, q10 ~ 1 predomina. O comportamento do período e amplitude resulta de uma combinação complexa entre a temperatura e corrente aplicada ou, equivalentemente, a distância do equilíbrio termodinâmico. Altas energias de ativação aparente foram obtidas em condições voltamétricas, não-oscilatórias, as quais implicam que o comportamento anti-Arrhenius observado sob regime oscilatório resulta de um acoplamento entre as rotas reacionais em vez de uma fraca dependência da temperatura nas etapas elementares. Mecanisticamente, os experimentos e o modelo matemático sugerem que o período em regime de (sobre)compensação de temperatura durante a eletro-oxidação de ácido fórmico sobre platina é governado pelo acoplamento entre as taxas reacionais de formação/remoção de monóxido de carbono e formato em condições oscilatórias. / Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, i.e. the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. It was studied in this master thesis the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 ºC, and the oscillations studied under galvanostatic control. Experimental results are compared to a new model proposed for formic acid electro-oxidation, which includes formate as an active intermediate and water dehydrogenation at high potentials. Under oscillatory conditions only non-Arrhenius behavior is observed. Over-compensation with temperature coefficient (q10, defined as the ratio between the rate constants at temperature T + 10 ºC and at T) < 1 is found in most cases, except that temperature compensation with q10 ~ 1 predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, non-oscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than from a weak temperature dependence of the individual steps. Mechanistically, the experiments and the mathematical model suggest that the period in temperature (over)compensation regime during electro-oxidation of formic acid at platinum is governed by the coupling among the reaction rates of formation/removal of carbon monoxide and formate coverage in oscillatory conditions.

Abstract More than 900 papers related to organosolv pulping have been reviewed in this thesis. From the information included in those papers it can be concluded that organosolv pulping processes are still in a developing stage and are not yet ready to seriously threat the position of the kraft process as the main pulp manufacturing process in the world. Distillation seems to be the main alternative as the process for recovering the solvent in organosolv pulping. A good reason for this is that using simple distillation no potentially harmful components are introduced to the process. The effect of feed composition on the operation of a separation sequence in an organosolv process using aqueous formic and acetic acids and corresponding peroxyacids was studied. When simple distillation was used as the separation method the effect was found to be significant. The no ideal nature of the formic acid-acetic acid-water mixture, which separation was studied, makes the ternary composition space to divide into four distillation regions. Which region the feed is located in, obviously determines the economy of the distillation sequence. Shortcut calculation methods cannot be recommended to be used for designing a distillation sequence for the ternary mixture studied, but they give useful information for the comparison of such sequences. They were used to choose a limited number of alternatives for studies with rigorous calculation methods. Minimum work of separation can also be used to make a satisfying estimate for the relative easiness of separation of the formic acid-acetic acid-water mixture. Thermal integration using pinch technology was also tested and found very useful for decreasing the thermal energy consumption of distillation processes. Thermodynamic efficiencies for separating the formic acid-acetic acid-water mixture by simple distillation were estimated. They were found to be lower than the average value for distillation presented in literature.

Problems presented in this paper concern the chemical equilibrium of methyl alcohol, formic acid, and methyl formate when combined.

The green production of formic acid and utilization of methanol over heterogeneous catalysis system were investigated in this study. The heterogeneous catalysts are widely used in the chemical industry. They offer high stability and reusability which can enhance the production ability and lower the production cost, it can be considered as the sustainable energy solution for the future. In this work, we demonstrated several different heterogeneous catalysts for sustainable formic acid production and methanol utilization, including the heteropoly acid supported mesoporous silica catalysts and multi-function mixed metal oxide catalysts. Detailed characterizations of the final products were carried out by N2 adsorption and desorption, XRD, HR-TEM, SEM, ICP-OES, XANES, NH3- TPD, Raman spectroscopy, and FTIR to identify the chemical properties and physical properties of the catalysts. We obtained 60 % glycerol conversion and 30 % formic acid selectivity with at least 3 rounds of usages in batch system over PV1Mo/SBA-15-p-DS catalyst. Moreover, the continuous methyl formate production with significantly high formation rate (16.7) has been achieved via our CuMgO-based catalysts, and the best Cu5MgO5 catalyst gives more than 80 % methanol conversion with constant selectivity to methyl formate even after 4 catalytic test (more than 200 h), revealing their potential for industrialization. For the methanol utilization reaction, the methanol homocoupling to form dimethoxymethane (DMM) has been investigated. The redox and acidic properties of catalysts both play a critical role in this reaction and the related to different product. The supported V2O5 catalyst achieves the best catalytic performance (62.1 % conversion and 85.6 % DMM selectivity) with a Ce/Al specific ratio of 1. This research not only provided the efficient catalysts for numerous application with high activity, but also discovered the relation between the catalytic performance and the nature of the materials. These findings might further help the researcher to solve the global environmental and energy issues in the near future.

Formic acid (FA) has been considered as one of the most promising materials for hydrogen storage today. The catalytic decarboxylation of formic acid ideally leads to the formation of CO2 and H2, and such CO2/H2 mixtures can be successfully applied in fuel cells. A large number of transition-metal based homogeneous catalysts with high activity and selectivity have been reported for the formic acid decarboxylation. In this presentation, we report ruthenium and rhodium complexes containing an N, N′-diimine ligand for the selective decomposition of formic acid to H2 and CO2 in water in the absence of any organic additives. Among them, the Ru complex could provide a TOF (turnover frequency) of 12 000 h–1 and a TON (turnover number) of 350 000 at 90 °C in the HCOOH/HCOONa aqueous solution. In addition to that, efficient production of high-pressure H2 and CO2 (24.0 MPa (3480 psi)) was achieved through the decomposition of formic acid with no formation of CO by this Ru complex. Moreover, well-defined ruthenium (II) PN3P pincer complexes were also developed for the reversible reaction-hydrogenation of carbon dioxide. Excellent product selectivity and catalytic activity with TOF and TON up to 13,000 h-1 and 33,000, respectively, in a THF/H2O biphasic system were achieved. Notably, effective conversion of carbon dioxide from the air into formate was conducted in the presence of an amine, allowing easy product separation and catalyst recycling.

The importance of Hydrogen (H2) in current global energy systems is undeniable. Moving from the energy systems depending on fossil fuel to energy systems that are carbon-free is a necessity, thus solutions such as hydrogen economy is required. Especially after recent geopolitical challenges in Europe which could make the energy acquisition a crucial problem. Liquid organic hydrogen carriers (LOHC) are applicable pathways for transitioning H2 into energy and to avoid the storage and transportation limitations of gaseous and liquid H2. Formic acid (FA) is an attractive alternative for such purposes due to its minimal level of toxicity and its significant volumetric storage capacity for H2. In this study, a Life cycle assessment (LCA) of the supply chain involving the Trans-Atlantic export of energy from Canada to Germany is conducted using formic acid as a LOHC and OxFA process to convert biomass to formic acid. The environmental impacts of all units and processes involved in this supply chain are examined, and the results are compared against other traditional systems for hydrogen production. A sensitivity analysis was also performed to recognize the crucial contributors and assess the processes and units that impose considerable influence on the overall environmental impact. / Thesis / Master of Applied Science (MASc) / Hydrogen (H2) plays a crucial role in transitioning from fossil fuel-based to carbon-free energy systems, a shift highlighted by recent geopolitical challenges in Europe. Liquid organic hydrogen carriers (LOHC) offer a solution for hydrogen storage and transport issues associated with its gaseous and liquid states. Formic acid (FA) is particularly promising as a LOHC due to its low toxicity and high hydrogen storage capacity. This study conducts a Life Cycle Assessment (LCA) of a supply chain that uses formic acid to export energy from Canada to Germany, involving the OxFA process for converting biomass to formic acid. The environmental impacts of all processes in this supply chain are evaluated and compared with traditional hydrogen production methods. Additionally, a sensitivity analysis identifies key contributors and assesses their impact on the overall environmental footprint.