Surface Properties of Calcinated Titanium Dioxide Probed by Solvatochromic Indicators: Relevance to Catalytic Applications

Titanium dioxide was obtained by hydrolysis of the corresponding ethoxide, followed by washing, drying, and calcination at 80, 160, 240, 320, 400, and 700 C, respectively. The following surface properties of the solids obtained were determined as a function of the calcinations temperature: T(Calcn); area by the BET method; BrOnsted acidity by titration with sodium hydroxide; empirical polarity, ET(30); Lewis acidity, alpha(Surf); Lewis basicity, beta(Surf); and dipolarity/polarizability pi*(Sturf), by use of solvatochromic indicators. Except for le surf whose value increased slightly, heating the samples resulted in a decrease of all of the above-mentioned surface properties, due to the decrease of surface hydroxyl groups. This conclusion has been corroborated by FTIR. Values of E(T)(30), alpha(Surf), and pi*(Surf) are higher than those of water and alcohols; the BrOnsted and Lewis acidities of the samples correlate linearly. The advantages of using solvatochromic indicators to probe the surface properties and relevance of the results to the applications of TiO(2) are discussed.

Crystal and molecular structures of three 2-sulphur-substituted cyclohexanones studied by X-ray crystallography and by ab initio molecular orbital calculations

The conformational features of three 2-sulphur-substituted cyclohexanone derivatives, which differ in the number of sulphur-bound oxygen atoms, i.e. zero (I), one (II) and two (III), were investigated by single crystal X-ray crystallography and geometry optimized structures determined using Hartree-Fock method. In each of (I)-(III) an intramolecular S center dot center dot center dot O(carbonyl) interaction is found with the magnitude correlated with the oxidation state of the sulphur atom, i.e. 2.838(3) angstrom in (I) to 2.924(2) angstrom in (II) to 3.0973(18) angstrom in (III). There is an inverse relationship between the strength of this interaction and the magnitude of the carbonyl bond. The supramolecular aggregation patterns are primarily determined by C-H center dot center dot center dot O contacts and are similarly influenced by the number of oxygen atoms in the molecular structures. Thus, a supramolecular chain is found in the crystal structure of (I). With an additional oxygen atom available to participate in C-H center dot center dot center dot O interactions, as in (II), a two-dimensional array is found. Finally, a three-dimensional network is found for (III). Despite there being differences in conformations between the experimental structures and those calculated in the gas-phase, the S center dot center dot center dot O interactions persist. The presence of intermolecular C-H center dot center dot center dot O interactions involving the cyclohexanone-carbonyl group in the solid-state, disrupts the stabilising intramolecular C-H center dot center dot center dot O interaction in the energetically-favoured conformation. (I): C(12)H(13)NO(3)S, triclinic space group P (1) over bar with a = 5.392(3) angstrom b = 10.731(6) angstrom, c = 11.075(6) angstrom, alpha = 113.424(4)degrees, beta = 94.167(9)degrees, gamma = 98.444(6)degrees, V = 575.5(6) angstrom(3), Z = 2, R(1) = 0.052; (II): C(12)H(13)NO(4)S, monoclinic P2(1)/n, a = 7.3506(15) angstrom, b = 6.7814(14) angstrom, c = 23.479(5) angstrom, beta = 92.94(3)degrees, V = 1168.8(4) angstrom(3), Z = 4, R(1) = 0.046; (III): C(12)H(13)NO(5)S, monoclinic P2(1)/c, a = 5.5491(11) angstrom, b = 24.146(3) angstrom, c = 11.124(3) angstrom, beta = 114.590(10)degrees, V = 1355.3(5) angstrom(3), Z = 4, R(1) = 0.051.

Hydrogen peroxide and supercritical carbon dioxide: a new bleaching stage for Eucalyptus kraft-O(2) pulps

Kraft pulp is currently bleached largely by the elemental chlorine free (ECF) technology with oxygen, chlorine dioxide, and hydrogen as active agents. This technology brought about significant environmental improvements in relation to standard processes based on chlorine gas and hypochlorite, but there is still need for further improvements. This study presents a novel environmentally friendly bleaching stage - the so-called `hydrogen peroxide in supercritical carbon dioxide`, P((SC-CO2)) - that can be adapted to current ECF bleaching processes, with preference in cases where hydrogen peroxide is already used. In this study, the P((SC-CO2)) stage was evaluated as a replacement to the last peroxide stage of the D(EP)DP bleaching sequence and to the first peroxide stage of the D(EP)DP sequence, for an oxygen delignified eucalypt kraft-O(2) pulp. The P((SC-CO2)) stage was run with 0.5% hydrogen peroxide, at 15% consistency, 70 degrees C, and 73 bar. The reaction time was 30 min. The performances of regular P stages and the new P((SC-CO2)) stage were compared. Promising results were observed with the DEP((SC-CO2))DP sequence; the P((SC-CO2)) decreased kappa number from 2.7 to 2.1, and the hexenuronic acid groups from 17.0 to 12.4 mmol kg(-1). The P((SC-CO2)) stage showed poor performance when applied in the D(EP)DP((SC-CO2)) sequence. It is concluded that the process presents potential but requires further optimization to improve selectivity and efficiency.

Carbon dioxide reforming of ethanol over Ni/Y(2)O(3)-ZrO(2) catalysts

Supported nickel catalysts of composition Ni/Y(2)O(3)-ZrO(2) were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y(2)O(3)-ZrO(2) in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO(2) conversion of 61% on the 5NiYZ catalyst at 800 degrees C, representing a better response than for the catalyst of the same composition prepared by wet impregnation. (C) 2009 Published by Elsevier B.V.

Imprensa e educação ambiental: poluição do ar por dióxido de enxofre (SO2) no município do Rio de Janeiro

Este trabalho tem como objetivo primeiro analisar o tratamento que a grande imprensa dispensou às notícias relativas à poluição do ar por dióxido de enxofre (S02) no município do Rio de Janeiro, nos anos de 1982-83. Foram consultados os seguintes diários: Jornal do Brasil, O Globo, Ultima Hora, Tribuna da Imprensa e O Dia. O primeiro capítulo apresenta a situação administrativa, legislativa e histórica do município do Rio de Janeiro, após o que julgamos importante a apresentação dos vãrios conceitos existentes sobre meio ambiente. Fornecemos também um quadro da situação ambiental de nosso municfpio. O capítulo terceiro discute então o que vem a ser educação ambiental sob vãrios pontos de vista. Procuramos também situar os jornais como educadores não formais e questionamos o cumprimento, pelos jornais da função que lhe e primeira: informar a população dos fatos que a cerca.

Effect of steeping conditions (sulfur dioxide, lactic acid, and temperature) on starch yield, starch quality, and germ quality from the Intermittent Milling and Dynamic Steeping process (IMDS) for a Brazilian corn hybrid

Effect of lactic acid, SO2, temperature, and their interactions were assessed on the dynamic steeping of a Brazilian dent corn (hybrid XL 606) to determine the ideal relationship among these variables to improve the wet-milling process for starch and corn by-products production. A 2x2x3 factorial experimental design was used with SO2 levels of 0.05 and 0.1% (w/v), lactic acid levels of 0 and 0.5% (v/v), and temperatures of 52, 60, and 68degreesC. Starch yield was used as deciding factor to choose the best treatment. Lactic acid added in the steep solution improved the starch yield by an average of 5.6 percentage points. SO2 was more available to break down the structural protein network at 0.1% than at the 0.05% level. Starch-gluten separation was difficult at 68degreesC. The lactic acid and SO2 concentrations and steeping temperatures for better starch recovery were 0.5, 0.1, and 52degreesC, respectively. The Intermittent Milling and Dynamic Steeping (IMDS) process produced, on average, 1.4% more starch than the conventional 36- hr steeping process. Protein in starch, oil content in germ, and germ damage were used as quality factors. Total steep time can be reduced from 36 hr for conventional wet-milling to 8 hr for the IMDS process.

Study of the carbon dioxide chemical fixation-activation by guanidines

Fixation of CO2 is one of the most important priorities of the scientific community dedicated to reduce global warming. In this work, we propose new methods for the fixation of CO2 using the guanidine bases tetramethylguanidine (TMG) and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]-pyrimidine (TBD). In order to understand the reactions occurring during the CO2 fixation and release processes, we employed several experimental methods, including solution and solid-state NMR, FTIR, and coupled TGA-FTIR. Quantum mechanical NMR calculations were also carried out. Based on the results obtained, we concluded that CO2 fixation with both TMG and TBD guanidines is a kinetically reversible process, and the corresponding fixation products have proved to be useful as transcarboxylating compounds. Afterward, CO2 thermal releasing from this fixation product with TBD was found to be an interesting process for CO2 capture and isolation purposes. (C) 2008 Elsevier Ltd. All rights reserved.

Selectivity of the cyclic carbonate formation by fixation of carbon dioxide into epoxides catalyzed by Lewis bases

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Photocatalytic Degradation of Phenol by Thermal Titanium Dioxide Thin Layer Electrodes

Electrochemical processes in industrial effluents have been studied as a means to obtain higher efficiency in wastewater treatment. Heterogeneous photocatalysis appears as a low-cost alternative through the use of lower wattage lamps and thermal TiO2 films. Photocatalysis became a clean process for water treatment due to hydroxyl radicals generated on semiconductor surface. Such radicals are able to degrade several organic compounds. This study used different electrodes and analytical methods for degradation of phenol molecules to reduce treatment costs, improve efficiency, and identify compounds formed during the decomposition of phenolic molecules. Thermal growth of TiO2 film was observed on the titanium electrode in rutile form. Application of an electrical potential on the Ti/TiO2 working electrode increases efficiency in reducing concentration of phenol after photocatalytic treatment. Still, high energy radiation (UVC) showed best degradation rates in photolytic process. Different compounds formed during the degradation of phenol were also identified in the UVC-PE treatment.

Carbon dioxide formation during initial stages of photodegradation of poly(ethyleneterephthalate) (PET) films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Surgical treatment of squamous cell carcinoma of tongue with carbon dioxide laser radiation (CO2)

In this clinical study, we proposed to observe the efficacy of the treatment of squamous cell carcinoma of the tongue (SCCT) by carbon dioxide (CO2) laser surgery. Twelve patients with SCCT were treated with excisional surgery using the CO2 laser with a spot size of 0.8 mm, 10 W, power density of 2.5 W/cm(2) in continuous mode, and under constant vacuum removal of the plume. The post surgical clinical evaluations were done every day until the sutures were removed and then every 7 days up to 1 month postoperatively. Subjects were re-examined quarterly until the fifth year post surgery. After 5 yr of follow-up for all subjects, there was no recurrence of the SCCT at the involved sites. The functional and aesthetic results observed were excellent. It is concluded that CO2 laser ablation of SCCT is an extremely useful surgical technique that can provide a clean field and is capable of providing surgical results consistent with accepted principles of oncological surgery. (C) 2012 Laser Institute of America.

The effect of Sb and Nb on the electrical conductivity of tin dioxide based ceramics

The electrical conductivity of Mn doped SnO2 systems prepared by an organic route (Pechini's method) has been investigated as a function of antimony and niobium concentration. The conductivity increases with the increase of both concentration ions, however, in a different manner. While the conductivity of niobium doped ceramics increases with the power of 1.6 for the entire range of concentrations studied (0.01-0.7 mol%), the conductivity of antimony doped ceramics increases with the power of 1.9 in the range 0.01-0.05 mol% of Sb; 3.7 in the range 0.05-0.30 mol% and 1.8 in the range 0.30-0.70 mol%. This behavior is attributed to the existence of two stable oxidation states for antimony: Sb3+ and Sb5+, while for niobium there is only one: Nb5+. The power of 3.7 for Sb would be related to the segregation of this ion on the grain boundary accompanied by an additional contribution coming from the substitution of Sn2+ by Sb3+ on the grain surface.

Carbon dioxide efflux in a rhodic hapludox as affected by tillage systems in southern Brazil

Os solos agrícolas podem atuar como dreno ou fonte de C atmosférico, dependendo do sistema de manejo adotado. Este estudo foi desenvolvido em experimento de longa duração (22 anos), durante o período de 30 dias do outono, com o objetivo de avaliar o impacto de sistemas de preparo de solo (preparo convencional-PC e plantio direto-PD) nas emissões de C-CO2 de um Latossolo Vermelho distrófico, em Cruz Alta, RS. As emissões de C-CO2 do solo foram avaliadas com câmaras dinâmica (Flux Chamber 6400-09, Licor) e estática (com captação em solução alcalina), imediatamente após a colheita da soja. A temperatura e a umidade do solo foram registradas, concomitantemente com as emissões de C-CO2, por meio de sensor de temperatura e TDR manual, respectivamente, integrantes do Licor-6400. Estimou-se que, em 30 dias, uma quantidade equivalente a menos de 30 % do C aportado pelos resíduos de soja foi emitida na forma de C-CO2. As emissões de C-CO2 no solo em PD foram similares às emissões do solo em PC, independentemente do tipo de câmara utilizada. Diferenças entre sistemas de preparo quanto à emissão de C-CO2, avaliadas com a câmara dinâmica, foram verificadas somente a curto prazo (leituras diárias), com o PD apresentando maiores emissões do que o PC no início do período experimental e menores no final. A câmara dinâmica foi mais eficiente do que a estática em captar as alterações das emissões de C-CO2 em função da variação da temperatura e a porosidade preenchida por água (PPA) no solo em PD, as quais explicaram 83 e 62 % das emissões de C-CO2, respectivamente. O fator Q10, que avalia a sensibilidade da emissão de C-CO2 à temperatura do solo, foi estimado em 3,93, indicando alta sensibilidade da atividade microbiana à temperatura do solo durante o outono. As emissões de C-CO2 registradas no solo em PD com a câmara estática foram correlacionadas às da câmara dinâmica, porém com valores subestimados em relação àquela notadamente nos maiores valores de fluxo. em condições de baixa temperatura e PPA, o preparo de solo induziu limitado incremento de emissão de C-CO2.

Study on the use of oxidant scrubbers for elimination of interferences due to nitrogen dioxide in analysis of atmospheric dimethylsulfide

Neste trabalho foi avaliado o desempenho de filtros para dióxido de nitrogênio, buscando evitar perdas durante a amostragem de sulfetos orgânicos, provocadas por oxidantes atmosféricos. Diferentes compostos e misturas foram usadas para recobrir superfícies sólidas empregadas na preparação destes filtros. Um sistema automatizado de análise em fluxo foi utilizado para comparar a eficiência de retenção de dióxido de nitrogênio pelos filtros. Entre os materiais testados na preparação dos filtros, as melhores escolhas foram papel ou lã de vidro impregnados com a mistura de sulfato de ferro (II), ácido sulfúrico e ácido pirogalico e ainda os filtros feitos de papel impregnados com trietanolamina. Os resultados obtidos em laboratório com mistura de gás padrão de dimetilsulfeto e experimentos em campo confirmaram a qualidade dos filtros e indicaram que eles podem ser utilizados para evitar a oxidação de sulfetos orgânicos durante a sua amostragem.