Theoretical and experimental approach of fuel gas and carbon black production from coal tar pitch by thermal plasma process.

The processing of coal tar pitch (CTP) to produce clean fuel gas and carbon black (CB) is studied in a plasma reactor equipped with a direct-current plasma torch. The composition of the gas produced and energy costs were estimated theoretically for the CTP pyrolysis and gasification processes by two oxidants, namely oxygen and water vapor. We have found that the main gaseous compounds obtained in the pyrolysis and gasification processes are hydrogen (H2), carbon monoxide (CO), and very often carbon dioxide (CO2). For the pyrolysis case, the mean value of the synthesis gas concentration reaches a major value of 98 vol.% (H2 - 81 vol.%, CO - 17. vol.%). However, only 23% of the initial CTP is transformed into gas phase at 1100 K and its content increases up to 37.4% at a temperature of 3000 K. For oxygen gasification, the syngas quantity is little less compared to the pyrolysis case and attains 96.6 vol.% (H2 - 26.5 vol.%, CO - 70.1 vol.%) for T > 1100 K. An intermediate syngas content for the water steam gasification is 97.8 vol.% (with H2 - 55.8 vol.% and CO - 42.0 vol.%). The CB produced was composed of well-defined spherical particles of 30-nm size. Furthermore, it is composed of carbon (98.2%), and followed by oxygen (1.8%) with a surface area of 97 m2 g-1. The thermal plasma system shows high efficiency in conversion of CTP into high-value-added products.

Urinary creatinine as a nutritional and urinary volume marker in sheep fed with tropical or temperate forages / Uso da creatinina urinária como marcador nutricional e de volume urinário em ovinos alimentados com forragem tropical ou temperada

To test the accuracy of creatinine as a marker for estimating urinary volume and its use as a nutritional index, the possible interference of forage intake and forage quality over creatinine excretion was evaluated. For this, sheep were fed different levels of pearl millet (Pennisetum americanum(L) Leeke) or Italian ryegrass (Lolium multiflorum Lam). The experiment consisted of a compilation of digestibility trials (n=6) with pearl millet or Italian ryegrass in completely randomized designs with four replications and four forage levels: 1.5, 2.0, 2.5% (kg dry matter (DM)/ 100 kg of live weight (LW)). The trials were repeated at different periods to evaluate how stable the average metabolic excretion of creatinine is. In each trial, total urine collection was performed individually during a period of 24 hours for five consecutive days and subsequently analyzed by colorimetry for creatinine and purine derivatives. The creatinine excretion was not affected (P>0.05) by forage offer or forage type, but there were period effects (P=0.0001). The average creatinine excretion for both forages was 0.21mmol/kg PV0,75. Linear regressions between the purine derivatives:creatinine index with total excretion of purine derivatives were detected for pearl millet (P<0.0001, R2= 0.64) and Italian ryegrass (P=0.02, R2=0.20). These results demonstrate that creatinine excretion is independent of the type and availability of forage and can be a marker for urinary volume prediction and nutritional measures under grazing systems.

Para testar a precisão da creatinina como marcador para estimativas de volume urinário e índice nutricional, foram avaliadas a possível influência do consumo e a qualidade da forragem sobre esse marcador. Para isso, ovinos foram alimentados com diferentes níveis de milheto (Pennisetum americanum (L) Leeke) ou azevém (Lolium multiflorum Lam). O experimento consistiu de uma compilação de ensaios de digestibilidade (n=6) com milheto ou azevém, em um desenho experimental de blocos completamente ao acaso, com quatro repetições e quatro níveis de forragem: 1,5; 2,0; 2,5% (kg de matéria seca (MS)/ 100kg de peso vivo (PV)). Os ensaios foram repetidos em diferentes períodos, com ambas as forragens, se para avaliar a estabilidade da excreção média de creatinina metabólica. Em cada ensaio, foi coletado o volume total de urina individualmente, durante períodos de 24 horas, por cinco dias consecutivos. Posteriormente, esses ensaios foram analisados por colorimetria para creatinina e derivados de purina. A excreção de creatinina não foi afetada (P>0,05) pelo consumo de forragem ou pelo tipo de forragem, mas foi influenciada pelo período (P=0,0001). A excreção média de creatinina para ambas as forragens foi 0,21mmol/kg PV0,75. Regressões lineares entre os índices derivados de purina:creatinina com a excreção total de derivados de purina foram detectadas para milheto (P<0,0001; R2=0,64) e azevém (P=0,02; R2=0,20). Os resultados demonstraram que a excreção de creatinina é independente do tipo e do consumo de forragem e pode ser usada como marcador preditivo do volume urinário e do status nutricional em sistemas de pastejo.

Imaging the molecular channel in acetaldehyde photodissociation: roaming and transition state mechanisms.

The roaming dynamics in the photodissociation of acetaldehyde is studied through the first absorption band, in the wavelength interval ranging from 230 nm to 325 nm. Using a combination of the velocity-map imaging technique and rotational resonance enhanced multiphoton ionization (REMPI) spectroscopy of the CO fragment, the branching ratio between the canonical transition state and roaming dissociation mechanisms is obtained at each of the photolysis wavelengths studied. Upon one photon absorption, the molecule is excited to the first singlet excited S(1) state, which, depending on the excitation wavelength, either converts back to highly vibrationally excited ground S(0) state or undergoes intersystem crossing to the first excited triplet T(1) state, from where the molecule can dissociate over two main channels: the radical (CH(3) + HCO) and the molecular (CO + CH(4)) channels. Three dynamical regions are characterized: in the red edge of the absorption band, at excitation energies below the T(1) barrier, the ratio of the roaming dissociation channel increases, largely surpassing the transition state contribution. As the excitation wavelength is increased, the roaming propensity decreases reaching a minimum at wavelengths ∼308 nm. Towards the blue edge, at 230 nm, an upper limit of ∼50% has been estimated for the contribution of the roaming channel. The experimental results are interpreted in terms of the interaction between the different potential energy surfaces involved by means of ab initio stationary points and intrinsic reaction coordinate paths calculations.

A slice imaging and multisurface wave packet study of the photodissociation of CH3I at 304 nm.

The role of the conical intersection between the (1)Q(1) and (3)Q(0) excited states in the photodissociation of CH(3)I at 304 nm is investigated drawing a comparison between the adiabatic--through direct absorption to the (3)Q(1) state--and non-adiabatic--via the (1)Q(1)→(3)Q(0) conical intersection--production of I atoms in the ground (2)P(3/2) state. The versatility of the slice imaging technique in combination with resonance enhanced multiphoton ionization (REMPI) detection of I((2)P(3/2)) atoms allow distinct measurements of the competing processes. The I((2)P(3/2)) atom kinetic energy distributions (KEDs) obtained in both cases reflect inverted vibrational progressions of the ν(2) umbrella mode of the CH(3) co-product. The experimental results show a satisfactory agreement with multisurface wave packet calculations using a reduced dimensionality (pseudotriatomic) model carried out on the available ab initio potential energy surfaces.

Photodissociation of pyrrole-ammonia clusters by velocity map imaging: mechanism for the H-atom transfer reaction.

The photodissociation dynamics of pyrrole-ammonia clusters (PyH·(NH(3))(n), n = 2-6) has been studied using a combination of velocity map imaging and non-resonant detection of the NH(4)(NH(3))(n-1) products. The excited state hydrogen-atom transfer mechanism (ESHT) is evidenced through delayed ionization and presents a threshold around 236.6 nm, in agreement with previous reports. A high resolution determination of the kinetic energy distributions (KEDs) of the products reveals slow (∼0.15 eV) and structured distributions for all the ammonia cluster masses studied. The low values of the measured kinetic energy rule out the existence of a long-lived intermediate state, as it has been proposed previously. Instead, a direct N-H bond rupture, in the fashion of the photodissociation of bare pyrrole, is proposed. This assumption is supported by a careful analysis of the structure of the measured KEDs in terms of a discrete vibrational activity of the pyrrolyl co-fragment.

Imaging the radical channel in acetaldehyde photodissociation: competing mechanisms at energies close to the triplet exit barrier.

The photodissociation of acetaldehyde in the radical channel has been studied at wavelengths between 315 and 325 nm using the velocity-map imaging technique. Upon one-photon absorption at 315 nm, the molecule is excited to the first singlet excited state S(1), which, in turn, undergoes intersystem crossing to the first excited triplet state T(1). On the triplet surface, the molecule dissociates into CH(3) and HCO radicals with large kinetic energy release (KER), in accordance with the well characterized exit barrier on T(1). However, at longer wavelengths (>320 nm), which correspond to excitation energies just below the triplet barrier, a sudden change in KER is observed. At these photolysis wavelengths, there is not enough energy to surpass the exit barrier on the triplet state, which leaves the possibility of unimolecular dissociation on S(0) after internal conversion from S(1). We have characterized the fragments' KER at these wavelengths, as well as determined the energy partitioning for the radical fragments. A new accurate estimate of the barrier height on T(1) is presented.

A femtosecond velocity map imaging study on B-band predissociation in CH3I. I. The band origin.

A femtosecond pump-probe experiment, coupled with velocity map ion imaging, is reported on the second absorption band (B-band) of CH(3)I. The measurements provide a detailed picture of real-time B-band predissociation in the band origin at 201.2 nm. Several new data are reported. (i) A value of 1.5+/-0.1 ps has been obtained for the lifetime of the excited state, consistent within errors with the only other direct measurement of this quantity [A. P. Baronavski and J. C. Owrutsky, J. Chem. Phys. 108, 3445 (1998)]. (ii) It has been possible to measure the angular character of the transition directly through the observation of fragments appearing early with respect to both predissociation lifetime and molecular rotation. (iii) Vibrational activity in CH(3) has been found, both in the umbrella (nu(2)) and the symmetric stretch (nu(1)) modes, with estimates of relative populations. All these findings constitute a challenge and a test for much-wanted high level ab initio and dynamics calculations in this energy region.

The photodissociation of CH(3)I in the red edge of the A-band: Comparison between slice imaging experiments and multisurface wave packet calculations.

The photodissociation of methyl iodide at different wavelengths in the red edge of the A-band (286-333 nm) has been studied using a combination of slice imaging and resonance enhanced multiphoton ionization detection of the methyl fragment in the vibrational ground state (nu=0). The kinetic energy distributions (KED) of the produced CH(3)(nu=0) fragments show a vibrational structure, both in the I((2)P(3/2)) and I( *)((2)P(1/2)) channels, due to the contribution to the overall process of initial vibrational excitation in the nu(3)(C-I) mode of the parent CH(3)I. The structures observed in the KEDs shift toward upper vibrational excited levels of CH(3)I when the photolysis wavelength is increased. The I((2)P(3/2))/I( *)((2)P(1/2)) branching ratios, photofragment anisotropies, and the contribution of vibrational excitation of the parent CH(3)I are explained in terms of the contribution of the three excited surfaces involved in the photodissociation process, (3)Q(0), (1)Q(1), and (3)Q(1), as well as the probability of nonadiabatic curve crossing (1)Q(1)<--(3)Q(0). The experimental results are compared with multisurface wave packet calculations carried out using the available ab initio potential energy surfaces, transition moments, and nonadiabatic couplings, employing a reduced dimensionality (pseudotriatomic) model. A general qualitative good agreement has been found between theory and experiment, the most important discrepancies being in the I((2)P(3/2))/[I((2)P(3/2))+I( *)((2)P(1/2))] branching ratios. Inaccuracies of the available potential energy surfaces are the main reason for the discrepancies.

Imaging transient species in the femtosecond A-band photodissociation of CH3I.

A nonresonant femtosecond laser pulse centered at 802 nm is used to probe the real time photodissociation dynamics of CH(3)I in the A-band at 267 nm. Using multiphoton ionization with this probe laser pulse and velocity map ion imaging of CH(3)(+), we have followed the time evolution of the translational energy and spatial anisotropy of the CH(3) fragment, which in turn has permitted to image the C-I bond breaking from the initial Franck-Condon region up to the final products along the reaction coordinate. Given the temporal width of our pump and probe laser pulses (approximately 80 fs), a mechanism is proposed by which transient species are probed by simultaneous absorption of pump and probe laser pulses through intermediate Rydberg and ionic states of CH(3)I while the pump and probe pulses overlap in time. This study shows how the combination of femtosecond multiphoton ionization and ion imaging techniques provides an ideal tool to resolve in time the different stages of the bond breaking event in a polyatomic molecule.

Imaging the photodissociation of CH3SH in the first and second absorption bands: the CH3(X2A1)+SH(X2Pi) channel.

The CH3(X2A1)+SH(X2Pi) channel of the photodissociation of CH3SH has been investigated at several wavelengths in the first 1 1A"<--X 1A' and second 2 1A"<--X1A' absorption bands by means of velocity map imaging of the CH3 fragment. A fast highly anisotropic (beta=-1+/-0.1) CH3(X2A1) signal has been observed in the images at all the photolysis wavelengths studied, which is consistent with a direct dissociation process from an electronically excited state by cleavage of the C-S bond in the parent molecule. From the analysis of the CH3 images, vibrational populations of the SH(X2Pi) counterfragment have been extracted. In the second absorption band, the SH fragment is formed with an inverted vibrational distribution as a consequence of the forces acting in the crossing from the bound 2 1A" second excited state to the unbound 1 1A" first excited state. The internal energy of the SH radical increases as the photolysis wavelength decreases. In the case of photodissociation via the first excited state, the direct production of CH3 leaves the SH counterfragment with little internal excitation. Moreover, at the longer photolysis wavelengths corresponding to excitation to the 1 1A" state, a slower anisotropic CH3 channel has been observed (beta=-0.8+/-0.1) consistent with a two step photodissociation process, where the first step corresponds to the production of CH3S(X2E) radicals via cleavage of the S-H bond in CH3SH, followed by photodissociation of the nascent CH3S radicals yielding CH3(X2A1)+S(X3P0,1,2).

Slice imaging of the photodissociation of acetaldehyde at 248 nm. Evidence of a roaming mechanism.

The photodissociation of acetaldehyde in the molecular channel yielding CO and CH(4) at 248 nm has been studied, probing different rotational states of the CO(nu = 0) fragment by slice ion imaging using a 2+1 REMPI scheme at around 230 nm. From the slice images, clear evidence of the co-existence of two different mechanisms has been obtained. One of the mechanisms is consistent with the well-studied conventional transition state in which CO products appear rotationally excited, and the second is consistent with a roaming mechanism. This roaming mechanism is characterized by a low rotational energy disposal into the CO fragment as well as by a very low kinetic energy release, corresponding to a high internal energy in the CH(4) counter-fragment.

Low-temperature rotational relaxation of CO in self-collisions and in collisions with Ne and He.

The low-temperature rotational relaxation of CO in self-collisions and in collisions with the rare-gas atoms Ne and He has been investigated in supersonic expansions with a combination of resonance-enhanced multiphoton ionization (REMPI) spectroscopy and time-of-flight techniques. For the REMPI detection of CO, a novel 2 + 1' scheme has been employed through the A(1)Pi state of CO. From the measured data, average cross sections for rotational relaxation have been derived as a function of temperature in the range 5-100 K. For CO-Ne and CO-He, the relaxation cross sections grow, respectively, from values of approximately 20 and 7 A(2) at 100 K to values of approximately 65-70 and approximately 20 A(2) in the 5-20 K temperature range. The cross section for the relaxation of CO-CO grows from a value close to 40 A(2) at 100 K to a maximum of 60 A(2) at 20 K and then decreases again to 40 A(2) at 5 K. These results are qualitatively similar to those obtained previously with the same technique for N(2)-N(2), N(2)-Ne, and N(2)-He collisions, although in the low-temperature range (T < 20 K) the CO relaxation cross sections are significantly larger than those for N(2). Some discrepancies have been found between the present relaxation cross sections for CO-CO and CO-He and the values derived from electron-induced fluorescence experiments.

[Prevalence of fecal incontinence in diabetic patients: epidemiological study of patients assisted as outpatients at the Clinical Hospital of the Medical School at the University of São Paulo]. / Prevalência da incontinência anal no diabético: estudo epidemiológico com base na população atendida em regime ambulatorial no Hospital das Clínicas da Faculdade de Medicina da Universidade de São Paulo.

The object of this research was to establish the prevalence of fecal incontinence in those diabetics attended as outpatients at the Hospital das Clínicas da Faculdade de Medicina da Universidade de São Paulo. Individual verbal interviewing was the an adopted method. The classification of diabetes mellitus of World Health Organization was employed (1985). Data was aggregated relative sex, age, color, type of diabetes mellitus, fecal incontinence, duration of diabetes mellitus, peripheral neuropathy, intestinal habits (normal, constipation and diarrhea), urgency to evacuate, sensation of incomplete evacuation, urinary incontinence, vaginal deliveries and its characteristics. The study involved 258 diabetics, 167 of female sex having an average age of 56.2 years (17 to 78 years of age) and 91 of the male sex having average age of 55.8 years (10 to 74 years of age). With relation to color, 57% were white, 28.7% mullato, 11.2% black and 3.1% yellow. Fecal incontinence was prevalent in 18.6% of the cases studied. It occurred also in types I and II diabetics with predominance in the male sex. It also occurred in diabetics having an average history of 10.8 years to onset of illness. Peripheral neuropathy was observed in 8.5% of the diabetics investigated however no association was observed between the peripheral neuropathy and fecal incontinence. Constipation occurred in 29.5% of the patients and diarrhea in 21.3%. Incomplete evacuation was apparent in 15.1% of diabetics and urgency to evacuate in 12.8%. A relationship was identified between fecal incontinence with diarrhea and incomplete evacuation in the group investigated. Total vaginal deliveries was 458 with 70 episiotomies and 25 by forceps. There was no statistical evidence of association between the average number of vaginal deliveries, episiotomies and forceps in diabetics demonstrating or not demonstrating fecal incontinence. Urinary incontinence was more prevalent that fecal incontinence. No relationship was determined between urinary and fecal incontinence for the purpose of the present study.