Low-temperature oxidation of CO over Pd/CeO2-TiO2 catalysts with different pretreatments

A comprehensive study of the low-temperature oxidation of CO was conducted over Pd/TiO2, Pd/CeO2, and Pd/CeO2-TiO2 pretreated by a series of calcination and reduction processes. The catalysts were characterized by N-2 adsorption, XRD, H-2 chemisorption, and diffuse-reflectance infrared Fourier transform spectroscopy. The results indicated that Pd/CeO2-TiO2 has the highest activity among these catalysts, whether in the calcined state or in the reduced state. The activity of all of the catalysts can be improved significantly by the pre-reduction, and it seems that the reduction at low temperature (LTR. 150 degrees C) is more effective than that at high temperature (HTR, 500 degrees C), especially for Pd/CeO2 and Pd/TiO2. The catalysts with various supports and pretreatments are also different in the reaction mechanisms for CO oxidation at low temperature. Over Pd/TiO2, the reaction may proceed through a surface reaction between the weakly adsorbed CO and oxygen (Langmuir-Hinshelwood). For Ce-containing catalysts, however, an alteration of reaction mechanism with temperature and the involvement of the oxygen activation at different sites were observed, and the light-off profiles of the calcined Pd/CeO2 and Pd/CeOi-TiO2 show a distortion before CO conversion achieves 100%. At low temperature, CO oxidation proceeds mainly via the reaction between the adsorbed CO on Pd-0 sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface, whereas at high temperature it proceeds via the reaction between the adsorbed CO and oxygen. The high activity of Pd/CeO2-TiO2 for the low-temperature CO oxidation was probably due to the enhancements of both CO activation, caused by the facilitated reduction of Pd2+ to Pd-0, and oxygen activation, through the improvement of the surface oxygen supply and the oxygen vacancies formation. The reduction pretreatment enhances metal-support interactions and oxygen vacancy formation and hence improves the activity of CO oxidation. (c) 2005 Elsevier Inc. All rights reserved.

Low temperature heat capacity of (S)-ibuprofen

Molar heat capacities of ( S)-ibuprofen were precisely measured with a small sample precision automated adiabatic calorimeter over the temperature range from 80 to 370 K. Experimental heat capacities were fitted into a polynomial equation of heat capacities ( C-p,C- m) with reduced temperature ( X), [ X = f(T)]. The polynomial equations for ( S)-ibuprofen were C-p,C- m(s) = - 39.483 X-4 - 66. 649 X-3 + 95. 196 X-2 + 210. 84 X + 172. 98 in solid state and C-p,C- m(L) = 7. 191X(3) + 4. 2774 X-2 + 56. 365 X + 498. 5 in liquid state. The thermodynamic functions relative to the reference temperature of 298. 15 K, H-T - H-298.15 and S-T - S-298.15, were derived for the( S)-ibuprofen. A fusion transition at T-m = (324. 15 +/- 0. 02) K was found from the C-p - T curve. The molar enthalpy and entropy of the fusion transition were determined to be (18. 05 +/- 0. 31) kJ.mol(-1) and (55. 71 +/- 0. 95) J.mol(-1).K-1, respectively. The purity of the ( S)-ibuprofen was determined to be 99. 44% on the basis of the heat capacity measurement. Finally, the heat capacities of ( S)-ibuprofen and racemic ibuprofen were compared.

Alkanes-assisted low temperature formation of highly ordered SBA-15 with large cylindrical mesopores

Highly ordered SBA-15 silicas with large cylindrical mesopores (similar to 15 nm) are successfully obtained with the help of NH4F by controlling the initial reaction temperatures in the presence of excess amounts of alkanes.

Development of a triple stage heat transformer for the recycling of low temperature heat energy

Absorption heat transformers are thermodynamic systems which are capable of recycling industrial waste heat energy by increasing its temperature. Triple stage heat transformers (TAHTs) can increase the temperature of this waste heat by up to approximately 145˚C. The principle factors influencing the thermodynamic performance of a TAHT and general points of operating optima were identified using a multivariate statistical analysis, prior to using heat exchange network modelling techniques to dissect the design of the TAHT and systematically reassemble it in order to minimise internal exergy destruction within the unit. This enabled first and second law efficiency improvements of up to 18.8% and 31.5% respectively to be achieved compared to conventional TAHT designs. The economic feasibility of such a thermodynamically optimised cycle was investigated by applying it to an oil refinery in Ireland, demonstrating that in general the capital cost of a TAHT makes it difficult to achieve acceptable rates of return. Decreasing the TAHT's capital cost may be achieved by redesigning its individual pieces of equipment and reducing their size. The potential benefits of using a bubble column absorber were therefore investigated in this thesis. An experimental bubble column was constructed and used to track the collapse of steam bubbles being absorbed into a hotter lithium bromide salt solution. Extremely high mass transfer coefficients of approximately 0.0012m/s were observed, showing significant improvements over previously investigated absorbers. Two separate models were developed, namely a combined heat and mass transfer model describing the rate of collapse of the bubbles, and a stochastic model describing the hydrodynamic motion of the collapsing vapour bubbles taking into consideration random fluctuations observed in the experimental data. Both models showed good agreement with the collected data, and demonstrated that the difference between the solution's temperature and its boiling temperature is the primary factor influencing the absorber's performance.

Ultra-fine pitch stencil printing for a low cost and low temperature flip-chip assembly process

This paper presents the results of a packaging process based on the stencil printing of isotropic conductive adhesives (ICAs) that form the interconnections of flip-chip bonded electronic packages. Ultra-fine pitch (sub-100-mum), low temperature (100degC), and low cost flip-chip assembly is demonstrated. The article details recent advances in electroformed stencil manufacturing that use microengineering techniques to enable stencil fabrication at apertures sizes down to 20mum and pitches as small as 30mum. The current state of the art for stencil printing of ICAs and solder paste is limited between 150-mum and 200-mum pitch. The ICAs-based interconnects considered in this article have been stencil printed successfully down to 50-mum pitch with consistent printing demonstrated at 90-mum pitch size. The structural integrity or the stencil after framing and printing is also investigated through experimentation and computational modeling. The assembly of a flip-chip package based on copper column bumped die and ICA deposits stencil printed at sub-100-mum pitch is described. Computational fluid dynamics modeling of the print performance provides an indicator on the optimum print parameters. Finally, an organic light emitting diode display chip is packaged using this assembly process

Low temperature crystal structures of two rhodanine derivatives, 3-amino rhodanine and 3-methyl rhodanine: geometry of the rhodanine ring

Rhodanines (2-thio-4-oxothiazolidines) are synthetic small molecular weight organic molecules with diverse applications in biochemistry, medicinal chemistry, photochemistry, coordination chemistry and industry. The X-ray crystal structure determination of two rhodanine derivatives, namely (I), 3-aminorhodanine [3-amino-2-thio-4-oxothiazolidine], C3H4N2OS2, and (II) 3-methylrhodanine [3-methyl-2-thio-4-oxothiazolidine], C4H5NOS2, have been conducted at 100 K. I crystallizes in the monoclinic space group P2(1)/n with unit cell parameters a = 9.662(2), b = 9.234(2), c = 13.384(2) angstrom, beta = 105.425(3)degrees, V = 1151.1(3) angstrom(3), Z = 8 (2 independent molecules per asymmetric unit), density (calculated) = 1.710 mg/m(3), absorption coefficient = 0.815 mm(-1). II crystallizes in the orthorhombic space group Iba2 with unit cell a = 20.117(4), b = 23.449(5), c = 7.852(2) angstrom, V = 3703.9(12) angstrom(3), Z = 24 (three independent molecules per asymmetric unit), density (calculated) = 1.584 mg/m(3), absorption coefficient 0.755 mm(-1). For I in the final refinement cycle the data/restraints/parameter ratios were 2639/0/161, goodness-of-fit on F-2 = 0.934, final R indices [I > 2sigma(I)] were R1 = 0.0299, wR2 = 0.0545 and R indices (all data) R1 = 0.0399, wR2 = 0.0568. The largest difference peak and hole were 0.402 and -0.259 e angstrom(-3). For II in the final refinement cycle the data/restraints/parameter ratios were 3372/1/221, goodness-of-fit on F(2) = 0.950, final R indices [I > 2sigma(I)] were R1 = 0.0407, wR2 = 0.1048 and R indices (all data) R1 = 0.0450, wR2 = 0.1088. The absolute structure parameter = 0.19(9) and largest difference peak and hole 0.934 and -0.301 e angstrom(-3). Details of the geometry of the five molecules (two for I and three for II) and the crystal structures are fully discussed. Corresponding features of the molecular geometry are highly consistent and firmly establish the geometry of the rhodanine

Central nervous system drugs: Low temperature X-ray structures of (I) the base 5-(2,3-dichlorophenyl)-2,4-diamino-6-fluoromethyl-pyrimidine (4030W92) and (II) 5-(2,6-dichlorophenyl)-1-H-2,4-diamino-6-methyl-pyrimidine methanesulphonic acid salt (227C89)

The X-ray crystal structures of (I), the base 4030W92, 5-(2,3-dichlorophenyl)-2,4-diamino-6-fluoromethyl-pyrimidine, C11H9Cl2FN4, and (II) 227C89, the methanesulphonic acid salt of 5-(2,6-dichlorophenyl)-1-H-2,4-diamino-6-methyl-pyrimidine, C11H11Cl2N4 center dot CH3O3S, have been carried out at low temperature. A detailed comparison of the two structures is given. Structure (I) is non-centrosymmetric, crystallizing in space group P2(1) with unit cell a = 10.821(3), b = 8.290(3), c = 13.819(4) angstrom, beta = 105.980(6)degrees, V = 1191.8(6) angstrom(3), Z = 4 (two molecules per asymmetric unit) and density (calculated) = 1.600 mg/m(3). Structure (II) crystallizes in the triclinic space group P (1) over bar with unit cell a = 7.686(2), b = 8.233(2), c = 12.234(2) angstrom, alpha = 78.379(4), beta = 87.195(4), gamma = 86.811(4)degrees, V = 756.6(2) angstrom(3), Z = 2, density (calculated) = 1.603 mg/m(3). Final R indices [I > 2sigma(I)] are R1 = 0.0572, wR2 = 0.1003 for (I) and R1 = 0.0558, wR2 = 0.0982 for (II). R indices (all data) are R1 = 0.0983, wR2 = 0.1116 for (I) and R1 = 0.1009, wR2 = 0.1117 for (II). 5- Phenyl-2,4 diaminopyrimidine and 6-phenyl-1,2,4 triazine derivatives, which include lamotrigine (3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine), have been investigated for some time for their effects on the central nervous system. The three dimensional structures reported here form part of a newly developed data base for the detailed investigation of members of this structural series and their biological activities.

Low temperature crystal structure of N-Acetyl-L-Glutamic acid: comparison with the DFT calculated structure

N-acetyl-L-glutamic acid, crystallizes in the orthorhombic space group P2(1)2(1)2(1) with unit cell parameters a = 4.747(3), b = 12.852(7), c = 13.906(7) Å, V = 848.5(8) Å3, Z = 4, density (calculated) = 1.481 mg/m3, linear absorption coefficient 0.127 mm−1. The crystal structure determination was carried out with MoKalpha X-ray data measured with liquid nitrogen cooling at 100(2) K temperature. In the final refinement cycle the data/restraints/parameter ratios were 1,691/0/131; goodness-of-fit on F(2) = 1.122. Final R indices for [I > 2sigma(I)] were R1 = 0.0430, wR2 = 0.0878 and R indices (all data) R1 = 0.0473, wR2 = 0.0894. The largest electron density difference peak and hole were 0.207 and −0.154 eÅ(−3). Details of the molecular geometry are discussed and compared with a model DFT structure calculated using Gaussian 98.