Introduction Silver catalysts possess unique catalytic properties in the epoxidation of non-allylic alkenes. A high loading of silver, low-surface-area support (α-Al 2 O 3 ) and promoter(s) are required for good performance of
Irradiation of α-Al2O3 (Corundum) was carried out in contact with acidic media and with different doses (100-to-2500 kGy) and dose-rates (0.9, 2.6 and 6.1 kGy·h−1) of γ-rays. Simultaneously parallel experiments were carried out using the same procedure, but preheated at 150°C for two days and then irradiated without acidic media. The solid thus obtained was used to determine the effect of γ-irradiation on the sorption capacities of microamounts of fission products from strongly alkaline aqueous solutions of uranium. The results revealed that the effect of γ-irradiation of α-Al2O3 and the acidic media in which it is immersed, is associated with a stable matrix resistant to significant changes in the composition of the surface layer; whilst it seems that the effect of γ-irradiation of preheated α-Al2O3, is connected with changes of surface-OH groups strongly affected by heat treatment and irradiation dose.
Polyaniline/α-Al2O3 (PANI/α-Al2O3) composites were synthesized by in situ polymerization through ammonium persulfate ((NH4)2S2O8, APS) oxidized aniline using HCl as dopant. XRD and FTIR were used to characterize the PANI/α-Al2O3 composites. The thermal stabilities and glass transition temperature (T g) of PANI/α-Al2O3 composites were tested using thermogravimetric (TG) method and modulated differential scanning calorimetry (MDSC) technique. The results of TG showed that the thermal stability of PANI/α-Al2O3 composite increased and then decreased with the increase in α-Al2O3 content. The derivative thermogravimetry (DTG) curves showed one step degradation of PANI when the α-Al2O3 content was lower than 52.5 mass%, and exhibited two steps degradation when the α-Al2O3 content was higher than 63.6 mass%. The MDSC curves showed that the T g of PANI/α-Al2O3 composites increased and then decreased with the augment of α-Al2O3 for the interaction between PANI chains and the surface of α-Al2O3.
We have studied by means of differential microcalorimetry the adsorption process of 1-propanol on α-Al2O3 at the temperatures of 25, 50, 100, 150 and 200°C, respectively. Both amounts of adsorbed alcohol and heats released decrease as the temperature of adsorption increases. At very low coverage, the high value of differential heat shows a strong irreversible chemisorption on active sites (Lewis acid sites) (qdiff>200 kJ·mol−1). Moreover, we carried out some thermokinetic investigations on heat emission peaks at different coverage degree (different equilibrium pressure of 1-propanol vapour as a function of time) and at different temperatures of adsorption, at same coverage.
A differential microcalorimeter (E. Calvet) was used to study the processes of adsorption of five aliphatic alcohols (C1-C5) on α-Al2O3 at 25, 50, 100, 150 and 200°C. In particular, the importance of the thermokinetic study of the chemisorption of such alcohols
at different experimental temperatures was demonstrated, with regard to the variations in the thermokinetic parameters (tmax, t1/2 and t0) and the evolution of the alcohol vapor pressure on the adsorbent during the adsorption process. It was concluded that:
all the heat emission peaks of alcohol adsorption have the same rounded shape at 25°C;
on passing from methanol to 1-pentanol, the area of the adsorption peaks increases as the chain length or molecular weight
on passing from 25 to 200°C, the shape of the adsorption peaks becomes more pointed.
The enthalpy ofα-Al2O3 (pure synthetic sapphire) was measured by means of a high-temperature drop calorimeter in the temperature range from 900 to 1900 K. The results may be interpolated by the polynomial with the estimated multiple correlation coefficient squared 0.99953: (accuracy ±0.4%),
A computerized adiabatic calorimeter for heat capacity measurements in the temperature range 80–400 K has been constructed. The sample cell of the calorimeter, which is about 50 cm3 in internal volume, is equipped with a platinum resistance thermometer and surrounded by an adiabatic shield and a guard shield. Two sets of 6-junction chromel-copel thermocouples are mounted between the cell and the shields to indicate the temperature differences between them. The adiabatic conditions of the cell are automatically controlled by two sets of temperature controller. The reliability of the calorimeter was verified through heat capacity measurements on the standard reference material α-Al2O3. The results agreed well with those of the National Bureau of Standards (NBS): within 0.2% throughout the whole temperature region. The heat capacities of high-purity graphite and polystyrene were precisely measured in the interval 260–370 K by using the above-mentioned calorimeter. The results were tabulated and plotted and the thermal behavior of the two materials was discussed in detail. Polynomial expressions for calculation of the heat capacities of the two substances are presented.
A fully automated adiabatic calorimeter controlled on line by a computer used for heat capacity measurements in the temperature range from 80 to 400 K was constructed. The hardware of the calorimetric system consisted of a Data Acquisition/Switch Unit, 34970A Agilent, a 7 1/2 Digit Nano Volt /Micro Ohm Meter, 34420A Agilent, and a P4 computer. The software was developed according to modern controlling theory. The adiabatic calorimeter consisted mainly of a sample cell equipped with a miniature platinum resistance thermometer and an electric heater, two (inner and outer) adiabatic shields, two sets of six junction differential thermocouple piles and a high vacuum can. A Lake Shore 340 Temperature Controller and the two sets of differential thermocouples were used to control the adiabatic conditions between the cell and its surroundings. The reliability of the calorimeter was verified by measuring the heat capacities of synthetic sapphire (α-Al2O3), Standard Reference Material 720. The deviation of the data obtained by this calorimeter from those published by NIST was within ±0.1% in the temperature range from 80 to 400 K.
Al(NO 3 ) 3 12 1,000 γ-Al 2 O 3 Citric acid 38 1,200 CA 2 , α-Al 2 O 3 , CA 6