Surface area instrumentation

The powders have been characterized by the following methods XRD with a Philips 1130 (CoKa radiation) diffractometer, simultaneous TG-DTG-DTA analyses with a Setaram TG92 instrument, FT- IR and FT-FIR spectroscopies with a Nicolet Magna 750 spectrometer, FT-Raman spectroscopy with a Bruker RFSIOO instrument. Surface area and porosity were performed at 77 K by the BET method. 

Vibrational Spectroscopy. Infrared absorption spectra may be obtained using convention IR or FTIR instrumentation the catalyst may be present as a compressed disk, allowing transmission spectroscopy. If the surface area is high, there can be enough chemisorbed species for their spectra to be recorded. This approach is widely used to follow actual catalyzed reactions see, for example. Refs. 26 (metal oxide catalysts) and 27 (zeolitic catalysts). Diffuse reflectance infrared reflection spectroscopy (DRIFT S) may be used on films [e.g.. Ref. 28—Si02 films on Mo(llO)]. Laser Raman spectroscopy (e.g.. Refs. 29, 30) and infrared emission spectroscopy may give greater detail [31]. 

AFM images of PET film surfaces have also recently been measured [156] and they showed a microroughness of PET films of the order of 1 nm averaged over a surface area of 200 x 200 nmJ. In some cases atomic lateral resolution is achieved [39] when e.g. dialkylamonium (C16) layers adsorbed on mica from cyclohexane are examined [157]. The interpretation of AFM data is at present not always clear and further advances will be made with improved instrumentation. Up till now, only very specific examples of polymeric structure have been investigated,... 

A serious limitation of the STM technique so far is its lack of chemical sensitivity. Generally, STM is not specific for the elemental species in multi-component systems, though there are special cases where the direction of charge flow is well known as shown for the GaAs(llO) surface. The surface area which one is looking at by STM is typically quite small. The problem of how representative the obtained tunnel vision is, is at least partly solved by considerably increasing the total scan range of STM/SPM instruments. 

Surface areas were determined from the adsorption isotherms of nitrogen at 77 K, using a Micromeritics ASAP 200 instrument. Powder X-ray diffraction patterns were obtained with a CGR theta 60 instrument using CuKa monochromated radiation. Reducibility and the amount of Cu species were determined by temperature programmed reduction (TPR) with H2 (H2/Ar 3/97, vol/vol). The experimental set up has been described previously [6]. 

Electrochemical nuclear magnetic resonance (NMR) is a relatively new technique that has recently been reviewed (Babu et al., 2003). NMR has low sensitivity, and a typical high-held NMR instrument needs 10 to 10 NMR active atoms (e.g., spins), to collect good data in a reasonable time period. Since 1 cm of a single-crystal metal contains about 10 atoms, at least 1 m of surface area is needed to meet the NMR sensitivity requirement. This can be met by working with carbon-supported platinum... 

For a thermometer to react rapidly to changes in the surrounding temperature, the magnitude of the time constant should be small. This involves a high surface area to liquid mass ratio, a high heat transfer coefficient and a low specific heat capacity for the bulb liquid. With a large time constant, the instrument will respond slowly and may result in a dynamic measurement error. 

In gas chromatography the value of the partition coefficient d ends only on the type of stationary phase and the column temperature. It is independent of column type and instrumental parameters. The proportionality factor in equation (l.ll) is called the phase ratio and is equal to the ratio of the volume of the gas (Vg) and liquid (V ) phases in the column. For gas-solid (adsorption) chromatography the phase ratio is given by the volume of the gas phase divided by the surface area of the stationary phase. 

Two types of instruments are employed to determine the specific surface area by permea-metry. Those of the first type are called constant pressure systems, and the Fisher subsieve sizer is a typical example that belongs to such systems. Instruments of the second type are known as constant volume permeameters, and the apparatus devised by Blain is an example. 

The reference Pt-Ba/y-Al203 (1/20/100 w/w) catalyst shows surface area values in the range 140-160 m2/g, a pore volume of 0.7-0.8cc/g and an average pore radius close to 100 A (measured by N2 adsorption-desorption at 77 K by using a Micromeritics TriStar 3000 instrument). Slight differences in the characterization data are associated to various batches of the ternary catalyst [24,25],... 

The specific surface area of the fresh and used catalysts was measured by nitrogen adsorption method (Sorptometer 1900, Carlo Erba Instruments). The catalysts were outgassed at 473 K prior to the measurements and the Dubinin equation was used to calculate the specific surface area. The acidity of investigated samples was measured by infrared spectroscopy (ATI Mattson FTIR) by using pyridine (>99.5%, a.r.) as a probe molecule for qualitative and quantitative determination of both Bronstcd and Lewis acid sites (further denoted as BAS and LAS). The amounts of BAS and LAS were calculated from the intensities of corresponding spectral bands by using the molar extinction coefficients reported by Emeis (23). Full details of the acidity measurements are provided elsewhere (22). 

Some properties of the rock used in this study were measured The cation exchange capacity (cec) was determined by the barium sulfate method as described by Mortland and Mellor (33). Surface area was measured by using a Digisorb Meter (Micromeritics Instrument Corporation) through nitrogen adsorption. Estimation of mineral composition and indentification of the rock were performed by X-ray diffraction. 

The surface area of graphite is determined by nitrogen adsorption using a BET single point method (equipment is available from Quatachrome Instruments, Boynton Beach, FL, USA). 

The chemical composition of the samples was determined using an inductively Coupled plasma atomic emission spectrometer (ICP-AES) JY 38 from Jobin Yvon. Specific surface area values were determined by BET method using a Micromeritics Instrument Corp. FlowSorb 2300. The basicity of the materials was studied by temperature programmed desorption (TPD) of C02 used as a probe molecule. The equipment was described in a previous work [7]. FTIR spectra of pellets pressed at 2.5xl08 Pa were recorded with a Vector 22 spectrometer from Brucker. The samples were diluted with KBr (lOOmg KBr - 1.5mg of the sample). 

Nitrogen adsorption was performed at -196 °C in a Micromeritics ASAP 2010 volumetric instrument. The samples were outgassed at 80 °C prior to the adsorption measurement until a 3.10 3 Torr static vacuum was reached. The surface area was calculated by the Brunauer-Emmett-Teller (BET) method. Micropore volume and external surface area were evaluated by the alpha-S method using a standard isotherm measured on Aerosil 200 fumed silica [8]. Powder X-ray diffraction (XRD) patterns of samples dried at 80 °C were collected at room temperature on a Broker AXS D-8 diffractometer with Cu Ka radiation. Thermogravimetric analysis was carried out in air flow with heating rate 10 °C min"1 up to 900 °C in a Netzsch TG 209 C thermal balance. SEM micrographs were recorded on a Hitachi S4500 microscope. 

The XRD patterns of the catalysts were obtained before and after the catalytic reaction by a Rigaku MiniflexII X-Ray diffractometer. The BET surface areas of the samples were measured with a QUNTACHROMNova2200 automatic adsorption instrument. 

Physical properties of calcined catalysts were investigated by N2 adsorption at 77 K with an AUTOSORB-l-C analyzer (Quantachrome Instruments). Before the measurements, the samples were degassed at 523 K for 5 h. Specific surface areas (,S BEX) of the samples were calculated by multiplot BET method. Total pore volume (Vtot) was calculated by the Barrett-Joyner-Halenda (BJH) method from the desorption isotherm. The average pore diameter (Dave) was then calculated by assuming cylindrical pore structure. Nonlocal density functional theory (NL-DFT) analysis was also carried out to evaluate the distribution of micro- and mesopores. 

This chapter on micromeritics will deal specifically with surface area, porosimetry, and density measurements. It is designed to introduce the importance of the specific technique in pharmaceutics and briefly describe the theory, instrumentation, and data collection involved. Examples are presented to... 

A number of commercial surface area instruments are available, and varying levels of sophistication exist. In this section, a general overview of the instrumentation will be presented, and options will be mentioned when applicable. 

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