Isothermal instrument

Isothermal instruments are usually of two basic design types adiabatic and heat conduction calorimeters. 

The Shimadzu GC-15A and GC-16A systems are designed not only as independent high-performance gas chromatographs but also as core instruments (see previously) for multi-GC systems or computerised laboratory automation systems. Other details of these instruments are given in Table 5.1. The Shimadzu GC-8A range of instruments do not have a range of built-in detectors but are ordered either as temperature-programmed instruments with thermal conductivity detection (TCD), flame ionisation detection (FID), or flame photometric detectors (FPD) detectors or as isothermal instruments with TCD, FID, or electron capture detectors (ECD) (Table 5.1). 

To extract h from Eq. (5.8.4), one must determine for each resolved wavenumber interval the unknown quantities r and This is conveniently achieved by measuring two known sources in addition to the object of interest. Deep space may be one convenient reference and a warm blackbody may serve as the other. In case of an isothermal instrument temperature, 5 (7]) is the Planck function corresponding... 

Suppose that this isothermal instrument views a 200 K blackbody. The detector sees only objects of its own temperature. The motion of the interferometer mirror inside this perfectly isothermal enclosure caimot affect the net flux at the detector the interferogram must be zero. Consequently, the amplitude A2(v), which is the Fourier component for wavenumber v of the interferogram, must also be zero and Eq. (5.13.12) simplifies to... 

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]. 

Instrumentation. H and NMR spectra were recorded on a Bruker AV 400 spectrometer (400.2 MHz for proton and 100.6 MHz for carbon) at 310 K. Chemical shifts (< are expressed in ppm coupling constants (J) in Hz. Deuterated DMSO and/or water were used as solvent chemical shift values are reported relative to residual signals (DMSO 5 = 2.50 for H and 5 = 39.5 for C). ESl-MS data were obtained on a VG Trio-2000 Fisons Instruments Mass Spectrometer with VG MassLynx software. Vers. 2.00 in CH3CN/H2O at 60°C. Isothermal titration calorimetry (ITC) experiments were conducted on a VP isothermal titration calorimeter from Microcal at 30°C. 

Thermal decomposition was performed using a SDT Q-600 simultaneous DSC-TGA instrument (TA Instruments). The samples (mass app. 10 mg) were heated in a standard alumina 90 il sample pan. All experiments were carried out under air with a flow rate of 0.1 dm3/min. Non-isothermal measurements were conducted at heating rates of 3, 6, 9, 12, and 16 K/min. Five experiments were done at each heating rate. 

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. 

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. 

Thermal Analysis. The DuPont Instruments Model 9900, computer controlled thermal analyzer and Model 951 TGA module were used in the experiments, using a gas flow rate of 100 cc/min. Experiments were performed in dynamic and isothermal mode using air and argon. 

The surface pressure-area (tc-A) isotherm measurements and LB film transfer were performed with the use of a KSV 5000 minitrough (KSV Instrument Co., Finland) operated at a continuous speed for two barriers of 10 cm2/min at 20°C. The buffer used in the present work was composed of 10 mM MES, 2 mM ascorbic acid sodium salt, and a given concentration of salt or polymers (pH =7.0). The accuracy of the surface pressure measurement was 0.01 mN/m. Monolayers of the PS I were transferred at 10 mN/m on hydrophobic substrate surface by horizontal lifting method. 

Isoperibolic instruments have been developed to estimate enthalpies of reaction and to obtain kinetic data for decomposition by using an isothermal, scanning, or quasi-adiabatic mode with compensation for thermal inertia of the sample vessel. The principles of these measuring techniques are discussed in other sections. 

Other instruments include the Calvet microcalorimeters [113], some of which can also run in the scanning mode as a DSC. These are available commercially from SETARAM. The calorimeters exist in several configurations. Each consists of sample and reference vessels placed in an isothermally controlled and insulated block. The side walls are in intimate contact with heat-flow sensors. Typical volumes of sample/reference vessels are 0.1 to 100 cm3, The instruments can be operated from below ambient temperatures up to 300°C (some high temperature instruments can operate up to 1000°C). The sensitivity of these instruments is better than 1 pW, which translates to a detection limit of 1 x 10-3 W/kg with a sample mass of 1 g. 

As discussed in Section 2.3.1.2, SEDEX [103, 104] and SIKAREX [106] instruments are also used isothermally. In the case of the SIKAREX, the temperature of the sample is held by a heating coil at constant temperature by establishing a constant rate of heat exchange to the jacket (held about 50 to 100°C below the sample temperature). By measuring the electrical input, a negative copy of the reaction heat profile is obtained. Typical sensitivity of the equipment is 0.5 W/kg operating with a sample size of 10 to 30 g and in a temperature range of 0 to 300°C. 

A liquid flow microcalorimeter, the thermal activity monitor (TAM), is commercially available from ThermoMetric (formerly LKB/Bofors). This instrument consists of two glass or steel ampules with a volume of 3 to 4 cm3 (25 cm3 ampule available with a single detector), placed in a heat sink block. Recently, an injection-titration sample vessel was developed which acts as a microreactor. This vessel is provided with flow-in, flow-out, and titration lines, with a stirring device. The isothermal temperature around the heat sink is maintained by a controlled water bath. Each vessel holder, containing an ampoule, is in direct contact with a thermopile array, and the two arrays are joined in series so that their output voltages subtract. The two pairs of thermopile arrays are oppositely connected to obtain a differential output,... 

Investigation of the global rates of reaction can be carried out in instrumented bench-scale equipment, such as the RC1 (Mettler-Toledo) plus on-line chemical analysis. Commercially available equipment allows well-controlled process conditions, and can be used in a variety of modes (e.g., isothermal, adiabatic, temperature programmed). The test volumes, which may be up to 2 liters depending on the energy involved, enable reasonable simulation of process conditions, and are more representative than very small samples, particularly for mixed phase systems. The scale of such equipment permits the collection of accurate data. 

There are three solution components, ethanol, acetone, and water. If a flame ionization detector is used, there will be only two peaks, since water will not give a peak Set up the instrument for isothermal operation at 100°C. The two peaks should be nicely resolved and each run should take only a few minutes. 

Some investigations require a preselected temperature program. For example, a substance should be dried at a special temperature, and afterwards one wants to know the complete heating behavior from room temperature to the selected temperature, with an isothermal step and uncontrolled cooling (Fig. 14 D). For such problems some of the commercial instruments are prepared either by computer, or by simple switching clock-programs which allow one to follow a preprogrammed course,... 

As mentioned above, titration methods have also been adapted to calorimeters whose working principle relies on the detection of a heat flow to or from the calorimetric vessel, as a result of the phenomenon under study [195-196,206], Heat flow calorimetry was discussed in chapter 9, where two general modes of operation were presented. In some instruments, the heat flow rate between the calorimetric vessel and a heat sink is measured by use of thermopiles. Others, such as the calorimeter in figure 11.1, are based on a power compensation mechanism that enables operation under isothermal conditions. 

Analogously to the dynamic method, the energy equivalent of the calorimeter, k.Q, can be obtained by performing calibration experiments in the isothermal mode of operation, using electrically generated heat or the fusion of substances with well-known A us//. Recommendations for the calibration of the temperature scale of DSC instruments for isothermal operation have also been published [254,270]. 

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