Programmed temperature

Van Den Dool, H. and P.D. Kratz (1963), Generalization of the retention index system including linear temperature programmed gas-liquid partition chromatography . J. Chromatogr, Vol. 11, p. 463. 

TPD Temperature-programmed desorption [171, 172] The surface is heated and chemisorbed species desorb at characteristic temperatures Characterization of surface sites and desorption kinetics... 

TPRS Temperature-programmed Same as TPD reaction spectroscopy [174] Spectroscopy of Emitted Neutrons Same as TPD... 

Temperature-programmed desorption (TPD) is amenable to simple kinetic analysis. The rate of desorption of a molecular species from a uniform surface is given by Eq. XVII-4, which may be put in the form... 

Sequences such as the above allow the formulation of rate laws but do not reveal molecular details such as the nature of the transition states involved. Molecular orbital analyses can help, as in Ref. 270 it is expected, for example, that increased strength of the metal—CO bond means decreased C=0 bond strength, which should facilitate process XVIII-55. The complexity of the situation is indicated in Fig. XVIII-24, however, which shows catalytic activity to go through a maximum with increasing heat of chemisorption of CO. Temperature-programmed reaction studies show the presence of more than one kind of site [99,1(K),283], and ESDIAD data show both the location and the orientation of adsorbed CO (on Pt) to vary with coverage [284]. 

Studies to determine the nature of intermediate species have been made on a variety of transition metals, and especially on Pt, with emphasis on the Pt(lll) surface. Techniques such as TPD (temperature-programmed desorption), SIMS, NEXAFS (see Table VIII-1) and RAIRS (reflection absorption infrared spectroscopy) have been used, as well as all kinds of isotopic labeling (see Refs. 286 and 289). On Pt(III) the surface is covered with C2H3, ethylidyne, tightly bound to a three-fold hollow site, see Fig. XVIII-25, and Ref. 290. A current mechanism is that of the figure, in which ethylidyne acts as a kind of surface catalyst, allowing surface H atoms to add to a second, perhaps physically adsorbed layer of ethylene this is, in effect, a kind of Eley-Rideal mechanism. 

The temperature-programmed desorption of NO2 shows a maximum rate at 330 K using a heating rate of 7.53°C/sec. Take A to be lO sec , and assume that Eq. XVIII-1 applies. (Note Ref. 344.)... 

TPD Temperature programmed desorption After pre-adsorption of gases on a surface, the desorption and/or reaction products are measured while the temperature Increases linearly with time. Coverages, kinetic parameters, reaction mechanism... 

Thenual desorption spectroscopy (TDS) or temperature progranuned desorption (TPD), as it is also called, is a simple and very popular teclmique in surface science. A sample covered with one or more adsorbate(s) is heated at a constant rate and the desorbing gases are detected with a mass spectrometer. If a reaction takes place diirmg the temperature ramp, one speaks of temperature programmed reaction spectroscopy (TPRS). 

Alongside tliese teclmiques, microbalance measurements of adsorjDtion capacities and kinetics, microcalorimetric measurements of adsorjDtion processes and temperature-programmed desorjDtion of base molecules have provided useful infonnation about tire tliennochemistry of adsorjDtion processes and tire acidity characteristics of zeolites [46]. 

Thermal analysis iavolves techniques ia which a physical property of a material is measured agaiast temperature at the same time the material is exposed to a coatroUed temperature program. A wide range of thermal analysis techniques have been developed siace the commercial development of automated thermal equipment as Hsted ia Table 1. Of these the best known and most often used for polymers are thermogravimetry (tg), differential thermal analysis (dta), differential scanning calorimetry (dsc), and dynamic mechanical analysis (dma). 

Specific Commercial Rotational Viscometers. Information on selected commercial rotational viscometers can be found ia Table 7. The ATS RheoSystems Stresstech rheometer is an iastmment that combines controlled stress as well as controlled strain (shear rate) and oscillatory measurements. It has a torque range of 10 to 50 mN-m, an angular velocity range of 0 to 300 rad/s, and a frequency range of seven decades. Operation and temperature programming (—30 to 150°C higher temperatures optional) are computer controlled. 

Cehte or firebrick packing for glc columns is often treated with TMCS, DMCS, or other volatile silylating agents (see Table 1) to reduce tailing by polar organic compounds. A chemically bonded methyl siUcone support is stable for temperature programming to 390°C and allows elution of hydrocarbons up to C q (20). 

The best quahty to be found may be a temperature, a temperature program, a concentration, a conversion, a yield of preferred product, a cycle period for a batch reaction, a daily production level, a land of reactor, a size for a reactor, an arrangement of reactor elements, provisions for heat transfer, profit or cost, and so on—a maximum or minimum of some of these factors. Among the constraints that may be imposed on the process are temperature range, pressure range, corrosiveness, waste disposal, and others. 

After adequate analitical prepai ation according to standai d EPA method 608 samples were analysed gas chromatographic on a gas chromatograph 8500 Perkin Elmer, in glass and capilar columns using a capture electron detector and mass spectrometry, temperature program. 

Figure 3.13 shows the thermal stability of immobilized ODN and PNA. The signal for the Thy- and Cyt-bases obtained with temperature-programmed (TP) SIMS starts to decrease at approximately 150 °C for ODN and 200 °C for PNA. This variance is caused by the different strengths of binding between the bases and the sugar-phosphate and peptide backbones, respectively. 

Temperature programming was introduced in the early days of GC and is now a commonly practiced elution technique. It follows that the temperature programmer is an essential accessory to all contemporary gas chromatographs and also to many liquid chromatographs. The technique is used for the same reasons as flow programming, that is, to accelerate the elution rate of the late peaks that would otherwise take an inordinately long time to elute. The distribution coefficient of a solute is exponentially related to the reciprocal of the absolute temperature, and as the retention volume is directly related to the distribution coefficient, temperature will govern the elution rate of the solute. 

Furthermore, after time (tp) between (tp) and (tp+At) during a temperature program at a rate of a°C per unit time and an initial temperature of (To), the effective retention... 

For example, consider an open tubular column with the dimensions previously defined, operated at constant mass flow rate of helium (which is normal for temperature programming purposes), then, from Poiseuille s equation, after time (t),... 

It is seen that the viscosity of the gas will change significantly during a temperature program and, thus, at a constant gas mass flow rate, the inlet pressure will rise proportionally. This increase in inlet pressure will result in an increase in the inlet/outlet pressure ratio and, as a consequence, will extend the retention time and oppose the effect of any increase in temperature. It also follows that the effect of... 

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