Temperature, sample

Many spectrometers are equipped with facilities to monitor and regulate the temperature within a probe head. Usually the sensor takes the form of a thermocouple whose tip is placed close to the sample in the gas flow used to provide temperature regulation. However, the readings provided by these systems may not reflect the true temperature of the sample unless they have been subject to appropriate calibration. One approach to such calibration is to measure a specific NMR parameter that has a known temperature dependence to provide a more direct reading of sample temperature. Whilst numerous possibilities have been proposed as reference materials [41], two have become accepted as the standard temperature calibration samples for solution spectroscopy. These are methanol for the range 175-310 K and 1,2-ethanediol (ethylene glycol) for 300-400 K. 

For the low temperature calibration, neat MeOH is used, with a trace of HCl to sharpen the resonances, for which the following equation holds [42,43]  

Before making temperature measurements, the sample should be allowed to equilibrate for at least 5-10 minutes at each new temperature, and it is also good practice to take a number of measurements to ensure they do not vary before proceeding with the calculation. 

Many spectrometers are equipped with facilities to monitor and regulate the temperature within a prohe head. Usually the sensor takes the form of a thermoeouple whose tip is placed close to the sample in the gas flow used to provide temperature regulation. However, the readings provided by these systems may not reflect the hue temperature of the sample 

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Sample size is 100 ml and distillation conditions are specified according to the type of sample. Temperature and volume of condensate are taken simultaneously and the test results are calculated and reported as boiling temperature as a function of the volume recovered as shown in Table 2.1. 

A novel modification of the STM supplements images with those due to the thermopower signal across the tip-sample temperature gradient [49]. Images of guanine on graphite illustrate the potential of this technique. 

Adsorbates can physisorb onto a surface into a shallow potential well, typically 0.25 eV or less [25]. In physisorption, or physical adsorption, the electronic structure of the system is barely perturbed by the interaction, and the physisorbed species are held onto a surface by weak van der Waals forces. This attractive force is due to charge fiuctuations in the surface and adsorbed molecules, such as mutually induced dipole moments. Because of the weak nature of this interaction, the equilibrium distance at which physisorbed molecules reside above a surface is relatively large, of the order of 3 A or so. Physisorbed species can be induced to remain adsorbed for a long period of time if the sample temperature is held sufficiently low. Thus, most studies of physisorption are carried out with the sample cooled by liquid nitrogen or helium. 

Ions generated in the ion source region of the instrument may have initial velocities isotropically distributed in tliree dimensions (for gaseous samples, this initial velocity is the predicted Maxwell-Boltzmaim distribution at the sample temperature). The time the ions spend in the source will now depend on the direction of their initial velocity. At one extreme, the ions may have a velocity Vq in the direction of the extraction grid. The time spent in the source will be... 

There are two main applications for such real-time analysis. The first is the detemiination of the chemical reaction kinetics. Wlien the sample temperature is ramped linearly with time, the data of thickness of fomied phase together with ramped temperature allows calculation of the complete reaction kinetics (that is, both the activation energy and tlie pre-exponential factor) from a single sample [6], instead of having to perfomi many different temperature ramps as is the usual case in differential themial analysis [7, 8, 9, 10 and H]. The second application is in detemiining the... 

Dielectric Strength. Dielectric failure may be thermal or dismptive. In thermal breakdown, appHed voltage heats the sample and thus lowers its electrical resistance. The lower resistance causes still greater heating and a vicious circle, leading to dielectric failure, occurs. However, if appHed voltage is below a critical value, a stabilized condition may exist where heat iaput rate equals heat loss rate. In dismptive dielectric failure, the sample temperature does not iacrease. This type of failure is usually associated with voids and defects ia the materials. 

Reports of sterilisation (qv) against bacteria by nonthermal effects have appeared, but it is generally beheved that the effect is only that of heating (164). Because microwave heating often is not uniform, studies in this area can be seriously flawed by simplistic assumptions of uniform sample temperature. 

Dijferential Thermal Analysis (DTA) A sample and inert reference material are heated at a controlled rate in a single heating block. If an exothermic reaction occurs, the sample temperature will... 

Reactive System Screening Tool (RSST) The RSST is a calorimeter that quickly and safely determines reactive chemical hazards. It approaches the ease of use of the DSC with the accuracy of the VSP. The apparatus measures sample temperature and pressure within a sample containment vessel. Tne RSST determines the potential for runaway reactions and measures the rate of temperature and pressure rise (for gassy reactions) to allow determinations of the energy and gas release rates. This information can be combined with simplified methods to assess reac tor safety system relief vent reqiiire-ments. It is especially useful when there is a need to screen a large number of different chemicals and processes. 

Sample temperatures may be below ambient. If the sample vessel is liquid-full, a hazard results due to overpressurization as the hquid expands. Venting may be required, but it can distort the results. This safety hazard must be accounted for in the procedure and in interpreting the laboratoiy results. 

Sample temperatures may be above ambient. If the temperature is significantly above ambient, personnel must be protected against burns. 

In the ARC (Figure 12-9), the sample of approximately 5 g or 4 ml is placed in a one-inch diameter metal sphere (bomb) and situated in a heated oven under adiabatic conditions. Tliese conditions are achieved by heating the chamber surrounding the bomb to the same temperature as the bomb. The thermocouple attached to the sample bomb is used to measure the sample temperature. A heat-wait-search mode of operation is used to detect an exotherm. If the temperature of the bomb increases due to an exotherm, the temperature of the surrounding chamber increases accordingly. The rate of temperature increase (selfheat rate) and bomb pressure are also tracked. Adiabatic conditions of the sample and the bomb are both maintained for self-heat rates up to 10°C/min. If the self-heat rate exceeds a predetermined value ( 0.02°C/min), an exotherm is registered. Figure 12-10 shows the temperature versus time curve of a reaction sample in the ARC test. 

The vent sizing package (VSP) was developed by Fauskes Associates, Inc. The VSP and its latest version VSP2 employ the low thermal mass test cell stainless steel 304 and Hastelloy test cell with a volume of 120 ml contained in a 4-1, high-pressure vessel as shown in Figure 12-13. The typical ([t-factor is 1.05-1.08 for a test cell wall thickness of 0.127-0.178 mm. Measurements consist of sample temperature Tj and pressure Pj, and external guard temperature Tj and... 

The inlet gas line should have taps for gas sampling, temperature measurement, pressure measurement, and for an injection nozzle for... 

Direct observations of the decompositions of a wide range of inorganic compounds [231—246], which are unstable in the electron beam, particularly azides and silver halides, have provided information concerning the mechanisms of radiolysis these are often closely related to the processes which operate during thermal decomposition. Sample temperatures estimated [234] to occur at low beam intensity are up to 470 K while, at higher intensity, 670 K may be attained. 

The sample temperature should be sufficiently high to ensure sufficient conductivity of the solid electrolyte and thus avoid charging of the solid electrolyte. This means temperatures above 300°C for YSZ and above 100°Cfor p"-Al203. 

The various sohd sulfur allotropes are all more or less yellow at 20 °C but the scale ranges from the deep orange-yellow of to the pale yellow of S. The color also depends on the particle size As finer the particles as lighter the color impression. Chemically produced Ss has in fact occasionally been obtained as a colorless material at room temperature which only slowly turns yellow as the initially tiny crystals grow [61]. The sample temperature is also of decisive influence (thermochromic effect) [10] (see above). 

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