Specific heat transitional metals

The thermal expansion coefficient, the electric resistivity, and the specific heat of metallic nanosolids or alloys increase inversely with solid size whereas the temperature coefiicient of resistivity and the critical temperature for magnetic transition drop inversely with solid size [46]. The emerging freedom of size... 

The saturation coverage during chemisorption on a clean transition-metal surface is controlled by the fonnation of a chemical bond at a specific site [5] and not necessarily by the area of the molecule. In addition, in this case, the heat of chemisorption of the first monolayer is substantially higher than for the second and subsequent layers where adsorption is via weaker van der Waals interactions. Chemisorption is often usefLil for measuring the area of a specific component of a multi-component surface, for example, the area of small metal particles adsorbed onto a high-surface-area support [6], but not for measuring the total area of the sample. Surface areas measured using this method are specific to the molecule that chemisorbs on the surface. Carbon monoxide titration is therefore often used to define the number of sites available on a supported metal catalyst. In order to measure the total surface area, adsorbates must be selected that interact relatively weakly with the substrate so that the area occupied by each adsorbent is dominated by intennolecular interactions and the area occupied by each molecule is approximately defined by van der Waals radii. This... 

The idea that new phenomena could be present in 3He at very low temperatures arose from thermal measurements. The first observation was the anomaly in the specific heat at the normal superfluid transition which reminded the behaviour of specific heat at the superconductive transition in metals (Fig. 2.11) [34-36]. 

The melting transition of ultra-pure metals is usually used for calibration of DSC instruments. Metals such as indium, lead, and zinc are useful and cover the usual temperature range of interest. Calibration of DSC instruments can be extended to temperatures other than the melting points of the standard materials applied through the recording of specific heat capacity of a standard material (e.g., sapphire) over the temperature range of interest. Several procedures for the performance of a DSC experiment and the calibration of the equipment are available [84-86]. A typical sensitivity of DSC apparatus is approximately 1 to 20 W/kg [15, 87]. 

The orbitals of the d states in clusters of the 3d, 4d, and 5d transition elements (or in the bulk metals) are fairly localized on the atoms as compared with the sp valence states of comparable energy. Consequently, the d states are not much perturbed by the cluster potential, and the d orbitals of one atom do not strongly overlap with the d orbitals of other atoms. Intraatomic d-d correlations tend to give a fixed integral number of d electrons in each atomic d-shell. However, the small interatomic d-d overlap terms and s-d hybridization induce intraatomic charge fluctuations in each d shell. In fact, a d orbital contribution to the conductivity of the metals and to the low temperature electronic specific heat is obtained only by starting with an extended description of the d electrons.7... 

The transport of heat in metallic materials depends on both electronic transport and lattice vibrations, phonon transport. A decrease in thermal conductivity at the transition temperature is identified with the reduced number of charge carriers as the superconducting electrons do not carry thermal energy. The specific heat and thermal conductivity data are important to determine the contribution of charge carriers to the superconductivity. The interpretation of the linear dependence of the specific heat data on temperature in terms of defects of the material suggests care in interpreting the thermal conductivity results to be described. 

The amount of heat required to raise the temperature of a material is related to the vibrational and rotational motions thermally excited within the sample. Polymers typically have relatively (compared with metals) large specific heats, with most falling within the range of 1 to 2 kJ kg-1 K . Replacement of hydrogen atoms by heavier atoms such as fluorine or chlorine leads to lower Cp values. The Cp values change as materials undergo phase changes (such as that at the T ) but remain constant between such transitions. 

The large phase shifts t 2 give a large enhancement of the resistivity when transitional metals are dissolved in other metals. A survey for solid metals is given by Friedel (1956), and for solutions of Fe and Co in liquid germanium and tin by Dreirach et al (1972). The resonance will also enhance the electronic specific heat and the Pauli paramagnetism, but these quantities cannot be treated quantitatively without including correlation as shown in Chapter 3. 

At small concentrations of Pd there will be a conduction-band resonance at each transitional-metal atom, and the resistance depends on the phase shifts. For Ag-Pd the resonance only just extends over the Fermi energy, giving very small residual resistance and specific-heat enhancement for Cu-Ni they are much larger. 

Controlled microwave heating is a new enabling tool that helps the medicinal and combinatorial chemist to rapidly both optimize reaction conditions and perform small-scale target syntheses. In this short review, we have presented examples of microwave heating in high-speed medicinal chemistry. More specifically, we have mainly described microwave-enhanced synthesis of protease inhibitors using transition-metal catalysis. In all depicted examples, the main chemical effort was directed towards convenient and reliable pro-... 

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