Gases phase transitions

Wight C A and Armentrout P B 1993 Laser photoionization probes of ligand-binding effects in multiphoton dissociation of gas-phase transition-metal complexes ACS Symposium Series 530 61-74... 

Since an analyte and interferent are usually in the same phase, a separation often can be effected by inducing a change in one of their physical or chemical states. Changes in physical state that have been exploited for the purpose of a separation include liquid-to-gas and solid-to-gas phase transitions. Changes in chemical state involve one or more chemical reactions. 

In 1990, Schroder and Schwarz reported that gas-phase FeO" " directly converts methane to methanol under thermal conditions [21]. The reaction is efficient, occuring at 20% of the collision rate, and is quite selective, producing methanol 40% of the time (FeOH+ + CH3 is the other major product). More recent experiments have shown that NiO and PtO also convert methane to methanol with good efficiency and selectivity [134]. Reactions of gas-phase transition metal oxides with methane thus provide a simple model system for the direct conversion of methane to methanol. These systems capture the essential chemistry, but do not have complicating contributions from solvent molecules, ligands, or multiple metal sites that are present in condensed-phase systems. 

Methane-to-methanol conversion by gas-phase transition metal oxide cations has been extensively studied by experiment and theory see reviews by Schroder, Schwarz, and co-workers [18, 23, 134, 135] and by Metz [25, 136]. We have used photofragment spectroscopy to study the electronic spectroscopy of FeO" " [47, 137], NiO [25], and PtO [68], as well as the electronic and vibrational spectroscopy of intermediates of the FeO - - CH4 reaction. [45, 136] We have also used photoionization of FeO to characterize low lying, low spin electronic states of FeO [39]. Our results on the iron-containing molecules are presented in this section. 

The mobile phase in LC-MS may play several roles active carrier (to be removed prior to MS), transfer medium (for nonvolatile and/or thermally labile analytes from the liquid to the gas state), or essential constituent (analyte ionisation). As LC is often selected for the separation of involatile and thermally labile samples, ionisation methods different from those predominantly used in GC-MS are required. Only a few of the ionisation methods originally developed in MS, notably El and Cl, have found application in LC-MS, whereas other methods have been modified (e.g. FAB, PI) or remained incompatible (e.g. FD). Other ionisation methods (TSP, ESI, APCI, SSI) have even emerged in close relationship to LC-MS interfacing. With these methods, ion formation is achieved within the LC-MS interface, i.e. during the liquid- to gas-phase transition process. LC-MS ionisation processes involve either gas-phase ionisation (El), gas-phase chemical reactions (Cl, APCI) or ion evaporation (TSP, ESP, SSI). Van Baar [519] has reviewed ionisation methods (TSP, APCI, ESI and CF-FAB) in LC-MS. 

Gas phase transition metal cluster chemistry lies along critical connecting paths between different fields of chemistry and physics. For example, from the physicist s point of view, studies of clusters as they grow into metals will present new tests of the theory of metals. Questions like How itinerant are the bonding electrons in these systems and Is there a metal to non-metal phase transition as a function of size are frequently addressed. On the other hand from a chemist point of view very similar questions are asked but using different terminology How localized is the surface chemical bond and What is the difference between surface chemistry and small cluster chemistry Cluster science is filling the void between these different perspectives with a new set of materials and measurements of physical and chemical properties. 

TREVOR AND KALDOR Gas-Phase Transition Metal Cluster Complexes... 

The field of gas-phase transition metal cluster chemistry has expanded rapidly due to the development of the laser vaporization source and the fast flow chemical reactor. The work from the three major laboratories have been reviewed. Many additional laboratories are developing cluster chemistry programs and will soon certainly make significant contributions. 

Conclusions. Time-resolved CO laser absorption spectroscopy can provide information useful in characterizing the primary photochemical channels in gas-phase transition metal carbonyls. We have found that product vibrational energy distributions indicate that W(CO)g and Cr(CO>6 dissociate via different... 

If only the solvation of the gas-phase stationary points are studied, we are working within the frame of the Conventional Transition State Theory, whose problems when used along with the solvent equilibrium hypothesis have already been explained above. Thus, the set of Monte Carlo solvent configurations generated around the gas-phase transition state structure does not probably contain the real saddle point of the whole system, this way not being a correct representation of the conventional transition state of the chemical reaction in solution. However, in spite of that this elemental treatment... 

The triple point is the location at which all three phases boundaries intersect. At the triple point (and only at the triple point), all three phases (solid, liquid, and gas) coexist in dynamic equilibrium. Below the triple point, the solid and gas phases are next-door neighbors, and the solid-to-gas phase transition occurs directly. 

The temperature at which a phase transition occurs is dependent on pressure (Figure 7). At atmospheric pressure (1 atm) the solid-to-liquid phase transition occurs at 0 °C and the liquid-to-gas phase transition occurs at 100 °C. If we increase the pressure, say to 100 atm, the solid-to-liquid phase transition occurs at a temperature slightly less than 0°C (—0.74°C) however, the liquid-to-gas phase transition occurs at a much greater temperature (312°C). If we decrease the pressure, say to 0.1 atm, the solid-to-liquid phase transition occurs at a temperature slightly greater than 0°C (0.004 °C) and the liquid-to-gas phase transition occurs at a lower temperature (46 °C). If we decrease the pressure further to below the triple point, there is no solid-to-liquid phase transition rather, the solid-to-gas phase transition occurs directly. At a pressure of 0.001 atm, the sublimation temperature is — 20.16°C. 

We re all used to seeing solid/liquid and liquid/gas phase transitions, but behavior at the critical point lies so far outside our normal experiences that it s hard to imagine. A gas at the critical point is under such high pressure and its molecules are so close together, that it becomes indistinguishable from a liquid. A... 

Helium-4 Normal-Superfluid Transition Liquid helium has some unique and interesting properties, including a transition into a phase described as a superfluid. Unlike most materials where the isotopic nature of the atoms has little influence on the phase behavior, 4He and 3He have a very different phase behavior at low temperatures, and so we will consider them separately Figure 13.11 shows the phase diagram for 4He at low temperatures. The normal liquid phase of 4He is called liquid I. Line ab is the vapor pressure line along which (gas + liquid I) equilibrium is maintained, and the (liquid + gas) phase transition is first order. Point a is the critical point of 4He at T= 5.20 K and p — 0.229 MPa. At this point, the (liquid + gas) transition has become continuous. Line be represents the transition between normal liquid (liquid I) and a superfluid phase referred to as liquid II. Along this line the transition... 

K. Kokot, Z. Knez, D. Bauman, S-L-G (solid-liquid-gas) phase transition of cocoa butter in supercritical CO2, Acta Alimentaria 28 (1999) 197-208. 

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