Transition from mixed crystals

Transition from Mixed Crystals to Addition Compounds and Eutectics. 

Another phenomenon to be detected by X-ray crystallography is the formation of mixed crystals, as observed in the mixed coupling of azo pigments or the solid solutions of quinacridone pigments. A change in the angles of the reflected X-rays of a mixed crystal indicates a transition from one crystal phase to another. If, how-... 

Sprik et al, 1993 Signorini et al, 1990), a typical example being the orientational disorder associated with NH in NH Br. Detailed simulations have been reported on (NaCN),, t(KCN),t and other mixed alkali halides and alkali cyanides. Other systems studied include potassium and calcium nitrate crystals and their mixtures. The transition from the crystalline to the superionic conductor phase in solid electrolytes has also been successfully investigated. Molecular dynamics studies of Agl were carried out by Parrinello, Rahman Vashishta (1983). LijSO has been investigated by molecular dynamics by Impey et al. (1985). Here, the Li ions become mobile at high temperatures. The ions exhibit orientational disorder and the orientational... 

The resistivities of the mixed crystals are shown in Fig. 6.22. It can be seen that (as indeed follows from the phase diagram, Fig. 6.20) the transition to the insulating state occurs with larger x for increasing temperature, probably because of the high entropy of the AF insulator above its Neel temperature. 

The EPR of a Mn2+ impurity in mixed crystal N ClajIm has been observed38 between X-band and 250 GHz. Spectra from three magnetically inequivalent, but physically equivalent, Mn2+ ions were observed. The temperature dependence of the linewidth revealed phase transitions at 228 K and 242 K. The analysis of all the spectra was consistent with a model of an axially symmetric crystal field... 

G. Tammann found that potassium and sodium chlorides form a continuous series of mixed crystals between 660° and 500°. Since neither salt has a transition point, the phenomena observed when the mixed crystals are cooled must be attributed to separation of the components. With diminishing temperature, therefore, either the attractive forces within the molecules of the respective chloride must increase, or those between the unlike molecules must be greatly weakened. The results obtained by etching the individual crystals at the ordinary temperature indicate that the intra-molecular forces of the potassium chloride crystals differ from those of the sodium chloride crystal, or, more precisely, that certain lattice regions are more closely united in the former, whilst such differences are not observed in the latter. In the light of these observations, it is surprising that the X-ray analysis indicates the same lattice for each crystal. 

F. Wallerant found that when mixed crystals are formed with increasing proportions of rubidium nitrate, the transformation point of caesium nitrate was lowered from 161°, until, with 75 per cent, of RbNOa, it reaches 145° the transition... 

Mixed crystals are formed by replacement of some host molecules by others similar in dimensions and in their interactions with neighbours. Impurity or "guest molecules with lower transition energies can capture or trap excitation energy from the host crystal. 

In the inverted band a quite different pattern of intensity distribution is to be expected. In the pure crystal the topmost level alone is active it remains the strongest under all conditions. As the trap is deepened, some intensity moves from the topmost level downward through the band into the bottom level, which breaks out of the band and eventually becomes practically a localized state of the trapping molecule. Thus the presence of guest molecules awakens spectral activity in normally inactive levels, and should enable the extent and character of the pure crystal band structure to be studied experimentally. The point is illustrated in the diagrammatic spectra in Fig. 6, illustrating the transitions in one-dimensional mixed crystals for trap depths from zero (pure crystal) to d = 3.6. In each case the intensities are adjusted to make the lowest transition have unit intensity this... 

Preferential Enrichment is a secondary phenomenon caused by a polymorphic transition occurring during crystallization from a highly supersaturated solution. This unique dynamic enantiomeric resolution phenomenon has proved to be observable for a fairly ordered racemic mixed crystal showing a polymorphism a solvent-assisted solid-to-sohd type of polymorphic transition from the kinetically-formed metastable crystalline phase comprising homochiral R and S chains into the thermodynamically stable crystalline phase consisting of a heterochiral 2D sheet structure during crystallization is responsible for this phenomenon. That is, it is essential that homochiral R and S ID chain structures are stable in solution while a heterochiral 2D sheet structure is stable in the crystal. 

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