Phase anomalous

The reports were that water condensed from the vapor phase into 10-100-/im quartz or pyrex capillaries had physical properties distinctly different from those of bulk liquid water. Confirmations came from a variety of laboratories around the world (see the August 1971 issue of Journal of Colloid Interface Science), and it was proposed that a new phase of water had been found many called this water polywater rather than the original Deijaguin term, anomalous water. There were confirming theoretical calculations (see Refs. 121, 122) Eventually, however, it was determined that the micro-amoimts of water that could be isolated from small capillaries was always contaminated by salts and other impurities leached from the walls. The nonexistence of anomalous or poly water as a new, pure phase of water was acknowledged in 1974 by Deijaguin and co-workers [123]. There is a mass of fascinating anecdotal history omitted here for lack of space but told very well by Frank [124]. 

Werner A, Sohmid F, Muller M and Binder K 1997 Anomalous size-dependenoe of interfaoial profiles between ooexisting phases of polymer mixtures in thin film geometry a Monte-Carlo study J. Chem. Phys. 107 8175... 

When initiator is first added the reaction medium remains clear while particles 10 to 20 nm in diameter are formed. As the reaction proceeds the particle size increases, giving the reaction medium a white milky appearance. When a thermal initiator, such as AIBN or benzoyl peroxide, is used the reaction is autocatalytic. This contrasts sharply with normal homogeneous polymerizations in which the rate of polymerization decreases monotonicaHy with time. Studies show that three propagation reactions occur simultaneously to account for the anomalous auto acceleration (17). These are chain growth in the continuous monomer phase chain growth of radicals that have precipitated from solution onto the particle surface and chain growth of radicals within the polymer particles (13,18). 

The freezing point diagram for the hydrazine—water system (Eig. 1) shows two low melting eutectics and a compound at 64 wt % hydrazine having a melting point of —51.6°C. The latter corresponds to hydrazine hydrate [7803-57-8] which has a 1 1 molar ratio of hydrazine to water. The anomalous behavior of certain physical properties such as viscosity and density at the hydrate composition indicates that the hydrate exists both in the Hquid as well as in the soHd phase. In the vapor phase, hydrazine hydrate partially dissociates. 

Fig. 1. (a) Phase matched second harmonic generation (2cJ = 0.49 fiTo) at cj = 0.98 where = refractive index by ordinary rays and = by extraordinary rays, (b) Hypothetical anomalous dispersion phase matching at 850 nm in similar a crystal having a Lorent2ian absorption centered at 650... 

Phase information can also be obtained by Multiwavelength Anomalous Diffraction experiments... 

The intensity differences obtained in the diffraction pattern by illuminating such a crystal by x-rays of different wavelengths can be used in a way similar to the method of multiple isomorphous replacement to obtain the phases of the diffracted beams. This method of phase determination which is called Multiwavelength Anomalous Diffraction, MAD, and which was pioneered by Wayne Hendrickson at Columbia University, US, is now increasingly used by protein cystallographers. 

X-ray data are recorded either on image plates or by electronic detectors The rules for diffraction are given by Bragg s law Phase determination is the major crystallographic problem Phase information can also be obtained by Multiwavelength Anomalous Diffraction experiments... 

The well defined change in compressibility of the fee alloy at 2.5 GPa clearly indicates the expected behavior of a second-order phase transition. The anomalously high value of the compressibility for the pressure-sensitive fee alloy is demonstrated in the comparison of compressibilities of various ferromagnetic iron alloys in Table 5.1. The fee Ni alloy, as well as the Invar alloy, have compressibilities that are far in excess of the normal values for the... 

A pecuhar sohd phase, which has been discovered not too long ago [172], is the quasi-crystalline phase. Quasi-crystals are characterized by a fivefold or icosahedral symmetry which is not of crystallographic type and therefore was assumed to be forbidden. In addition to dislocations which also exist in normal crystals, quasi-crystals show new types of defects called phasons. Computer simulations of the growth of quasicrystals [173] are still somewhat scarce, but an increasing number of quasi-crystalline details are studied by simulations, including dislocations and phasons, anomalous self-diffusion, and crack propagation [174,175]. 

Heterogeneous copolymerization of acrylamide causes redistribution comonomers between phases I and II. This leads to a change of copolymer composition in phases I and II. As a result, the values of ri and change. This accounts for anomalous widening of the experimental composition distribution curves as compared with theoretical curves. 

FegNi. Frozen phonon calculations combined with the determination of the electron-phonon matrix in the framework of the theory of Varma and Weber have been carried out for the ferrous alloy. The resulting phonon dispersion for the bet phase was already presented elsewhere . As expected, no softening or anomalous curvatures have been detected. This confirms the existence of a bet ground state for FesNi. 

Figure 1. Phase diagram of the Ti - H system. Points are related to the anomalous ductility behavior.

Other ductility behavior showed alloys with x = 1-25 and 1.54 whose ductility A (T) jumped near 300°C, passed through a maximum at about 350°C, passed through a maximum at about 350°C, and again decreased at higher test temperatures. Points in Fig. 1 correspond to temperatures of anomalous Au(T) behavior for appropriate hydrogen contents. A clear correlation is observed between the ductility anomalies and special lines in the phase diagram, it i.e., all points fall at the boundaries of the two-phase regions or at the line equidistant from these boundaries. 

The C, values for Sb faces are noticeably lower than those for Bi. Just as for Bi, the closest-packed faces show the lowest values of C, [except Bi(lll) and Sb(lll)].28,152,153 This result is in good agreement with the theory428,429 based on the jellium model for the metal and the simple hard sphere model for the electrolyte solution. The adsorption of organic compounds at Sb and Bi single-crystal face electrodes28,152,726 shows that the surface activity of Bi(lll) and Sb(lll) is lower than for the other planes. Thus the anomalous position of Sb(lll) as well as Bi(lll) is probably caused by a more pronounced influence of the capacitance of the metal phase compared with other Sb and Bi faces28... 

X-Ray diffraction from single crystals is the most direct and powerful experimental tool available to determine molecular structures and intermolecular interactions at atomic resolution. Monochromatic CuKa radiation of wavelength (X) 1.5418 A is commonly used to collect the X-ray intensities diffracted by the electrons in the crystal. The structure amplitudes, whose squares are the intensities of the reflections, coupled with their appropriate phases, are the basic ingredients to locate atomic positions. Because phases cannot be experimentally recorded, the phase problem has to be resolved by one of the well-known techniques the heavy-atom method, the direct method, anomalous dispersion, and isomorphous replacement.1 Once approximate phases of some strong reflections are obtained, the electron-density maps computed by Fourier summation, which requires both amplitudes and phases, lead to a partial solution of the crystal structure. Phases based on this initial structure can be used to include previously omitted reflections so that in a couple of trials, the entire structure is traced at a high resolution. Difference Fourier maps at this stage are helpful to locate ions and solvent molecules. Subsequent refinement of the crystal structure by well-known least-squares methods ensures reliable atomic coordinates and thermal parameters. 

The semiconducting properties of the compounds of the SbSI type (see Table XXVIII) were predicted by Mooser and Pearson in 1958 228). They were first confirmed for SbSI, for which photoconductivity was found in 1960 243). The breakthrough was the observation of fer-roelectricity in this material 117) and other SbSI type compounds 244 see Table XXIX), in addition to phase transitions 184), nonlinear optical behavior 156), piezoelectric behavior 44), and electromechanical 183) and other properties. These photoconductors exhibit abnormally large temperature-coefficients for their band gaps they are strongly piezoelectric. Some are ferroelectric (see Table XXIX). They have anomalous electrooptic and optomechanical properties, namely, elongation or contraction under illumination. As already mentioned, these fields cannot be treated in any detail in this review for those interested in ferroelectricity, review articles 224, 352) are mentioned. The heat capacity of SbSI has been measured from - 180 to -l- 40°C and, from these data, the excess entropy of the ferro-paraelectric transition... 

The concept of hyperconjugation arose from the discovery of apparently anomalous electron-release patterns for alkyl groups. By the field effect alone, the order of electron release for simple alkyl groups connected to an unsaturated system is fert-butyl > isopropyl > ethyl > methyl, and this order is observed in many phenomena. Thus, the dipole moments in the gas phase of PhCHa, PhC2Hs, PhCH(CHa)2, and PhC(CHa)a are, respectively, 0.37, 0.58, 0.65 and 0.700. ... 

A large amount of work has been done on this subject. Though a great deal is known, much is still poorly understood, and many results are anomalous and hard to explain. In this section, only approximate generalizations are attempted. The work discussed here, and the conclusions reached, pertain to reactions taking place in solution. Some investigations have also been carried out in the gas phase. ... 

Hendrickson WA, Smith JL, Sheriff S. Direct phase determination based on anomalous scattering. Methods Enzymol 1985 115 44-55. 

The additional delay causes a decrease in signal strength due to loss of magetization from transverse relaxation. Moreover, severe phase distortions, particularly for CH3 carbons, can produce anomalous results. A further modification of INEPT known as INEIH" incorporates an additional... 

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