Pure crystals

Decolorisation by Animal Charcoal. It sometimes hap pens (particularly with aromatic and heterocyclic compounds) that a crude product may contain a coloured impurity, which on recrystallisation dissolves in the boiling solvent, but is then partly occluded by crystals as they form and grow in the cooling solution. Sometimes a very tenacious occlusion may thus occur, and repeated and very wasteful recrystallisation may be necessary to eliminate the impurity. Moreover, the amount of the impurity present may be so small that the melting-point and analytical values of the compound are not sensibly affected, yet the appearance of the sample is ruined. Such impurities can usually be readily removed by boiling the substance in solution with a small quantity of finely powdered animal charcoal for a short time, and then filtering the solution while hot. The animal charcoal adsorbs the coloured impurity, and the filtrate is usually almost free from extraneous colour and deposits therefore pure crystals. This decolorisation by animal charcoal occurs most readily in aqueous solution, but can be performed in almost any organic solvent. Care should be taken not to use an excessive quantity... 

The theory underlying the removal of impurities by crystaUisation may be understood from the following considerations. It is assumed that the impurities are present in comparatively small proportion—usually less than 5 per cent, of the whole. Let the pure substance be denoted by A and the impurities by B, and let the proportion of the latter be assumed to be 5 per cent. In most instances the solubilities of A (SJ and of B (/Sb) are different in a particular solvent the influence of each compound upon the solubility of the other will be neglected. Two cases will arise for an3 particular solvent (i) the impurity is more soluble than the compound which is being purified (/Sg > SA and (ii) the impurity is less soluble than the compound Sg < S ). It is evident that in case (i) several recrystallisations will give a pure sample of A, and B will remain in the mother liquors. Case (ii) can be more clearly illustrated by a specific example. Let us assume that the solubility of A and 5 in a given solvent at the temperature of the laboratory (15°) are 10 g. and 3 g. per 100 ml. of solvent respectively. If 50 g. of the crude material (containing 47 5 g. of A and 2-5 g. of B) are dissolved in 100 ml. of the hot solvent and the solution allowed to cool to 15°, the mother liquor will contain 10 g. of A and 2-5 g. (i.e., the whole) of B 37-5 g. of pure crystals of A will be obtained. 

The process of growing a pure crystal is sensitive to a host of process parameters that impact the iacorporation of impurities ia the crystal, the quality of the crystal stmcture, and the mechanical properties of the crystal rod. For example, the crystal-pulling mechanism controls the pull rate of the crystallisa tion, which affects the iacorporation of impurities ia the crystal, and the crystal rotation, which affects the crystal stmcture. 

Impurity-produced plasmas in semiconductors do not have to be compensated by charges of the opposite sign. These plasmas can be produced by introduction of either electron donors or electron scavengers, ie, hole producers, into semiconductor lattices. Thek densities range from a lower limit set by the abihty to produce pure crystals particles/cm ) to values in excess of 10 particles/cm. Plasmas in semiconductors generally are dilute, so that... 

Dissolution of Silver. Silver is dissolved by oxidising acids and alkaU metal cyanide solutions in the presence of oxygen. The latter method is the principal technique for dissolving silver from ore. Silver has extensive solubiUty in mercury (qv) and low melting metals such as sodium, potassium, and their mixtures. Cyanide solutions of silver are used for electroplating and electroforming. The silver is deposited at the cathode either as pure crystals or as layers on a mandrel. 

Physical, Sulfamic acid is a diy acid having oithorhombic crystals. The pure crystals ate nonvolatile, nonhygroscopic, colodess, and ododess. The acid is highly stable up to its melting point and may be kept for years without change in properties. Selected physical properties of sulfamic acid are hsted in Table 1. Other properties are available in the hterature (5—8). 

Available Grades. Rhovanil Extra Pure is the trade name of the food-grade vanillin of Rhc ne-Poulenc, worldwide leader in the diphenols area. The following grades are commercially available Rhovanil Extra Pure crystallized, Rhovanil Pine Mesh, Rhovanil Pree Plow, and Rhovanil Liquid. 

Crystal Morphology. Size, shape, color, and impurities are dependent on the conditions of synthesis (14—17). Lower temperatures favor dark colored, less pure crystals higher temperatures promote paler, purer crystals. Low pressures (5 GPa) and temperatures favor the development of cube faces, whereas higher pressures and temperatures produce octahedral faces. Nucleation and growth rates increase rapidly as the process pressure is raised above the diamond—graphite equiUbrium pressure. 

By beginning with methane, the diamonds formed have only in them. These tiny diamonds may then be used as the carbon source to form large (5 mm) single crystals by growth from molten catalyst metal in a temperature gradient. The resulting nearly pure crystals have outstanding thermal conductivities suitable for special appHcations as windows and heat sinks (24). 

NaBH4 has also been crystd from isopropylamine by dissolving it in the solvent at reflux, cooling, filtering and allowing the solution to stand in a filter flask connected to a Dry-ice/acetone trap. After most of the solvent was passed over into the cold trap, crystals were removed with forceps, washed with dry diethyl ether and dried under vacuum. [Kim and Itoh J Phys Chem 91 126 1987.] Somewhat less pure crystals were obtained more rapidly by using Soxhlet extraction with only a small amount of solvent and extracting for about 8h. The... 

Therefore, if the solubility data for a substance are known, it is a simple matter to calculate the potential yield of pure crystals that could be obtained from batch crystallization (equations 7.4 and 7.6). Conversely, the degree of evaporation to produce a specified yield may be estimated (equation 7.8). 

Fig. 5. The one that has non-zero values only near q=0.0 corresponds to twelve Cu atoms on the nn-shell, ci=100%. It is known that an atom on a site surrounded by like atoms behaves somewhat like an atom in a pure crystal, and would have little net charge. The conditional probability centered near q=0.2 corresponds to ci=0%, with all the neighboring atoms Zn. Such an atom behaves like a Cu impurity in a Zn crystal. The probabilities Pcu(ci,q) for ci=25%, 50%, and 75% have their centers between these limits, llte conditional probabilities have a structure themselves. Extrapolating, it should be possible to write Pcu(ci>q) a sum of the conditional probabilities Pcu(ci,C2,q) where C2 is the concentration of Cu atoms on the second nn-shell. That probability could, in turn, be written as the sum of probabilities PCu(ci,C2,C3,q), where eg is the concentration of Cu atoms on the third nn-shell.

For example, consider the chemical composition of a very old crystal of pitchblende, U308. We may presume that this crystal was formed at a time when chemical conditions for its formation were favorable. For example, it may have precipitated from molten rock during cooling. The resulting crystals tend to exclude impurities. Yet, careful analysis shows that every deposit of pitchblende contains a small amount of lead. This lead has accumulated in the crystal, beginning at the moment the pure crystal was formed, due to the radioactive decay of the uranium. 

A single crystallisation is unlikely to lead to the isolation of pure crystals. In practice the product recovered in this process contains about 90% 11 a-hydroxyprogeterone with low levels of other products (especially 5 a-pregnane-3,20-dione and 60, lla-dihydroxyprogesterone). An example of a manufacturer who uses microbial 11a hydroxylation is Upjohn progesterone is used as substrate. 

Color black (pure crystal is transparent and colorless)... 

The presence of isotopic impurities causes clear effects in the vibrational spectra. Almost all modes studied so far show frequency shifts on S/ S substitution [81, 107]. The average shift of the internal modes is ca. 0.6 cm , and of the external modes it is 0.1-0.3 cm (Tables 3, 4 and 5). Furthermore, the isotopomers which are statistically distributed in crystals of natural composition can act as additional scattering centers for the phonon propagation. Therefore, in such crystals the lifetime of the phonons is shortened in comparison with isotopically pure crystals and, as a conse-... 

Lattice Vacancies and Interstitials Defects such as lattice vacancies and interstitials fall into two main categories intrinsic defects, which are present in pure crystal at thermodynamic equilibrium, and extrinsic defects, which are created when a foreign atom is inserted into the lattice. 

Here m is the mode order (m — 1,3,5. .., usually 1 for polyethylenes), c the velocity of light, p the density of the vibrating sequence (density of pure crystal) and E the Young s modulus in the chain direction. The LAM band has been observed in many polymers and has been widely used in structural studies of polyethylenes [94—99,266], as well as other semi-crystalline polymers, such as poly (ethylene oxide) [267], poly(methylene oxide) [268,269] and isotactic poly(propylene) [270,271], The distribution of crystalline thickness can be obtained from the width of the LAM mode, corrected by temperature and frequency factors [272,273] as ... 

Chin, et al. (1972) measured the hardnesses of Na and K halides (Cl, Br, and I) containing various additions of Ca++, Sr++, or Ba++. Then they extrapolated the measurements back to zero additions to get values for the pure crystals. They found that the latter depended linearly on the Young s moduli of their crystals. Gilman (1973) found an equally good correlation with the shear stiffnesses, where FI = 1.37 x 10 2 C44 (d/cm2) in excellent agreement with Equation 9.1. A comparison of the data and the theory is given in Figure 9.5. 

A straightforward estimate of the maximum hardness increment can be made in terms of the strain associated with mixing Br and Cl ions. The fractional difference in the interionic distances in KC1 vs. KBr is about five percent (Pauling, 1960). The elastic constants of the pure crystals are similar, and average values are Cu = 37.5 GPa, C12 = 6 GPa, and C44 = 5.6 GPa. On the glide plane (110) the appropriate shear constant is C = (Cu - C12)/2 = 15.8 GPa. The increment in hardness shown in Figure 9.5 is 14 GPa. This corresponds to a shear flow stress of about 2.3 GPa. which is about 17 percent of the shear modulus, or about C l2n. 

Trends in the hardnesses of molecular crystals are similar to those of inorganic crystals (Stephens et al., 2003). Thus, mixed crystals are harder than their pure components, crystals with foreign solutes are harder than pure crystals, and molecular crystals may be anisotropic. 

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