Crystalline Decomposition

Finally, DSC is used in the broader area of polymer evaluation to measure glass-transition temperature, degree of crystallinity, decomposition profile, etc. Current computer control and storage facilities available with thermal analysis equipment allow data to be comprehensively evaluated, reanalyzed, and compared, reducing the need for repeat analyses. 

The amino-acids are colourless, crystalline substances which melt with decomposition. They are mostly soluble in water and insoluble in alcohol. 

The crystalline sodium sulphide (NajS,9H20) used to prepare the disulphide is very deliquescent, and only a sample which has been kept in a well-stoppered bottle and therefore reasonably dry should be used. A sample from a badly-stoppered bottle may contain, in addition to the crystals, a certain amount of aqueous solution, in which hydrolysis and partial decomposition will have occurred such a sample should therefore be rejected. Add 4 2 g. of finely powdered sulphur to a solution of 16 g. of the crystalline sodium sulphide in 60 ml. of water, and boil the mixture gently for a few minutes until a clear solution of the disulphide is obtained. 

Identification of Amines. Picric acid combines with many amines to give crystalline picrates, of general formula B,(NO )aCeHjOH, where B is a molecule of a monacidic base. These picrates have usually sharp melting- or decomposition-points, and serve to characterise the amines concerned. They may be formed either by (a) direct union of the acid and the base in a suitable solvent, or (6) by the interaction of sodium picrate and a salt of the amine in aqueous solution. 

The latter upon decomposition with dilute hydrochloric acid yields laevo sec.-octyl hydrogen phthalate the crystalline brucine salt, when similarly treated, affords the dextro sec.-octyl hydrogen phthalate. These are reerystallised and separately hydrolysed with sodium hydroxide solution to yield pure I- and d-sec.-octyl alcohols ... 

Nitronium salts are colourless, crystalline and very hygroscopic nitronium perchlorate and sulphate are unstable and liable to spontaneous decomposition, whereas nitronium tetrafluoroborate and other complex fluoro-salts are relatively stable. 

The physical and chemical properties are less well known for transition metals than for the alkaU metal fluoroborates (Table 4). Most transition-metal fluoroborates are strongly hydrated coordination compounds and are difficult to dry without decomposition. Decomposition frequently occurs during the concentration of solutions for crysta11i2ation. The stabiUty of the metal fluorides accentuates this problem. Loss of HF because of hydrolysis makes the reaction proceed even more rapidly. Even with low temperature vacuum drying to partially solve the decomposition, the dry salt readily absorbs water. The crystalline soflds are generally soluble in water, alcohols, and ketones but only poorly soluble in hydrocarbons and halocarbons. 

In some appHcations the high heat stabiHty of the micropowder can be utilized over a reasonably wide temperature range. A maximum service temperature is normally 260°C, provided the crystalline melting point is between 320 and 335°C. Exposure above 300°C leads to degradation and possible evolution of toxic decomposition products. 

Hexamethylenetetramine. Pure hexamethylenetetramine [100-97-0] (also called hexamine and HMTA) is a colorless, odorless, crystalline sohd of adamantane-like stmcture (141). It sublimes with decomposition at >200° C but does not melt. Its solubiUty in water varies Htde with temperature, and at 25°C it is 46.5% in the saturated solution. It is a weak monobase aqueous solutions are in the pH 8—8.5 range (142). Hexamethylenetetramine is readily prepared by treating aqueous formaldehyde with ammonia followed by evaporation and crystallisation of the soHd product. The reaction is fast and essentially quantitative (142). 

Cyclizine Hydrochloride. l-(Diphenylmethyl)-4-methylpipera2ine monohydrochloride [303-25-3] (Mare2ine) (17) is a white crystalline powder, or small colorless crystals, that is odorless or nearly so and has a bitter taste. It melts indistinctly and with decomposition at ca 285°C. One gram of cycli2ine hydrochloride [303-25-3] is soluble in 115 mL water, 115 mL ethanol, and 5 mL chloroform it is insoluble in diethyl ether. It may be made by the synthesis shown in Reference 15. 

Potassium iodate [7758-05-6] KIO, mol wt 214.02, 59.30% I, forms white, odorless crystals or a crystalline powder. It has a density 3.98 g/mL and mp of 560°C with partial decomposition. Potassium iodate is rapidly formed when potassium iodide is fused with potassium chlorate, bromate, or perchlorate. The solubihty in water is 9.16 g/100 g H2O at 25°C and 32.2 g/100 g H2O at 100°C. KIO is extensively used as an oxidizing agent in analytical chemistry and as amaturing agent and dough conditioner (see Bakery processes and leavening agents). 

Nickel formate dihydrate [15694-70-9] Ni(HCOO)2 is a green monoclinic crystalline compound which melts with decomposition to nickel... 

The ultraphosphates are situated between P O q and the metaphosphates. These comparatively Htde-known, highly cross-linked polymers contain at least some of the phosphoms atoms as triply coimected branching points. This stmctural feature is quite unstable toward hydrolysis. Ultraphosphates undergo rapid decomposition upon dissolution. In amorphous ultraphosphates, the cross-linking is presumably scattered randomly throughout the stmctural matrix in contrast, crystalline ultraphosphates have a regular pattern. 

Starch is made thermoplastic at elevated temperatures ia the presence of water as a plasticizer, aHowiag melt processiag alone or ia blends with other thermoplastics (192—194). Good solvents such as water lower the melt-transition temperature of amylose, the crystalline component of starch, so that processiag can be done well below the decomposition—degradation temperature. 

Aluminum nitrate is available commercially as aluminum nitrate nonahydrate [7784-27-2], A1(N02)3 9H20. It is a white, crystalline material with a melting point of 73.5°C that is soluble in cold water, alcohols, and acetone. Decomposition to nitric acid [7699-37-2], HNO, and basic aluminum nitrates [13473-90-0], A1(0H) (N03) where x + = 3, begins at 130°C, and dissociation to aluminum oxide and oxides of nitrogen occurs above 500°C. 

Ammonium sulfate [7783-20-2], (NH 2 U4, is a white, soluble, crystalline salt having a formula wt of 132.14. The crystals have a rhombic stmcture d is 1.769. An important factor in the crystallization of ammonium sulfate is the sensitivity of its crystal habit and size to the presence of other components in the crystallizing solution. If heated in a closed system ammonium sulfate melts at 513 2° C (14) if heated in an open system, the salt begins to decompose at 100°C, giving ammonia and ammonium bisulfate [7803-63-6], NH HSO, which melts at 146.9°C. Above 300°C, decomposition becomes more extensive giving sulfur dioxide, sulfur trioxide, water, and nitrogen, in addition to ammonia. 

When sublimed, anthraquinone forms a pale yeUow, crystalline material, needle-like in shape. Unlike anthracene, it exhibits no fluorescence. It melts at 286°C and boils at 379°—381°C. At much higher temperatures, decomposition occurs. Anthraquinone has only a slight solubiUty in alcohol or benzene and is best recrystallized from glacial acetic acid or high boiling solvents such as nitrobenzene or dichlorobenzene. It is very soluble in concentrated sulfuric acid. In methanol, uv absorptions of anthraquinone are at 250 nm (e = 4.98), 270 nm (4.5), and 325 nm (4.02) (4). In the it spectmm, the double aUyflc ketone absorbs at 5.95 p.m (1681 cm ), and the aromatic double bond absorbs at 6.25 p.m (1600 cm ) and 6.30 pm (1587 cm ). 

AH the bis- and tri-unsaturated prostanoids display sensitivity to atmospheric oxygen similar to that of polyunsaturated fatty acids and Hpids. As a result, exposure to the air causes gradual decomposition although the crystalline prostanoids ate less prone to oxygenation reactions than PG oils or solutions. 

Physical Properties. Anhydrous sodium sulfite [7757-83-7] Na2S02, is an odorless, crystalline soHd and most commercial grades other than by-product materials are colorless or off-white (331—334). It melts only with decomposition. The specific gravity of the pure soHd is 2.633 (15.4°C). Sodium sulfite is quite soluble in water. It has a maximum solubiHty of 28 g/100 g sol at 33.4°C at higher and lower temperatures, it is less soluble in water. Below this temperature, the heptahydrate crystallizes above this temperature, the anhydrous salt crystallizes. Sodium sulfite is soluble in glycerol but insoluble in alcohol, acetone, and most other organic solvents. 

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