Free states

C2H4N2O3, NH2CONHCOOH. Unknown in the free state as it breaks down immediately to urea and COi- The NH4, Ba, Ca, K and Na salts are known and are prepared by treating ethyl allophanate with the appropriate hydroxide. The esters with alcohols and phenols are crystalline solids, sparingly soluble in water and alcohol. They are formed by passing cyanic acid into alcohols or a solution of an alcohol or phenol in benzene. The amide of allophanic acid is biuret. Alcohols are sometimes isolated and identified by means of their allophanates. 

Certain other amino-acids occur in a few proteins, and others, not necessarily a- or l-amino-acids, are found naturally in the free state or as constituents of peptides. 

C7H6O4. Crystallizes with IH2O m.p. 199" C. It occurs in the free state in the onion and other plants is a constituent of one group of tannins, and is a product of the alkaline decomposition of resins. 

Solids materials that are insoluble in hydrocarbon or water can be entrained in the crude. These are called bottom sediments and comprise fine particles of sand, drilling mud, rock such as feldspar and gypsum, metals in the form of minerals or in their free state such as iron, copper, lead, nickel, and vanadium. The latter can come from pipeline erosion, storage tanks, valves and piping systems, etc. whatever comes in contact with the crude oil. 

Fluorine in the free state is too reactive to be of a direct practical value, but it may be used to prepare other compounds of fluorine, which are then used as fluorinating agents, for example chlorine... 

The confinement term is unique because it alone causes a dependence of the binding free energy on the choice of unit concentration in the standard state the volume available per ligand molecule in the free state, and hence the compression factor, depend on the unit concentration. 

Conformational Adjustments The conformations of protein and ligand in the free state may differ from those in the complex. The conformation in the complex may be different from the most stable conformation in solution, and/or a broader range of conformations may be sampled in solution than in the complex. In the former case, the required adjustment raises the energy, in the latter it lowers the entropy in either case this effect favors the dissociated state (although exceptional instances in which the flexibility increases as a result of complex formation seem possible). With current models based on two-body potentials (but not with force fields based on polarizable atoms, currently under development), separate intra-molecular energies of protein and ligand in the complex are, in fact, definable. However, it is impossible to assign separate entropies to the two parts of the complex. 

This synthesis of the pyrrole ring system, due to Knorr, consists in the condensation of an a-aminoketone with a 1,3-diketone or the ester of a p-keto-acid, a-Aminoketones are unstable in the free state, readily undergoing self-condensation consequently they must be prepared, by the reduction of an a-nitroso (or oximino) ketone, in the presence of the 1,3-diketone or p-ketoester, to ensure rapid interaction. 

The initial product, nitrosobenzene, is so easily reduced to p-phenylhydroxyl-amine that it has never been isolated in the free state, but its presence has been established by reaction in solution with hydroxylamine to 3deld a phenyldi-azonium salt, which couples readily with a a-naphthylamine to form the dyestuff phenyl-azo-a-naphthylamine (compare Section IV,77) ... 

A contact between two plates is considered provided that one of the plates has a crack. In a stress free state both plates remain at a given distance from each other. The plate displacements satisfy two restrictions of inequality type. The first restriction describes the nonpenetration between the plates, and it is considered in the exterior of the domain. The second one describes the nonpenetration between crack faces. 

The second plate (which has no cracks) can be in contact with the first plate (which has the crack). We assume that the plates remain at a distance (5 > 0 from each other in the stress free state, 5 = const (see Fig.3.3). They may be in contact due to exterior forces. The mid-surface of the second plate is precisely fl, which corresponds to the negative value of the coordinate By that the first plate is called the upper plate and the second one the lower plate. 

Sihceous matter other than clay may occur in the free state as sand, quartz fragments, and chert, and in the combined state as feldspar, mica, talc (qv), and serpentine. Metallurgical and chemical limestones should contain less than 1% alumina and 2% siUca. 

Occurrence. Niobium and tantalum usually occur together. Niobium never occurs as the metal, ie, ia the free state. Sometimes it occurs as a hydroxide, siUcate, or borate most often it is combiaed with oxygen and another metal, forming a niobate or tantalate ia which the niobium and tantalum isomorphously replace one another with Htde change ia physical properties except density. Ore concentrations of niobium usually occur as carbonatites and are associated with tantalum ia pegmatites and alluvial deposits. Principal niobium-beariag minerals can be divided iato two groups, the titano- and tantalo-niobates. 

Aminophenol. This compound forms white plates when crystallized from water. The base is difficult to maintain in the free state and deteriorates rapidly under the influence of air to pink-purple oxidation products. The crystals exist in two forms. The a-form (from alcohol, water, or ethyl acetate) is the more stable and has an orthorhombic pyramidal stmcture containing four molecules per unit cell. It has a density of 1.290 g/cm (1.305 also quoted). The less stable P-form (from acetone) exists as acicular crystals that turn into the a-form on standing they are orthorhombic bipyramidal or pyramidal and have a hexamolecular unit (15,16,24) (see Tables 3—5). 

Sodium is not found ia the free state ia nature because of its high chemical reactivity. It occurs naturally as a component of many complex minerals and of such simple ones as sodium chloride, sodium carbonate, sodium sulfate, sodium borate, and sodium nitrate. Soluble sodium salts are found ia seawater, mineral spriags, and salt lakes. Principal U.S. commercial deposits of sodium salts are the Great Salt Lake Seades Lake and the rock salt beds of the Gulf Coast, Virginia, New York, and Michigan (see Chemicals frombrine). Sodium-23 is the only naturally occurring isotope. The six artificial radioisotopes (qv) are Hsted ia Table 1 (see Sodium compounds). 

Dextrose (D-glucose) is by far the most abundant sugar in nature. It occurs either in the monosaccharide form (free state) or in a polymeric form of anhydrodextrose units. As a monosaccharide, dextrose is present in substantial quantities in honey, fmits, and berries. As a polymer, dextrose occurs in starch, cellulose (qv), and glycogen. Sucrose is a disaccharide of dextrose and fmctose. 

Triterpenes. The triterpenes (30 carbon atoms) are widely found in nature, especially plants, both in the free state and as esters or glycosides. A smaller but important group, including lanosterol [79-63-0] (114), occurs in animals. The triterpene hydrocarbon, squalene [111-02-4] (115), occurs in the hver oils of certain fish, especially those of sharks. 

Benzoic acid in the free state, or in the form of simple derivatives such as salts, esters, and amides, is widely distributed in nature. Gum benzoin (from styrax ben in) may contain as much as 20% benzoic acid in the free state or in combinations easily broken up by heating. Acaroid resin (from anthorrhoca haslilis) contains from 4.5 to 7%. Smaller amounts of the free acid are found in natural products including the scent glands of the beaver, the bark of the black cherry tree, cranberries, pmnes, ripe cloves, and oil of anise seed. Pern and Tolu balsams contain benzyl benzoate the latter contains free benzoic acid as well. The urine of herbivorous animals contains a small proportion of the glycine derivative of benzoic acid, hippuric acid [495-69-2] (CgH CONHCH2COOH). So-called natural benzoic acid is not known to be available as an item of commerce. 

Carbamic acid [463-77-4] NH2COOH, is the hydrated form of isocyanic acid [75-13-8] H—N=C=0. It is not known in the free state hydrolysis rapidly gives ammonia and carbon dioxide. 

Abrasive. Dentifrices have the unique ability to remove extrinsic tooth stains, which are caused by agents such as berries, tea, smoking, antibiotics, and certain bacteria as they attach to the dental pellicle. These stains can be removed only by abrasive cleaning a toothbmsh alone is not adequately effective. It has been shown that only 4% of a test population were able to maintain thein teeth in an acceptably stain-free state without an abrasive and that 18% of the population were "heavy" stainers (2). However, colored materials found in dental plaque are removable without abrasives. 

Vinyl alcohol does not exist in the free state and all attempts to prepare it have led instead to the production of its tautomer, acetaldehyde. 

By reaction of polyhydroxy compounds with a carbonic acid derivative, a series of related polymers may be produced with carbonate (—0 C0 0—) linkages, the polymers being referred to as polycarbonates. Carbonic acid, C0(0H)2, itself does not exist in the free state but by means of ester exchange Figure 20.1) (1) and phosgenation techniques (II) it is possible to produce useful products. 

The two intermediates of commercial furan resins are furfural and furfuryl alcohol. Furfural occurs in the free state in many plants but is obtained commercially by degradation of hemicellulose constituents present in these plants. There are a number of cheap sources of furfural, and theoretical yields of over 20% (on a dry basis) may be obtained from both com cobs and oat husks. In practice yields of slightly more than half these theoretical figures may be obtained. In the USA furfural is produced in large quantities by digestion of com cobs with steam and sulphuric acid. The furfural is removed by steam distillation. 

Sinapine, CjgHjjOgN, was isolated as a thiocyanate from black mustard seeds (Brassica nigra) by Henry and Garot." Will and Laubenheimer first noted that sinapine occurs in white mustard seed in the form of the alkaloidal glucoside sinalbine, CajH jOuNgSg, which, on hydrolysis by the enzyme myrosin, also present in the seed, furnished dextrose, p-hydroxybenzylthiocarbimide and sinapine sulphate. Owing to its instability sinapine is unknown in the free state. The thiocyanate can be recrystallised from water and converted into the acid sulphate by treatment with sulphuric acid. 

---