Aromatic hydrocarbons, heats

Since aliphatic hydrocarbons (unlike aromatic hydrocarbons, p. 155) can be directly nitrated only under very special conditions, indirect methods are usually employed for the preparation of compounds such as nitroethane, CjHsNO. When ethyl iodide is heated with silver nitrite, two isomeric compounds are formed, and can be easily separated by fractional distillation. The first is the true ester, ethyl nitrite, C,HiONO, of b.p. 17° its identity is shown by the action of hot sodium hydroxide solution, which hydrolyses it, giving ethanol and... 

A further difference between aliphatic and aromatic hydrocarbons is that only the latter are capable of direct sulphonation. Thus benzene when heated with concentrated sulphuric acid gives benzenesulphonic acid, a reaction which proceeds more readily, however, if chlorosulphonic acid is used instead of sulphuric acid an excess of chlorosulphonic acid however may convert the sul phonic acid into the sulphonyl chloride (c/. p. 181). 

SULPHONATION OF AROMATIC HYDROCARBONS Aromatic hydrocarbons may be mono-sulphonated by heating with a slight excess of concentrated sulphuric acid for benzene, oleum (7-8 per cent. SOj) gives somewhat better results. The reaction is usually complete when all the hydrocarbon has dissolved. Examples are ... 

An additional useful test is to distil the acid or its sodium salt with soda lime. Heat 0.5 g. of the acid or its sodium salt with 0 2 g. of soda lime in an ignition tube to make certain that there is no explosion. Then grind together 0-5 g. of the acid with 3 g. of soda hme, place the mixture in a Pyrex test-tube and cover it with an equal bulk of soda hme. Fit a wide dehvery tube dipping into an empty test-tube. Clamp the tube near the mouth. Heat the soda lime first and then the mixture gradually to a dull-red heat. Examine the product this may consist of aromatic hydrocarbons or derivatives, e.g., phenol from sahcyUc acid, anisole from anisic acid, toluene from toluic acid, etc. 

Fuming sulphuric acid test. Place 2 ml. of 20 per cent, fuming sulphuric acid in a dry test-tube, add 0 -5 ml. of the hydrocarbon and shake vigorously. Only the aromatic hydrocarbon dissolves completely heat is evolved, but excessive charring should be absent. 

Divide the heats of combustion by the number of carbons The two aromatic hydrocarbons (benzene and [18]annulene) have heats of combustion per carbon that are less than those of the nonaromatic hydrocarbons (cyclooctatetraene and [16]annulene) On a per carbon basis the aromatic hydrocarbons have lower potential energy (are more stable) than the nonaromatic hydrocarbons... 

Aromatic hydrocarbons with an unsaturated side chain undergo ring closure when heated with Lewis acids (56). 

The endoperoxides of polynuclear aromatic compounds are crystalline soHds that extmde singlet oxygen when heated, thus forming the patent aromatic hydrocarbon (44,66,80,81). Thus 9,10-diphenyl-9,10-epidioxyanthrancene [15257-17-7] yields singlet oxygen and 9,10-diphenylanthracene. 

Pitches can be transformed to a mesophase state by further chemical and physical operations. Heat treatment of conventional pitches results in additional aromatic polymeriza tion and the distillation of low molecular weight components. This results in an increase in size and concentration of large planar aromatic molecular species whereupon the precursor pitch is transformed to a mesophase state exhibiting the characteristics of nematic Hquid crystals (1). Additional heat treatment converts the mesophase pitch to an infusible aromatic hydrocarbon polymer designated as coke. 

Chlorinated rubber Air drying Solvent evaporation Aromatic hydrocarbons Good Good Very good Poor Good Very poor heat resistance... 

Simple aromatic hydrocarbons come from two main sources coal and petroleum. Coal is an enormously complex mixture made up primarily of large arrays of benzene-like rings joined together. Thermal breakdown of coal occurs when it is heated to 1000 °C in the absence of air, and a mixture of volatile products called coal for boils off. Fractional distillation of coal tar yields benzene, toluene, xylene (dimethylbenzene), naphthalene, and a host of other aromatic compounds (Figure 15.1). 

Naphthalene and other polycyclic aromatic hydrocarbons show many of the chemical properties associated with aromaticity. Thus, measurement of its heat of hydrogenation shows an aromatic stabilization energy of approximately 250 kj/mol (60 kcal/mol). Furthermore, naphthalene reacts slowly with electrophiles such as Br2 to give substitution products rather than double-bond addition products. 

Polysulfone It is a high performance amorphous plastic that is tough, highly heat resistant, strong and stiff. Products are transparent and slightly clouded amber in color. Material exhibits notch sensitivity and is attacked by ketones, esters, and aromatic hydrocarbons. Other similar types in this group include polyethersulfone, polyphenyl-sulfone, and polyarylsulfone. Use includes medical equipment, solar-heating applications and other performance applications where flame retardance, autoclavability and transparency are needed. 

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