of sodium, in absolute ether solution (A. Wurtz, Ann. chim. phys.,
1855 (3), 44. p. 275), 2RI+2Na=R·R+2NaI. They may also be
obtained by the reduction of the higher fatty acids with hydriodic
acid (F. Krafft, Ber., 1882, 15, pp. 1687, 1711), C𝑛H2𝑛O2+6HI=C𝑛H2𝑛+2+2H2O+3I2;
by the conversion of ketones into ketone
chlorides by the action of phosphorus pentachloride, these being
then reduced by hydriodic acid,
C𝑛H2𝑛+12CO→C𝑛H2𝑛+1CCl2→C𝑛H2𝑛+12CH2;
by the reduction of unsaturated hydrocarbons with hydrogen in the presence of a “contact” substance, such, for example, as reduced nickel, copper, iron or cobalt (P. Sabatier and J. B. Senderens, Ann. chim. phys., 1905 [8], 4, pp. 319, 433); by the elimination of carbon dioxide from the fatty acids on heating their salts with soda-lime or baryta, CH3CO2Na + NaOH=CH4+Na2CO3, or by heating their barium salts with sodium methylate in vacuo (I. Mai, Ber., 1889, 22, p. 2133); by the electrolysis of the fatty acids (H. Kolbe, Ann., 1849, 69, p. 257), 2C2H4O2=C2H6+2CO2+H2O; and by the action of the zinc alkyls on the ketone chlorides, (CH3)2CCl2 + Zn(CH3)2=C5H12+ZnCl2.
The principal members of the series are shown in the following table:—
Name. | Formula. | Melting- point. |
Boiling- point. |
Methane | CH4 | −184° | −164° (760 mm.) |
Ethane | C2H6 | −172·1° | −84·1° (749 „ ) |
Propane | C3H8 | −45° | −44·5° |
Normal Butane | C4H10 | — | +1° |
Isobutane | „ | — | −17° |
Normal Pentane | C5H12 | — | +36·3° |
Secondary Pentane | „ | — | +30·4° |
Tertiary Pentane | „ | — | +9° |
Hexane | C6H14 | — | +69° |
Heptane | C7H16 | — | 98–99° |
Octane | C8H18 | — | 125–126° |
Nonane | C9H20 | −51° | 150° |
Decane | C10H22 | −31° | 173–4° |
Undecane | C11H24 | −26·5° | 196° |
Dodecane | C12H26 | −12° | 214–216° |
Tridecane | C13H28 | −6·2° | 234° |
Tetradecane | C14H30 | +4° | 252° |
Pentadecane | C15H32 | +10° | 270° |
Hexadecane | C16H34 | +18° | 287° |
Heptadecane | C17H36 | +22° | 170° (15 mm.) |
Octadecane | C18H38 | +28° | 317° |
Nonadecane | C19H40 | +32° | 330° |
Eicosane | C20H42 | +37 | 205 (15 mm.) |
Heneicosane | C21H44 | +40° | 215° ( „ „ ) |
Docosane | C22H46 | +44° | 224° ( „ „ ) |
Tricosane | C23H48 | +48° | 234° ( „ „ ) |
Tetracosane | C24H50 | +51° | 243° ( „ „ ) |
Hexacosane | C26H52 | +58° | — |
Hentriacontane | C31H64 | +68° | 302° (15 mm.) |
Dotriacontane | C32H66 | +70·5° | 331° ( „ „ ) |
Pentatriacontane | C35H72 | +75° | 331° ( „ „ ) |
Dimyricyl | C60H122 | +102° | — |
The lowest members of the series are gases at ordinary temperature; those of carbon content C5 to C15 are colourless liquids, and the higher members from C15 onwards are crystalline solids. The highest members only volatilize without decomposition when distilled under diminished pressure. They are not soluble in water, although the lower and middle members of the series are readily soluble in alcohol and ether, the solubility, however, decreasing with increase of molecular weight, so that the highest members of the series are almost insoluble in these solvents. The specific gravity increases with the molecular weight but always remains below that of water. The paraffins are characterized by their great inertness towards most chemical reagents. Fuming sulphuric acid converts the middle and higher members of the series into sulphonic acids and dissolves the lower members (R. A. Worstall, Amer. Chem. Journ., 1898, 20, p. 664). Dilute nitric acid, when heated with the paraffins in a tube, converts them into secondary and tertiary nitro-derivatives (M. Konowalow, Ber., 1895, 28, p. 1852), whilst long boiling with strong nitric acid or nitro-sulphuric acid converts the middle and higher members of the series partly into primary mono- and di-nitro compounds and partly oxidizes them to carbonic, acetic, oxalic and succinic acids (Worstall, ibid., 20, p. 202; 21, p. 211). Fuming nitric acid only reacts slowly with the normal paraffins at ordinary temperature, but with those containing a tertiary carbon atom the reaction is very energetic, oxidation products (fatty acids and dibasic acids) and a small quantity of polynitro compounds are obtained (W. Markownikow, Centralblatt, 1899, 1, p. 1064; Ber., 1899, 32, p. 1441). Chlorine reacts with the paraffins, readily substituting hydrogen. Isomeric hydrocarbons in this series first appear with butane, the number increasing rapidly as the complexity of the molecule increases. For a means of determining the number of isomers see E. Cayley, Ber., 1875, 8, p. 1056; F. Hermann, Ber., 1898, 31, p. 91.
For Methane see Marsh Gas. Ethane, C2H6, occurs in crude petroleum. It may be prepared by the general methods given above; by heating mercury ethyl with concentrated sulphuric acid (C. Schorlemmer, Ann., 1864, 132, p. 234); or by heating acetic anhydride with barium peroxide (P. Schützenberger, Zeit. für Chemie, 1865, p. 703), 2(CH3CO)2O+BaO2=C2H6 + Ba(C2H3O2)2+2CO2. It is a colourless gas which can be liquefied at 4° C. by a pressure of 46 atmospheres. By slow combustion it yields first water and acetaldehyde, which then oxidizes to oxides of carbon and water (W. A. Bone; see Flame), whilst in ozonized air at 100° it gives ethyl alcohol, together with acetaldehyde and traces of formaldehyde (Bone, Proc. Chem. Soc, 1904, 29, p. 127).
Dimyricyl (hexacontane), C60H122, is prepared by fusing myricyl iodide with sodium (C. Hell and C. Hägele, Ber., 1889, 22, p. 502). It is only very slightly soluble in alcohol and ether.
PARAGON, a term for that which is a model of excellence
or pattern of perfection, hence some person or thing which has
no equal. The word was adopted from the O. Fr. paragon,
Mod. parangon, Ital. paragone and Span. paragon. The Spanish
has usually been taken as the source, and the word explained
as from the prepositional phrase para con, in comparison with.
But the word first appears in Italian, meaning a “touchstone.”
The Italian word may be connected with the Gr. παρακονᾶν, to
sharpen by the use of a whetstone (ἀκονή). The term has been
used in several technical applications, e.g. in printing, of a
large style of type between “great primer” and “double
pica,” now usually called “two-line long primer”; of a
diamond weighing more than 100 carats; and formerly of a
fabric used for hangings in the 17th and 18th centuries.
PARAGRAPH, a term for a section or division of written
or printed matter, which, as beginning a new subject, marking
a break in the subject, &c., is signified by beginning the section
on a new line set back or indented; also by the symbol, now ¶,
a reversed P, formerly ( or ), to mark such a division. The
Gr. παραγραφός (παρὰ and γράφειν, to write alongside or
beside) was used of the short horizontal line or stroke which
marked a line in a MS. where such a division occurs; and
παραγραφή of a marginal note, also the division so marked.
The word “paragraph,” besides these technical typographical
meanings, is also applied to the separate numbered sections
in an affidavit or other legal document, or in a statute, &c.,
and in journalism to a short item of news or brief notice of
events.
PARAGUAY, an inland republic of South America, between 20° 16′ 14" and 26° 31′ S. and 54° 37′ and 62° W. It is bounded on the N.W. by Bolivia, N. and E. by Brazil, S.E., S. and W. by Argentina. Pop. (1905 estimate), 631,347, including 50,000 Iguassú Indians; area, about 97,700 sq. m.
By the treaty of 1872 the Brazilian frontier was drawn up the Paraná from the mouth of the Iguassú or Y-Guazú (25° 30′ S.) to the Salto Grande or Great Cataract of La Guayra (24° 7′), thence west along the watershed of the Sierra de Maracayú, north along the Sierra de Ambaya to the sources of the Apá, and down that stream to its junction with the Paraguay. The Buenos Aires treaty of the 3rd of February 1876 fixed the frontier between Argentina and Paraguay, and assigned to Paraguay the portion of the Gran Chaco between Rio Verde and Bahia Negra; the appropriation of the portion between Rio Verde and the Pilcomayo was submitted to the arbitration of the president of the United States, who in 1878 assigned it to Paraguay. The frontier line towards Bolivia has long been in dispute.
Physical Features.—The river Paraguay, running from north to south, divides the republic into two sections, the eastern section, or Paraguay Oriental, being the most important. The