CARBON, SYNTHESES OF

the technical synthesis of organic compounds has only attained importance during the present century, it is still convenient to retain the artificial distinction between inorganic and organic chemistry, whether one includes the chemistry of all carbon compounds in the latter branch or considers only such compounds of carbon as contain atoms of carbon directly united to hydrogen, nitrogen or other carbon atoms. the artificial production of urea (wohler, 1828) by isomerisa- tion of ammonium cyanate showed that products of animal metabolism might be produced without the intervention of “vital force” and eventually it was recognised that any carbon compound of known constitution may be built up from carbon itself. the majority of organic compounds are still obtained from animal or vegetable sources or by distillation of oil and coal, but several products, formerly obtained by the distillation of wood are being rapidly displaced by synthetic products from carbon (coke). direct syntheses —carbon unites directly with hydrogen, sili- con, oxygen, sulphur and fluorine, whilst carbides of many metals are known and are usually produced by heating coke with a metallic oxide in the electric furnace. as actual or potential sources of organic compounds, methane, the oxides of carbon and calcium carbide are of greatest importance. methane yields certain substitution products on chlorina- tion from methyl chloride, ch3c; to carbon tetrachloride, cch. the first of these yields methyl alcohol on hydrolysis. carbon monoxide unites directly with caustic soda yielding sodium formate; the latter can be decomposed into hydrogen and sodium oxalate. complete reduction of carbon monoxide gives methane, by incomplete reduction it is possible to make methyl alcohol. carbon dioxide, with ammonia (g.v.), is a source of urea; further, it unites directly with sodium, giving the oxalate. acetylene.—calcium carbide and water give acetylene (g.v.). this hydrocarbon unites with water in presence of acids and mercury salts giving acetaldehyde, ch;.cho which can be poly- merised to alcohol, ch3.choii.ch:.cho; on loss of the ele- ments of water, the latter compound gives crotonaldehyde, ch;.ch:ch.cho. oxidation of acetaldehyde yields acetic acid, ch;.cooh, from which, by removal of the elements of water, acetic anhydride is produced. if, in addition, the ele- ments of carbon dioxide are also removed, acetone is formed. 2ch;. cooh = h.0+ co2+ ch3.co.ch;. butyl alcohol can be obtained from crotonaldehyde by catalytic hydrogenation. ch3.c1hi:ch.cho+4h = ch3.ch:.ch2.ch.oitt, acetylene also combines with chlorine giving tetrachloro- ethane, colfecl, from which hexachloroethane, coclg, trichloro- ethylene, coli;, pentachloroethane, c2hcl;, and dichloroethylene are obtainable. hydrolysis of trichloroethylene gives chloro- acetic acid, ch.c1].cooii, an intermediate in indigo synthesis. calcium carbide reacts with nitrogen at a high temperature giving calcium cyanamide, cn.ca, from which urea is obtainable (sec cyanamides; cyanides). tormates have been manufactured synthetically for several years before 1926; in the case of the other simpler carbon com- pounds the sources of supply afforded by natural products appeared to be sufficient, and confusion and delay were occa- sioned by disregard of the thermodynamic principles underlying gas reactions and lack of knowledge with regard to catalysts. using van’t hoff’s reaction tsochore d log. k/dt = —q/rt? the equilibrium attained in a reaction involving gases may be carbon, syntheses of calculated for an absolute temperature t if the heat of reaction, qo, at that temperature is known. this is possible if the heat of reaction at some definite temperature is known as well as the variation of the molecular heats of the reacting substances with changing temperature. thus, if the data are available, one may calculate in advance whether a reaction is likely to take place under experimental conditions. velocity of reaction.—velocities of reaction which are low at ordinary temperatures may be accelerated by heating; at the same time, the equilibrium is often displaced in a <lirection con- trary to that desired. an example is afforded in the synthesis of methyl alcohol, co+2h2:=ch3;0h+27-2 cal. catalysts are ineffective at ordinary temperature; on heating, equilibrium is displaced from right to left. on the other hand, since kk = pip-*/x, where pi,p2 and x represent the pressures of carbon monoxide, hydrogen and methyl! alcohol respectively, it is evident that increase of pressure will displace the equilibrium from left to right.. thus matignon (bull. soc. chim., 1925, iv. 37, pp. 827) calculates that at 227° c. (t=3500) if prp=1 (atmosphere) and pe= 2, then x=0-06, but if pr= 50 and pp= 100, then x=7,000. x 1s reduced to o-8 for the same values of pi and pe at 427° c. (t= 700). evidently for a given reaction and catalyst there will be an optimum tempcrature from the point of view of yield; above this temperature the equilibrium is unfavourable; below it, the velocity of reaction is too small. applying these principles, matignon shows that the following syntheses should be capable of accomplishment: aliphatic alco- hols generally; a lower one, e.g., ch30h, being transformed into the next higher homologue, c,han+1oh+co-4 2ll= crue ch.oh; ethyl alcohol from ethylene and water; hexane from ethylene and hydrogen; acetone from ethylene, carbon monoxide and hydrogen; and propyl alcohol from ethylene and methyl alcohol. little hope exists of reducing carbon monoxide to for- maldehyde, making ethyl alcohol from methane, carbon monox- ide and hydrogen or converting methane into a mixture of ethane and hydrogen. methane.—berthelot (1856) first synthesised methane, hydro- gen mixed with the vapour of carbon disulphide being passed over red-hot copper, cse+2hs+8cu=4cues+ch,. brodie (1873) obtained methane by passing electric sparks through a mixture of carbon monoxide and hydrogen whilst sabatier and senderens (1902) reduced both carbon monoxide and dioxide to methane using nickel (250°-300°) or cobalt as catalyst. bone and jerdan (1897) first obtained methane by the direct union of carbon and hydrogen; they found it was the only hydro- carbon produced on leading hydrogen over pure carbon at 1,200”. berthelot had previously found that carbon unites with hydro- gen at the temperature of the electric arc; he doubted the results of bone and jerdan. m. mayer and v. altmeyer (1907) studied the reaction between carbon and hydrogen in presence of nickel and cobalt as catalysts; the equilibrium, c-++-2h,72chy, was approached from both sides and, at 475°, the partial pressure of the methane actually exceeded that of the hydrogen. the direct production of methane from carbon and hydrogen is not promising, the gas occurs in large quantities naturally (oil- wells, mud volcanoes, fire-damp, etc.) and synthesis could be more readily effected by complete reduction of carbon monoxide by hydrogen, both being formed in the water-gas reaction. processes based on this reduction have been patented by elworthy. methane can also be obtained by decomposing aluminium carbide, alc3, with water. syntheses from methane.—the use of methane as a source of other carbon compounds is restricted, chlorination to methyl chloride and hydrolysis of the latter to methyl alcohol have been mentioned above. the regulated chlorination of methane has formed the subject of patents by walter (1909) and pfeiffer and szarvasy (tgro). another use of methane might be its oxidation to formaldehyde, ch,+02=ch.0+h,0. bone (1903) obtained small amounts by oxidation at 400°-500° in contact with porous tile and applications of the reaction have been patented by g. glock (1898), hansmann and co. (1906) and the verein fiir chemische industrie in mainz (1913). experiments carried out 535 at the royal naval cordite factory, holton heath (report of the department of scientific and industrial research, 1924-5), lead to the conclusion that formaldehyde would be recovered in too dilute solution for economical concentration. the chlorina- tion of methane has also been studied at holton heath; the pro- duction of carbon tetrachloride on a large scale appears to be practicable as, also, that of methyl chloride under certain cir- cumstances. traun (british patent 156148) states that methane is oxidised by carbon dioxide to formaldehyde at s00°-700° (up to 56% conversion). h. dreyfus (british patent 226243) pro- poses the realisation of the reactions, ch4+co=ch3.cho and ch4+ co2=ch3.cooh, at 12 to 50 atmospheres and tempera- tures of 120°-300°, the catalysts consisting of finelv-divided iron or nickel carbonate, the latter being preferably mixed with finely-divided nickel or iron. carbon monoxide—the oxides of carbon are formed by the combustion of carbon in air or oxygen or by the reaction between coke and steam at a high temperature. (c+h.2o=co+ hp, c-+2h,o=co.+ 2h.) formation of carbon monoxide is fa- voured by a high temperature, equilibrium in the reaction, co.+-c 2 2co, being displaced from left to right with increasing temperature. the reversibility of the reaction was discovered by h. sainte-claire deville (1864) and afterwards studied by boudouard (rgorl), schenck and zimmermann (1903), rhead and wheeler (1910, 1912) and jellinek and diethelm (1922). increased pressure favours production of carbon dioxide; at 1,000° and 1 atmosphere the amount of the latter gas is only o:7°% (by volume), but at 200 atmospheres this amount be- comes 47:7%. (calculated by jellinek and diethelm.) carbon monoxide is reduced by hydrogen in presence of a catalyst to methyl alcohol or methane; according to e. r. lush (british patent 180016), carbon monoxide and hydrogen yield formaldehyde when passed rapidly over a catalyst of copper, nickel and aluminia under certain conditions. with potassium hydride, potassium formate is produced and carbon liberated (moissan, 1902); caustic potash gives potassium formate (co+koh=h.cook, berthelot, 1856), whilst sodium alkyl- oxides yield sodium salts of fatty acids, e.g.:— phosgene.—phosgene (carbonyl chloride, cocl:) is formed by direct union with chlorine under the influence of light or on a suitable catalytic surface. losanitsch and jovitschitsch (1897) submitted mixtures of carbon monoxide, water, hydrogen, methane, hydrogen sulphide and ammonia to a dark electric discharge obtaining respectively formic acid, polymeric glycol- aldehyde, acetaldehyde, thioformaldehyde and formamide. formates.—berthelot’s synthesis of potassium formate was followed by the production of formates from carbon monoxide using caustic soda (geuther) and soda-lime (merz and tibiri¢a, 1880). de lambilly (british patent 3735, 12604—1893) prepared ammonium formate by leading carbon monoxide and damp ammonia over pumice or charcoal at 80° c. to rgo° c. mm. gold- schmidt (german patent 86419—1894) obtained a nearly quanti- tative yield by using a ground mixture of caustic soda and slaked lime at 6 or 7 atmospheres pressure and 150°—-170° c. aqueous alkaline solutions were used by r. koepp and co. (british patent 7875—1904 and 772—1906) and claims were made for a reaction between alkaline carbonates and carbon monoxide. exposure of fresh surfaces of the caustic soda is essential and may be effected by stirring, a small amount of water being subse- quently added (elektrochemische werke in bitterfeld, german patent 179515—1905). j*urther patents introduce no essentially new principle, e.g., meister, lucius and briining (british patent sor2—1908; g. a. hempel, german patent 248254). the nitrile of formic acid, iico2ii, is hydrocyanic acid, hcn. (see cya- nides.) oxalates—the formation of oxalates from formates, 2h. cook = 11.4 €c:0,k2, by heating above 400° was known in 1840. (dumas and stas, peligot.) several applications have been made of this reaction. goldschmidt (german patent 111078) heats sodium formate with its own weight of carbonate to 360°; elek- trochemische werke (german patent 144150) use previously made sodium oxalate. koepp & co. (german patent 161512) 536 use 1% alkali at 2090°-360°. the elektrochemische werke (german patent 204895) heat in vacuo at 280°, the gesellschaft fiir chemische industrie in basle pre-heat the vessel ancl keep the temperature above 400° throughout the course of the reaction (u.s. patent g95041) although landshoff and mever (german patent 269833) lay stress on keeping the reaction at 385° 400°. c. bochringer und soehne (german patent 229853) add a small amount of boric acid, g. a. hempel (u.s. patent 1070806) makes and decomposes the formate in the same vessel. methyl alcohol.—realisation of the reaction, co+2h.= ch30h, under the influence of an electric discharge has been recorded by solvay and slosse (1898) but sabatier and senderens were unable to arrest the reduction of carbon monoxide at the methyl alcohol stage. patents were taken by the badische anilin und soda-fabrik (german patents 203787, 295202, 295203) for the reduction of the oxides of carbon by hydrogen in the presence of catalysts (e.g., cerium, chromium, cobalt, manga- nese, molybdenum, asmium, palladium, titanium, zinc, their oxides and salts, carbides of iron, molybdenum and tungsten) with the object of obtaining liquid hydrocarbon mixtures suit- able as fuel. the reactions are generally described as carried out at about 300°-400° under 100 atmospheres pressure. synihol.—products of this nature (“synthol’) have been examined by fischer and tropsch and found to contain fatty acids, methyl, ethyl and propyl alcohols, various aldehydes, ketones, esters and hydrocarbons (brennstoff-chemie, 1923, 4, p. 276). e. r. lush (british patent 180016—1921) found that methyl alcohol, as well as formaldehyde was formed from carbon monoxide and hydrogen, and g. c. calvert (1921) claimed pro- duction of methyl alcohol in good yield by reduction of water gas. g. patart (french patent 540343) patented carrying out the reaction between one volume of carbon monoxide and two volumes of hydrogen at 300°-600° under high pressures in pres- ence of metals, their oxides or salts. the patents of the badische co. (british patents 228950, 2290714, 227147, 231285, 237030, 240955) claim a process for manufacturing methyl! alcohol very similar to that of patart. stress is laid on removing iron and nickel compounds from the reacting gases as well as the ordinary catalyst poisons; the cat- alyst masses must be free from iron, nickel and cobalt, or alter- natively they should only be present in traces provided that there are present at the same time other metallic catalysts which will prevent the iron, nickel or cobalt giving rise to methane or other hydrocarbons. contact masses consisting of mixtures of metallic oxides which cannot be reduced under the operating conditions of the reaction may be used; the most basic of the oxides emploved must pre- dominate in a mixture. contact masses practically free from the alkali metals or from mixtures of non-recucible oxides and a metal may be used. when a mixture of two or more metals whose oxides are reduced by hydrogen on carbon monoxide at ordinary pressures below 550° are employed, metals of the fourth to sev- enth groups, as well as boron, are excluded. the badische co. specifies pressures of 50 atmospheres and upwards and tempera- tures of 200°-600° c. when contact masses containing a difficultly reducible metallic oxide, with a little potasstum car- bonate are employed, higher alcohols are also formed; this takes place more readily on increasing the percentage of carbon monoxide and diminishing the rate of flow. besides the plant at merseburg, fresh units are to be opened at ludwigshofen and oppau; the production of methyl alcohol by the badische co. is estimated at about 15,000 tons for 1925 and 25,000 tons for 1926. the patart process is to be exploited in trance in the near future. (with regard to priority, see chem. trades jour., 1925, 76, pp. 600, 754. cf. british patent 180016, 2.5.) patart, in laboratory experiments, attained regular production of methyl alcohol at 400°-420° c. and 150 1o 250 atmospheres using zinc oxide as catalyst (chemie ct industrie, 1925, 13, 1, p. 179). e. audibert (2did. 186) utilises the suboxides of certain elements and describes the results when employing contact masses obtained by reducing uranium trioxide (uqos;) and chro- mic oxide (cr,o3) respectively, in contact with copper in both carbon, syntheses of cases. with an uranium suboxide and gas remaining in contact with the catalyst 60 to 80 sec. conversion was 8 to 10 per cent. in these experiments, temperatures of 220°-250° and 280°-300° and a pressure of 200 atmospheres were employed; the surplus gas was found to contain 1-2% carbon dioxide and up to 1% methane; the ratio i[.:co2 showed a small increase of 3-4 per cent. the condensed liquid was nearly pure methyl alcohol. the chromium suboxide at 325 °-250° gave a mixture of water, methyl alcohol and other organic compounds. carbon dioxide-—this gas can be used for the synthesis of carbamide (urea). basarow (1870) obtained it by heating am- monium carbamate (the product obtained thus, 2ni3-+-co,.= nh2.coonh),) to 130°-140°. dexter (1882) passed ammonia and carbon dioxide through a hot tube. fichter, steiger and stanisch (1916), finding the initial rate of urea formation accel- erated by a small amount of water, conclude that ammonium carbonate is the immediate source of urea, nhy.coonity+ ho <2 (nh4)2co3 72 co(n h2)o+ 2120 above 135°, only the second equilibrium need be considered, the ammonium carbamate disappearing. matignon and frejacques (1920-2) find urea formation is accelerated by catalysts at lower temperatures; they are without benefit at 150°. the badische anilin und soda-fabrik carry on the manufac- ture, apparently at 130°-140°. their suggestions include the use of silver- or lead-lined autoclaves; acceleration by catalysts, e.g., charcoal, sugar or carbamide itself; and addition of ro-20% ammonium carbonate. the equation shows that the reaction 1s incomplete, unaltered ammonia and carbon dioxide and, subse- quently, water can be distilled off under reduced pressure. (british patents 23939, 24042, 24117 of 1914, 145060, 182331.) frejacques (french patent 527733) heats ammonium car- bamate to 145°-200°, e.g., 2 to 4 hours at 150°, allows the temperature to fall to 65°-100° and removes carbon dioxide, ammonia and water, carbamide remaining in the autoclave. urea is also manufactured from calcium cyanamide. the isomerisation of ammonium thiocyanate gives thio-carbamide, cs(nt)e. it is used in the rubber and synthetic resin industries and is manufactured by the british cyanides co., ltd. carbon dioxide unites directly with sodium yielding sodium oxalate. haupt claims a process of spraying molten sodium with pre-heated carbon-dioxide. (german patent 286461.) acetylene.—( see 1.137.) this is obtained by the action of water on calcium carbide, (c,ca+2h.20 = celle+ca(oh):); there is an ex- tensive literature relating to generation and purification of the gas. acetaldehyde, acctic acid and acetone.—addition of the elements of water to acetylene gives acetaldehyde. ch:ch+h.o =ch;.cho. oxidation of acetaldehyde yields acetic acid, ch;.cooit. distilla- tion of calcium acetate gives acetone... ae h3c go)c a=caco;+ (ch3)2co, which may also be formed by catalytic decomposition of acetic acid, 2cii; cooh =h.0+ co, + (ch3).co. other products may also be obtained, thus acetaldehyde can be polymerised to ale ohol, removal of the elements of water from the latter compound gives crotonaldehyde and catalytic hydrogenation of crotonaldchyde yields butyl] alcohol. 2chs.cho->ch,;.choh. cha hoch; ch:ce.chosch3.c hly.chs.cheoh. = acetone vapour is dec pmiposedi in contact with certain metallic oxides giving methane and ketene, cti;.co.chs=cha-+- ha:co, and ketene can be used as an acetylating agent, roh +ch.2:co = r.oco.chs. irom sodium acetone and ac etylene a tertiary dlcohol of the con- stitution (chajec(oid).c:ch is obtained which can be employed in the manufacture of isoprene. acetylene was first converted into acetaldchyde by solution in sulphuric acid (specific gravity 1°35), dilution with water, and distillation (lagermark and eltckow, 1877). kutscherow (1881) used water and mercuric bromide, erd- mann and k6ethner (1808) passed acetylene through boiling dilute sulphuric acid to which mercuric oxide had been added. n. griinstein (1910) proposed the technical preparation of acetaldehyde from acetylene with the aid of mercury compounds in acid solution, working at a lower temperature than had been usual in laboratory experiments. his first patent, german patent 250356, was followed by others (german patents 253707, 253708, 267260, 270049). several patent applications by the consortium fiir elektrochemische industrie in niirnberg were withdrawn but fr. bayer and co. patented the use of aromatic carbon, syntheses of sulphonic acids in place of the mineral acids usually employed. (german patent 2017094.) the oxidation of acetaldehyde by air to acetic acid is slow at ordinary temperature, moreover, acetaldehyde, b.p. 21° c. is very volatile. griinstein, in conjunction with the chemische fabrik griesheim-elektron overcame this difficulty by dissolving the acetaldehyde in a large excess of acetic acid and blowing in air or oxygen at 7o°—-100° c. catalysts (e.g.,0- 1° uo; on weight of acctic acid) enable the use of a temperature of only 30° (british patent 17424—1911, 8076—1912; united states patent 1081959; german patent 261589; french patent 440658). meister, lucius and briining suggested the use of increased pressure together with a catalyst (british patent 10377—1914). patents referring to special points in converting acetylene to aldehyde have been numerous since tors. thus those of h. dreyfus (french patent 479656) and union carbide co. (united states patents 1213486, 1213487) relate to low hydrogen ion con- centration, acieries et forges de firminy (british patent 124194) to electrolytic regeneration of acid liquids containing mercury salts, deutsche gold- und silber-scheide anstalt (german patent 334357) to the interaction of steam and acetylene at high tem- peratures in pressure of a catalyst, societe anonyme de produits chimiques (maletra) (british patent 140784) and tokyo indus- trial laboratory (japanese patent 38752—-1921, chem. soc. abstr. 1922, 1, p. 523) to use of ferric compounds and of societe chimique des usines du rhene (british patent 238520) to acid solutions of ferrous and copper sulphates with metallic mercury. increased demand for acetic acid and acetone during the war was met by canadian electro products, a subsidiary of the sha- winigan water and power co. of montreal. according to j. t. rooney (chem. & afct. engincering, 1920, 22, p. 847) absorption vessels of acid-resisting iron were used to contain 60° sulphuric acid at 70° to which yellow mercuric oxide had been added, for dissolving the acetylene. the crude acetaldehyde was concen- trated to gg-100% and oxidised by air under pressure at 60°, manganese acetate being used as a catalyst. the vapour of acetic acid was decomposed into acetone, water and carbon dioxide by passing over iron balls coated with lime at 485°. acetylene is absorbed by acetic acid in presence of mercury salts with production of ethylidene acetate, chsch(ocochs).2 (griesheim-elektron, british patent 14246—1913; compare con- sortium fiir elektrochemische industrie, british patent 182112). this compound is decomposed above its boiling point giving acetic anhydride, ch .ch(qcoch3s).= ch3.cho+ (ch3.cqo).0. (bosnische elektrizitits a.g.). the production of acetic an- hydride in this way has been further developed by the societe chimique des usines du rhone. eihyl acetate—tischtschenko (1906) observed the production of ethyl acetate from acetaldehyde under the influence of alu- minium ethoxide, al(oc2h:;)3. improved methods of carrying out the reaction 2ch3.;cho=ch;.co.oc.h; have been patented by the consortium fiir elektro-chemische industrie (german patents 277111, 277187, 277188, 285990, 286812). | butaldchyde and butyl alcohol.—these compounds can be ob- tained by the catalytic hydrogenation of crotonaldehyde in pres- ence of 20-25% water or steam. (n. griinstein, british patent 147118.) nickel (5-15°} on pumice or kieselguhr is used as catalyst, optimum temperature r10-120°. formation of high boiling products is minimised by using a large excess of hydrogen. eihylene and ethyl alcohol.—the hydrogenation of acetylene usually proceeds completely to ethane or ethylene, when formed, partially polymerises. efforts to overcome these difficulties have been made by w. caro; lane, ryberg and kinberg; traube. as a product of the distillation of coal, ethylene is produced in large quantities at gas-works and coke-oven plants. concen- tration of ethylene has been effected by selective absorption by charcoal (bury at skinningrove) with a view to alcohol produc- tion. the compagnie des mines de bethune, who manufacture ammonia by the claude process, have adopted a different method. (chimie et industrie, 1925,13, i, 718.) the hydrogen ‘obtained from the coke-oven is purified by liquefaction of eth- ylene and benzene. the ethylene is absorbed in sulphuric acid 937 to form ethyl sulphuric acid which is hydrolysed on dilution and heating, the ethyl alcohol being distilled off. the residual dilute sulphuric acid is used for the manufacture of ammonium sulphate. acetylene and chlorine. —several compounds obtained with the help of acetylene and chlorine find application as solvents and, more recently, for synthetic purposes. berthelot and jungfleisch (1869) obtained an addition product of acetylene and antimony pentachloride, c2h».sbcl;, which gives dichloroethylene, chc: chcl, on distillation; with excess of antimony pentachloride, tetra-chloroethane, chic],cticl., is produced. the latter com- pound loses hydrogen chloride on treatment with alcoholic potash giving trichloroethylene, chici:cck. direct union of acetylene and chlorine may give rise toa violent reaction; to avoid this, the salzbergwerk neu-stassfurt (ger- man patent 174068) used sulphur chloride with a contact sub- stance, ¢.g., iron powder, and passed in acetylene and chlorine alternately. tetrachloroethane, a liquid boiling at 147°c., was thus obtained; saturation at the boiling point before distillation gave hexachloroethane c2clg. various modified processes have been proposed. tompkins (british patent r9568—1904) specified the presence of both anti- mony tri- and pentachlorides. lidholm (british patent 22094— 1905) diluted with carbon dioxide and exposed to the light of a mercury lamp. griesheim-elektron (british patent 13411— 1907) used a solid diluent. ornstein (british patent 2375—1911) led acetylene and chlorine at different places into previously prepared tetrachlorocthane containing iron. trichloroethylene—removal of hydrogen chloride may be effected in various ways. heating with milk of lime or slaked lime (consortium, german patents 171900, 208834); thermal decomposition (tompkins and clayton aniline co., ltd., british patent 23780—1906) ; action of metal chloride at 300° (griesheim- elektron, german patent 263457); use of thorium oxide (chem- ische fabrik buchau, german patent 274782); action of aqueous ammonia (cie. d’alais et de la camargue, british patent 132755). dichloroethylene is not only formed by direct union of acety- iene and chlorine (griesheim-elektron, british patent 16620— ror2) but also by reduction of tetrachloroethane with aluminium, iron or zinc and water (consortium, british patent 19576—1907). of these compounds, trichloroethylene has become a synthetic reagent. paterno and oglialoro (1874) obtained dichloroviny] ethyl ether by the action of alcoholic potash. chc1]:cch+ koc.h;= kci4+ chci:cc1.oc.h;. this, in turn, gives ethyl ethoxyacetate with an excess of the alcoholate, chci:ccl. ch; (geuther, 1873; nef, 1897). imbert and the consortium fiir efektrochemische inclustrie (german patent 216940) discovered that the last reaction proceeds in stages and gives a ready method of making ethyl chloroacetate. cohch.oc2hs + collsoh = chaclcooc2hs+c.h;scll water may be used at this stage in place of alcohol (german patents 209268, 210502), but complete hydrolysis gives chloroacetic acid (german patents 216716). hydrogen chloride acts on dichloroviny! ethyl ether giving chloroacetyl chloride. chchcci(oc.is) +hcl=cofeci+chrce coci. (consortium german patent 222194). reactions of this type have been studied by compton and vanderstichele (jour. chem. soc., 1920, i17, p. 691). by heating trichloroethylene with sulphuric acid containing a little water, monochloroacetic acid is formed (simon and chavanne, french patent 519833, united states patent 1304108). the reaction is possibly due to formation of an intermediate addition product which is then hydrolysed. chscl.cch.so.h +2h.0 =chlci. cooh +2eici+h2s04. since the product is free from dichloracetic acid it is useful in the synthesis of indigo. chlorinated propanes have been obtained by the action of aluminium chloride on mixtures of chloroform or carbontetrachloride with halogenated ethylenes (german patent 261689), e.g., ccly+chci:ccle = cclcila. ccl. bibliograpny.—fritz hauber, thermodynamics of technical gas reactions (london, 1908); fritz ullmann, enzyklopddie der techni- schen chemie, article “acetylen” (berlin, 1914); f. c. beilstein, handbuch der organischen chemie (berlin, 1918); sir t. e. thorpe, dictionary of applied chemistry (london, 1921); paul sabatier, la catalyse en chimie organique, trans. by e. e. reid (london, 1923); j. r. partington and w. g. shilling, specific heats of gases (london, 1925). see also forischritte der teerfarbenfabrikate (berlin, 1888 to date). qe ths} 538 carburetter: sce motor vehicles. cardiff, wales (see 5.316), had a population in 1g21 of 200,262; the estimate for 1923 was 226,200. the city has grown largely since 1910, most of the numerous industrial establish- ments being grouped round the docks. roath park, the largest in wales, has a miniature lighthouse in the lake as a memorial to capt. scott. new buildings in cathays park are the glamor- ganshire county hall (1911), and a technical college (1916). plymouth great wood (42 ac.), presented to the city by the late earl of plymouth, was opened in 1923. a large reservoir in taff fawr valley, begun in 1911, was finished after the world war, and, at. the end of 1925, a central power station was under con- struction at treforest. a tuberculosis hospital, the welsh national memorial to king edward vii., was opened in llandaff in 1913, and the national museum of wales has absorbed the municipal museum and art gallery, previously in the public library building. new churches include st. luke, canton (1911), st. joseph, cathays (1913) and st. samson (1923). in 1912 the parish of st. stephen was formed, in 1920 that of upper grange- town and in 1923 that of st. david. in 1922 the city boundaries were extended to include llandaff and most of six other outlying parishes, and the area of the borough was thus increased to 13,649 acres. cardiff has a considerable roman catholic population, and when wales was made a separate roman catholic province in 1916, it became the seat of the archbishop. cardinals, college of (sce 5.321).—the codex of canon law, ordered to be codified by pius x.and promulgated by bene- dict xv. by the bull, providentissima mater, in 1917, contains perhaps the last word to be said concerning the cardinalitial dignity and the privileges and duties attached to the office of those who wear the ruber galerus. the matter is there so well digested that little further compression is possible or comment necessary. the cardinals are described as the pope’s counsellors and ad- jutants in the three orders of 6 cardinal bishops, 50 cardinal priests and 14 cardinal deacons (the number symbolises the 70 elders). they are to be chosen freely from all countries for their doctrine, piety and prudence. at the moment (1926) the college contains 36 italians, 8 central europeans, 2 poles, 7 french, 5 spanish, 4 north americans, 2 english and one each from ire- land, portugal, holland and brazil. prohibitions.—from their number the code excludes bastards, even though legitimised by subsequent marriage, also those who have children or grandchildren by legitimate marriage themselves (this would have excluded the english cardinal weld) and also those who are related to a living cardinal by the first or second degree (this has been dispensed by pius xi. in favour of cardinal gasparri’s nephew). the cardinal bishop first in promotion be- comes dean of the sacred college, but only as first among equals. cardinals are required to live in rome, even the cardinal bishops of suburban sees. cardinals occupying sees abroad are required to approach the pope on arrival in rome, and not to leave without his permission. cardinals enjoy a number of privileges, the chief of which are as follows:— 1. to hear and absolve in confession anybody, anywhere, even the religious of both sexes, and even from reserved sins and censures, with a few very special exceptions such as revealing the secrets of the holy office. 2. to choose confessors for themselves and households on similar conditions. 3. to preach the word of god anywhere, 4. to celebrate or allow another to celebrate in their presence a mass on maundy thursday or three masses on christmas night. 5. to bless religious objects everywhere with every indulgence. 6. to erect with one blessing the stations of the cross in private or public oratories or churches, with all indulgences included. 7. to celebrate on portable altars mass in their private houses and wherever they go. | 8. to celebrate mass at sea. 9. to celebrate mass everywhere according to their own calen- ars. 10. to enjoy the privileged altar daily, 11. to gain in their private oratories the indulgences which are attached to public visits in the places where they are staying. carburetter—caribbean, the. 12. to give the episcopal blessing everywhere except in rome and there in churches only. 13- to wear the episcopal cross and mitre and carry the pastoral stall. 14. to celebrate mass in any private oratory without prejudice. 15. to pontificate with throne and canopy anywhere except in rome. 16. to receive the honours of the ordinary everywhere. 17. to confirm abroad the word they have heard from the pope. 18. to enjoy their oratories free from episcopal visitation. 19. to dispose freely, even by will, of the revenue of their benefices. 20. toconsecrate everywhere altars, abbots, and the like with the exception of the holy oils (unless the cardinal is a bishop) and a holy place, without leave of the ordinary. 21. to precede all prelates and patriarchs and legates except a cardinal legate in his own country. 22. toconfer tonsure and minor orders. 23. to confer confirmation. 24. to confer an indulgence of 200 days upon persons under their protection. . the inte?regnum.—the new code contains the constitution of pius x. vacante sede a postolica, which summarises most mi- nutely the duties of the cardinals between one pontificate and the next. the cardinals have no power, except in matter of im- mediate business. the offices of the cardinal camerlengo and grand penitentiary continue during the interregnum. the cardinals are required to mect and make the ceremonial ar- rangements for burying one pope and for electing another. the ingress of the cardinals into conclave and their closure is minutely ordered. secrecy is imposed upon all the cardinals and the con- clavists under pain of excommunication. (the details of the con- claves electing leo xiii. and pius x. were pretty well known, but the conclaves electing benedict xv. and pius xi. have been kept a profound secret; their tendencies being judged by historians entirely on ante-conclavicular knowledge concerning the pu pabili or probable candidates compared with the results.) by the com- missum nobis pius x. abolished the veto claimed by the catholic powers under an unwritten law. pius xi. extended the time al- lowed to cardinals travelling to the conclave, from 10 to 15 days. during the zoth century the red hat has been enjoyed by brit- ish subjects in england, ireland, canada and australia. the english-speaking cardinals are now the equal of those represent- ing any catholic power in any future conclave. (53415.") cardiology: see hfart, diseases of tie. caribbean, the.—e vents in the caribbean region during the period 1910-26 were dominated by the steady advance of the political and economic power of the united states. this de- velopment dated from the spanish-american war, which led to the annexation of porto rico in 1898 and to the occupation of cuba by american forces from 1899 to 1902. cuba’s later in- dependence was qualified by the platt amendment (see 7.604d) and by the lease to the united states of naval stations at bahia honda and guantanamo. the construction of the panama canal (9.2.) gave the united states another highly important vantage point in the region and brought virtually under american control the state of pan- ama. in santo domingo, where an amcrican receiver-general had been placed in charge of the customs-houses in 1907, recur- rent revolutions following nov. 1911 led to the military occupa- tion of the country by u.s. marines in 1916. the american flag was withdrawn in 1926, leaving as a reminder of the occupation only good roads, good schools, quick communications and a well- trained constabulary, together with the receiver of taxes to safe- guard interest payments on the external debt. a similar occupa- tion of haiti was authorised by president wilson in 1915. con- gress tacitly approved, as it did also in connection with similar situations in costa rica and nicaragua. in each case there was increased local prosperity, accompanied by larger american investments. in rot7 the united states acquired by purchase the danish west indics (virgin is., g.v.) with the dual purpose of securing thereby another potential naval basein close proximity to culebra, porto rico, and of preventing the installation in the danish west indies of what at the time was a great and growing european naval power. political grouping.—the political units of the caribbean in caricature 1926 were classifiable into four principal groups, american dependencies, such as porto rico and the virgin is.; virtual pro- tectorates of the united states, such as cuba and panama (with their own governments but subject to limitations imposed by treaties with the united states) and santo domingo, haiti and nicaragua (under partial control); independent republics, such as guatemala and venezuela; and, finally, insular and continental colonies of great britain, france and the netherlands. the latter include jamaica and french and dutch guiana. in all, these political divisions of the caribbean owe allegiance to 15 different national flags. in the british west indies in the period under review, there has been a fuller appreciation of the advantages accruing from the connection with the home govt., among which have been reciprocal trade agreements based on the principle of empire preference. a west indian contingent, over 20,000 strong, served in the world war under the british flag. in 1920 the prince of wales, while visiting these islands, took occasion to state that great britain would not dispose of her west indian possessions in part settlement of her world war debt. under the ottawa agreement (june 1920) the dominion of canada conceded to british west indian products a tariff preference ranging from 25 to 50% while provision was mate on a subsidy basis for greatly needed mail and steamship facilities. in return the islands conceded extensive favours to canadian products and trade. while sugar still remained king of the west indian trade, a rapid development of the petroleum deposits in trinidad took place. pan-americanism.—in large part the problem of the carib- bean is involved in the question of pan-americanism. in the decade 1915-25 washington has been the scene of political and financial conferences and of press, good roads and better business conferences, in all of which, with the other republics of latin speech, the republics of the caribbean have been well represented and have sought and found their advantage. the lessons of the decade have been many and varied. only a few need be mentioned here. it 1s clear now, if there ever was room for doubt, that territorial propinquity creates special relations between countries; that the panama canal, quite irrespective of the monroe doctrine, has given the united states a profound and increasing interest in these islands and the bordering mainland; that united states control of the caribbean is necessary to the naval protection and economic welfare of that region; that many of the islanders would rather be misgoverned by their own people than well governed from washington; that the islands irrespective of political complexion, have become important natural markets on a great commercial highway of limitless possibilities; that to prevent forcign intervention the united states must make certain that legitimate outside interests are protected; and last, that inescapably the united states is charged with the task of assisting the countries of the caribbean in their long-delayed quest of economic and political well-being. yet in spite of a more general recognition of the responsibilities that these icssons have driven home, it cannot be said that a systematic course of action has been followed. four policies, however, have been proposed, and it may perhaps be said without injustice that all have been practised—intermittently. these are: regulation, as in cuba and santo domingo; neutralisation, as in the central american states; annexation, as in porto rico; and abstention, as in many quarters. under these circumstances, the people of the caribbean can hardly be blamed for regarding the policy of washington as always individualistic and at times temperamental. ‘to most observers it seems that abstention is impossible and that regulation is the most practicable; but to suc- ceed, the policy of regulation must be systematically pursued. lhe political future.—in view of these conflicting currents, the immediate political future of the caribbean region is ‘obscure. notable changes in sentiment may, however, be noticed. in the united states 20 years ago there were individuals, and perhaps organised groups, who more or less openly sought the annexation of cuba. in 1926 there were no such groups. on the contrary, there are many persons in cuba who contrast the cost of govern- 939 ment to the porto ricans under the american flag with the cost and quality of government under the cuban flag and who sigh for at least fiscal control by the united states. in countries like cuba, santo domingo and haiti, where there have been in the period under review internal upheavals followed by foreign intervention, the paramount question is that of the degree of political education and stability acquired as a result of these experiences of imposed political and fiscal restraints naturally so irksome. it may be suggested that there are signs of an increasing aptitude for the tasks of self-government and a growing appreciation of the dangers as well as the advantages of foreign contacts. in the main the answer to the basic questions that the actual situation propounds must be left to the future. the increasing dominance of the united states in the carib- bean area cannot be ignored. it is almost daily emphasised. it is equally true that innumerable opportunities and even provoca- tions to extend the flag over these islands have been presented and that they have been, without the slightest hesitation and with the practically unanimous approval of the american pcople, ignored or flatly rejected. it would seem that the charge of american imperialism—at least as far as the caribbean is con- cerned—should no longer receive a respectful hearing. an era of progress.—\n the 20 vears 1905-25, with extraor- dinary rapidity and probably finally, the caribbean world has been removed from the list of “ backward areas” in which it figured so long. geographically, economically and _ politically, the islands of the american mediterranean have entered into the closest relations with the great continental power that has become at once the sponsor of their democratic institutions and the guarantor of their political independence. more than a century ago thomas jefferson foresaw it all, when he said that the islands of the caribbean protected or menaced the mouth of the mississippi. to-day the american seaway is not solely across the atlantic ocean, as it was when jefferson lived, but also due south through the diversified islands of the caribbean to the panama canal, the gateway to the markets beyond. (see panama canal.) (3.5) caricature (see 5.331), regarded merely as the comic pic- torial interpretation of life, followed normal lines between the years 19toand 1925, though the standard of representation greatly improved. in great britain punch continued to reflect the prejudices rather than the judgments of the educated middle class, and remained at the head of humorous publications. a comparison of the various artists’ work in that paper during the period under review is fraught with enlightenment, for artists whose drawings passed muster in 1910 had advanced almost be- yond recognition by 1925. regarded as draughtsmen j. a. shep- herd, george morrow, g. l. stampa, frank reynolds, bert thomas, lewis baumer, together with the regular cartoonists, sir bernard partridge and l. raven-hill, were amongst the fore- most black and white artists of the day. on the other hand true caricature, that is, individual por- traiture in which salient peculiarities are exaggerated with a view to making a definite comment, has never been generally appreciated in great britain since the early years of the roth century, and since then has not taken a prominent, or at all events a popular, place in the pictorial art of the country. true caricature demands of the artist an uncompromising honesty, which expediency has done little to encourage, and which squeam- ishness has found dificult of acceptance. iuropean caricature, however, unshackled by prejudice, is frequently vulgar and coarse, and it certainly typifies that “ brutality of the intellect ” which g. k. chesterton, in one of his stories, once declared to be its moving spirit. sir leslie ward (“ spy ” of vanity fair), who was “ ape’s ” successor, gradually reduced the physical exaggeration in his weekly caricature until it became a “ mere” portrait. amongst other occasional contributors to vanity fair in that paper’s later years should be mentioned a gifted amateur, roland le strange, who under the signature ‘‘ a-o” (abbreviated from armadillo) made various caricatures, that of sir harry keppel being of exceptional brilliance. 540 max beerbohni's work.—one outstanding caricaturist of the age was max beerbohm, whose immature work was first pub- caricature britain, france and germany during the preceding hundred years, is a solid contribution to historical commentary. his lished in the strand magazine and in pick-me-up. he made | lighter vein is admirably exemplified by rossetti and his circle a contribution to vanity fair with his amusingly delicate | and the series of the old and the young self, exhibited in 1921 drawing of george meredith and worked for the yellow book and zhe savoy. for some years his drawings were exhibited biennially at the leicester galleries, london, and reproduced fic, 1.—‘ h. m. hyndman" by kapp. in book form. the merit of his work, which was for many years quite independent of draughtsmanship or pictorial beauty, lies in his subtle appreciation of character, which he demonstrated as a rule without the grosser physicial exaggerations which found favour in the days of gillray. descriptive passages, often in the form of highly skilled parodies of his victims’ speech and writings, form an ironic accompaniment to the drawings, and indeed, in a wider sense, max beerbohm’s two vehicles of expres- sion complement each other. long practice in the use of pencil and wash gave his unconventional work, in which the representa- tion of idea always supplanted the representation of fact, a definite beauty which challenges the work of serious and normal artists on its own ground. the very earliest of beerbohm’s drawings undoubtedly show the influence of carlo pellegrini (‘‘ ape” of vanity fair), but he soon developed a style of his own based upon very accurate observation, although without academic knowledge of drawing. he was, so to speak, a caricaturist by nature, whilst other men such as kapp and “ quiz ” were artists first and caricaturists by chance. beerbohm’s best work was invariably done from mem- ory, with an unfaltering line and comcliness of grouping which fills the observer with delight. his aim was to expose the weak- nesses of the strong and his outlook was far too straightforward for him to avoid the charge of occasional malice. beginning, as he himself said, a “ petit maitre’? who would take nothing seriously, in his maturer work, still enlivened by a sense of the ridiculous, he ripened and ascended from cleverness to wisdom, from a rare spitefulness to an almost exuberant scorn. of three nations, dealing with the relative positions of great and 1925 respectively. in the latter notables are found in characteristic conversation$ with themselves in their own youth. these drawings show at its best max beerbohm’s pro- found insight into other men’s personalities. his work ably illustrates the impact of events upon a scholarly and cultivated mind, more prone to perceive the absurdity of wrongdoing than the evil, and of some forms of righteousness, the beauty equally with the absurdity. ilis expression is never heavy or pompous, he has no truck with the surface emotions, and his work, there- fore, never has and never will be, in a wide sense, popular. claud lovat fraser (d.1921) made a few caricatures from time to time of considerable distinction, his method being to “catch” a likeness in remarkably few lines. henry ospovat (dl. 1910) combined keen perception in true caricature with accomplished portraiture. edmond x. kapp was an excellent draughtsman and _ his “straight ’’? portraiture, usually in pencil or chalk, commands admiration. his caricatures are diverting and original, showing considerable observation not merely of a physical kind. his work appeared from time to time in the periodical press, and exhibi- tions of it were held at the leicester galleries, london. his most memorable caricatures were a series of judges which appeared in the law journal (1924), and a number of musical notabilities. kapp’s manner of drawing was extremely diverse, ranging from elaborate effects of light and shade made with broad-pointed chalk to a fine clean pen line. he was the first artist in great britain to make intelligible use of ‘‘ abstract ”’ drawing in con- junction with true caricature, and he shared with max beerbohm the distinction of making his drawings, apart from their ostensible purpose, of definite aesthetic interest. “ quiz” (powys evans) contributed weekly to the saturday review (london) from 1922 onwards. his caricatures, drawn in pen and ink, were variously successful, and occasionally brilliant. his comment is mainly physical. portraits from his hand ap- peared in the london mercury, among other artists who made from things new end old (heinemann, london) fic, 2.— diffidence ”’ (sir a. pinero and mr. j. conrad) by max beerbohm. successful caricatures from time to time were edmund dulac and his series of nine drawings exhibited in 1921 entitled tales | w. k. haselden, whose weekly illustrations to the dramatic with criticisms in punch were really of remarkable excellence. carnarvon—carnegie trusts extreme economy of line he contrived to unite likeness to his vic- tims with judgment on their performance or personality. will dyson, an australian who first became known as a contributor to the bulletin (sydney), made powerful caricatures in black and white, though his work came as a rule rather under the head of cartooning. other personal caricatures which appeared from time to time in the daily or periodical press consisted usually of large heads on little bodies—a convention which has the merit only of enabling the artist to draw especial attention to facial peculiarities, but which has the disadvantage of frequently in- verting the figurative as well as the physical truth. it remained for max beerbohm to put very small heads on very large bodies when that reversal of the usual procedure seemed warranted. german caricature—on the continent of europe the best personal caricature was undoubtedly produced in germany, where the satirical weekly paper sim plicissimus, formerly pub- lished from munich, and later from stuttgart, continued to lead the way in manner and content, followed by kiadderadatsch (berlin). jugend (munich) devoted less space and talent to cari- cature than formerly. the world war gave the german cari- caturists daily opportunities of malicious exposition of current events, and it was on the whole remarkable how they restrained themselves; their satire during those years was frequently tinged with manifest respect. caricature in simplicisstmus was outstanding, not only for the exccllent likeness to individual victims, but for the wealth of original and daring conventions by which such likenesses were built up. the best work in sim plicis- simus was done latterly by two scandinavians, olaf gulbransson, and ‘* blix,” who treated the affairs of the world at large week by week in a spirit of bitterness, sometimes entertaining, sometimes revolting in its harsh realism, but always skilful. the caricatures of e. theny, an old contributor, were remarkable for their fer- tility of invention and variety of treatment. in great britain, the name that most conspicuously emerged from the war in this respect was that of the dutch artist, louis raemaekers, who, though not to be highly regardcd as a carica- turist, contrived to adapt the skilled inventions of a continental techniguc to a bitter commentary on the conduct of the german army. in italy, musacchio contributed brilliant caricatures to the giernale d’ italia. french and american work.—lin france, the personal carica- tures of ‘ cabrol ”’ in l’ humanite were noteworthy for physical likeness skilfully caught by unusual means; but it is to be ob- served that the continental draughtsmen in this gezre seldom, in their estimate of individuals, went beneath the surface of re- ported utterances, and no particular insight into character was demonstrable, cither in the drawings themselves or the words written beneath them. very little true caricature worth mention appeared in other european countries during the period 1910-25, and in the united states, too, irony generally found expression in cartoons which typified rather than identified. exceptions are found in the drawings of ralph barton, whose caricatures ap- peared in the new york life, and, occasionally, in the work of boardman robinson, who became known also in great britain for his political cartoons in the outlook during 1922 and 1923. the best true caricature seen in the united states after 1910 was the work of a mexican, miguel covarrubias. (see caartoon.) bisliograpiy.—oliver onions, the work of itenry ospovat (1911); max beerbohm, a survey (1921), things new and old (1923), observations (1925); edmond x. kapp, personalities (1920), reflections (1922); bohun lynch, max beerbohm in perspective (1921); powys evans, the beggar’s opera (1922). ci. 1.) carnarvon, george edward stanhope molyneux herbert, 5th earl of (1866-1923), english egyptologist, was born at highclere, berkshire, june 26 1866 and educated at eton and trinity college, cambridge. in the course of extensive travels he acquired a knowledge of the near fast, but, though much interested in foreign politics, was prevented from taking part in public life owing to a motoring accident. always interested in egyptian archaeology and politics, he began exca- vations near thebes with mr. howard carter in 1906 and dis- covered tombs of the xii. and xviii. egyptian dynasties in the valley of the kings. a further concession having been obtained 541 in 1914, operations in another part of the valley were conducted after the war, resulting in the discovery by mr. carter in nov. 1922 of the antechamber of the tomb of tutankhamun (g.v.) of the xviii. dynasty. on feb. 16 1923 the sepulchral chamber was opened, the actual sarcophagus being discovered on jan. 3 1924. meanwhile lord carnarvon had died in egypt on april 5 1923, from the results of a mosquito bite and pneu- monia. see pie tomb of tut-ankh-amen by howard carter and a. c. mace (1923). carnegie, andrew (1835-1919), american capitalist and philanthropist (see 5.364), died at lenox, mass., aug. 11 19109. his ideals are shown by his benefactions (see carnegie trusts). in rg10 the pan-american union building erected in washington by carnegie at a cost of $850,oco was dedicated. in 1911 he established his last and greatest endowment, the carnegie corporation of new york, and before his death placed in its charge $125,000,000 to be used for promoting civilisation in whatever way should scem best to the trustees. in 1013 the hague peace palace, given by carnegie and costing $1,500,000, was dedicated. by the close of 1918 he had erected 2,505 library buildings (1,679 u.s.a.; 660 great britain and ireland; 125 canada; 41 clsewhere) at a cost of more than $56,000,000. he had provided 7,624 church organs throughout the world, costing about $6,220,000. in his will he provided that after certain enumerated bequests the residue of his estate (his family having already been provided for) should pass to the carnegie corporation. appraisal of the estate, smaller than had been estimated, was made in 1921 and showed a net value of $22,880,000. since according to the law of new york only half of an estate can be assigned as public bequests in case husband, wife, parent or child survive, the residue passing to the carnegie corporation was less than $11,000,000. before his death car- negie had made public gifts, including those mentioned above amounting to $350,000,000. if he did not die poor, as he claimed every man should, he at jeast gave away all but a relatively small portion of his wealth. his autobiography appeared in 1920. carnegie trusts, the sccond largest, and in some re- spects the most remarkable, group of charitable foundations in the world. andrew carnegic’s theory of wealth is summed up in the following sentence: ‘ this, then, is held to be the duty of the man of wealth: to set an example of modest, unostentatious living, shunning display or extravagance; to provide moderately for the wants of those dependent upon him; and, after doing so, to consider all surplus revenues which come to him simply as trust funds, which he is called upon to administer . . . the man of wealth thus becoming the mcre trustee and agent for his poorer brethren.” in this spirit, he founded the following trusts in the united kingdom and in america. i. trusts in the united kingdom carnegie trust for the universities of scotland (edinburgh).— founded in 1901 this has a capital of £2,000,000. one half of the income is to be applied to the improvement and expansion of the four scottish universities, chiefly in the field of research; one half to the payment of the whole or part of the fees of university students of scottish birth or extraction. carnegie dunfermline trust.— founded in 1903 with £750,000, this is the counterpart of the pittsburgh institute (see below). this trust is limited to the founder’s native city of dunfermline, but the income may be spent on anything which tends to bring ‘‘ sweetness and light ’’ to the community. the trustces are, however, charged to maintain the beautiful park known as pittencrieff glen, which was presented by the founder separately. they have established a number of institutes, a clinic, a craft school, a school of music and a physical training college, and have substantially assisted the public library, the baths and a large number of local societies, educational, literary and artistic. carnegie lero fund trust.—this fund is administered from dunfermline by the trustees who are in charge of the carnegie dunfermline trust. carnegie united kingdom trust (dunfermline) founded in 1913 with a capital of £2,000,000 this is the analogue of the 542 carnegie corp. of new york “ for the improvement of the well- being of the masses of the people of great britain and ireland by such means as are comprehended within the meaning of the word charitable.”’ this trust has carried on the founder’s library policy, having erected a number of public libraries, established more than roo county librarics and assisted many special libraries. it has published an edition of elizabethan music and a number of modern compositions. grants have been made for the erection of six child welfare model centres, to the old vic and sadiler’s wells theatres, london, as the nucleus of a national theatre for england, and to many musical and dramatic enter- prises. the trust has also taken a prominent part in rural development by founding county community councils. ii. trusts in the united states carnegie institute of pittsburgh—this consists of a group of cultural and educational departments of the municipal type, library, concert hall, technical college, museum and art gallery. the foundation really dates from 1881 when carnegie offered to provide a public library; this offer was accepted in 1886. the idea expanded until the institute was finally constituted as such in 1896. it has a capital of $28,000,000. carnegie institution of washingion.—founded in 1902 with a capital of $22,300,000, this is a great combination of research departments, working in collaboration and including: experi- mental evolution (1903); marine biology (1903); historical research (1902); economics and sociology (1904, discontinued 1917); terrestrial magnetism (1904); mount wilson observa- tory (1904); geophysical laboratory oe botanical research, including a laboratory in monterey, cal. (1905); nutrition (1906); meridian astrometry (1907); embryology (1914); eugenics record office (1917). the published reports of the institution constitute a highly valuable library of research and are presented in a liberal spirit to all well-established libraries. the numerous voyages of the non-magnetic ship ‘‘ carnegie,” designed to test the variations of the magnetic compass, may be specially mentioned. carnegie hero fund commission (pittsburgh) —tvhis is a group of foundations, dating from 1904, designed for the purpose of giving suitable recognition to persons engaged in peaceful occupations who risk thcir lives in heroic eflorts to save others. recognition takes the form of medals, pecuniary grants, pen- sions, educational help for children, etc. the funds are: u.s.a., canada and newfoundland $5,000,000 (1914); british isles $1,250,000 (1908); france $1,000,000 (1909); germany $1,500,000 (1910); norway $125,000 (1911); switzerland $130,0c0 (1911); netherlands $200,000 (1911); sweden $230,000 (1911); denmark $125,000 (1911); belgium $230,000 (1911); italy $750,000 (1911); total $10,540,000. carnegie foundation for the advancement of teaching (v ei) york).—this was founded originally in 1905 to provide pensions for teachers in the form of free gifts. the system was at first non-contributory, but after elaborate investigation, a new system was adopted by which colleges and teachers both contribute on a properly calculated actuarial basis. the foundation has also undertaken many inquiries in the field of education, and issued numerous reports. its capital is nearly $30,000,000. carnegie endowment for international peace-—founded in 1910 with a view to ‘“ the speedy abolition of international war between the so-called civilised nations,” this has a capital of $10,000,000. it is divided into three sections concerned respec- tively with “intercourse and education,” ‘ economics and history” and “ international law.” the endowment is very broad in its scope, being free to work in any way for the pro- motion of good fecling and understanding between the nations. since the world war one important project has been a series of volumes on european economics in connection with the war and its aftermath. carnegie corporation of new york.—founded in torr this is the largest in size and scope of all the carnegie foundations, its capital being $125,000,000. it exists for “ the advancement and diffusion of knowledge and understanding among the people of caro—carpathians, battles of the the united states.”” in 1917 its scope was extended to include canada and the british colonies. it may spend its large revenue through the other five american trusts or through any other suitable channels. its policy is in fact fluid, the founder having said in the deed, ‘‘ conditions upon the earth inevitably change. . i give my trustees full authority to change policy or causes hitherto aided when this, in their opinion, has become necessary or desirable.”” the corporation has done a great deal for the american library service, and for adult education generally, e.g., fine arts, the study of modern languages, law, engineering. all the above foundations, except the carnegie corporation of new york and the united kingdom trust, have functional or jocal limitations. the two general trusts work largely on the same lines, seeking to promote adult education in the widest sense of the term, to make accessible to the public at large the cultural resources of the community and especially to finance carefully devised pioneer experiments for which, without practical demon- stration, state subsidies and private liberality cannot be expected. see the annual reports issued by the various trusts; afanual of the public benefactions of a. carnegie (washington, 1920). see also libraries. (j. mi. m.) caro, nikodem (1871- _—+), german chemist, was born may 23 1871 at lodz. we studied at berlin university and at the technical high school, charlottenburg, and founded a public chemical laboratory. he was engaged in agricultural research work, and experimented on peat as a source of power. he inter- ested himself in the problems of calcium carbide and acetylene, and in the liquefaction of water gas for the production of hydro- gen, also in ammonia oxidation. in conjunction with frank, he devoted himself to the development of a process for the fixation of nitrogen (cyanamide) and organised the cyanamide industry founded theron. large works for this industry were also erected at piestcritz and chovzow. dr. caro made a special study of the question of bavarian sources of water-power with a view to utilising them in the chemical industry. carolus-duran (1837-10917), french painter (see s. 381), died in paris feb. 18 1017. carpathians, battles of the.—under this heading is recorded the fighting of the first four months of ro1r5 in the wooded carpathians, from the dukla pass, south of jaslo, to the rumanian border. the average height of the crest of the main ridge in this section of the range 1s between 2,500 and 3,000 feet. the slopes are steep on the galician side, gentler on the hunga- rian side. ‘the winter climate is extremely severe, the tempera- ture being often many degrees below zero; snowstorms and blizzards are frequent. why both sides chose these inhospitable highlands for a winter battle—for each side in turn attacked in great strength—invites some examination. object of the operations —for austro-hungary the main mo- tives were the relief of the fortress of przemysl and the security of the threatened plains of hungary. but conrad von hotzen- dorf, chief of the austrian general staff, hoped for more; the attacks, if successful, would develop into a large scale offensive against the southern flank of the whole russian battle line. on the russian side, the grand duke nicholas sought during this winter to secure his flanks as the necessary preliminary to a direct advance from the polish salient aimed at the heart of germany. the undisputed possession of the carpathian passes, with freedom to debouch at will into the hungarian plains below, would go far towards breaking the resistance of austro-hungary and so safeguarding the russian southern flank. the grand duke trusted to the greater endurance of his men under winter conditions to give them the advantage over enemies bred in less rigorous climates. he forgot that the russian is a plainsman, and that hill fighting requires a special aptitude and training. by the end of 1914 a continuous front had been established in the carpathians only as far east as baligrod. thence to the rumanian frontier, the conditions were those of open warfare; detachments on either side attacked and defended points of strategic importance, but no solid battle line had been formed. disposition of troops.—the disposition of the opposing forces _ carpathians, @ sandomierz g ee kielce ma. my nes. wee 4 sill be en ee att st or x? a: i ‘lee n rn re cain “ i sogm onic hr ds wh “yy 2] , : i 7c ?: eeaey a rr iy & i pe an ath i het wt wans branes nuingbe “4 a) 2 i i dal : a in when the campaign opened in mid-january were approximately as follows. the russian iii. army (radko dimitriev) extended from the vistula, northeast of cracow, by tarnev to about gorlice; on its left came brusilov’s viii. army, which stretched from gorlice to baligrod and held the important dukla pass. further east, webel’s dniester group (second-line infantry divi- sions and cossacks) had pushed up the slopes of the eastern carpathians, capturing the uzsok and wyszkow passes and overrunning the bukovina. the xi. army was besieging przemysl. on the austrian side, the iv. army (grand duke joseph ferdinand) faced radko-dimitriev, and boroevich’s iii. army was opposed to brusilov. further east, linsingen’s newly formed southern german army (four german and two austrian divisions and two cavalry divisions) had assembled at munkacs and was moving forward. further east still, beyond the wyszkow pass, the group of pflanzer-baltin extended up to dorna-vatra on the rumanian border. | austrian offensive-—the austrian offensive, which opened the campaign, was made by the right of boroevich’s iii. army, by linsingen’s southern army and by pflanzer-baltin’s group. the offensive began on jan. 23 1915. the attack of the iii. army, after an initial success which carried it to the line of the upper san, soon lost its impetus. the russians retaliated with a counter-offensive which began on jan. 26 against the left of boroevich’s army astride the mez6 laborcz railway; from now to the end of the battle the russians maintained the initiative in this part of the field, to which both sides began to transfer forces from other sectors of the front. linsingen’s southern army recaptured the uzsok and wyszkow passes and pushed battles of the 543 battles of the carpathians english mites . ii emetees ~ 50 100 approximate fine of mid of ily lhs eee « at end af april [95 sam russian armies in middle of january and at end of april cespoee, ‘vely 3 ®,, austrian or germanarmies » m9 oo ww@® bee, indy tines between armies» 99 99 pos " 4.x railw ions ww halicz sista tame ® se ke on rv pelanser-baltin) ** hy l gsi ”. ae ons is slowly forward on tuchla, but with the iit. army on its left fall- ing back before the russian counter attacks could accomplish little. meanwhile, pilanzer-baltin, whose group had been rein- forced in the last week of jan. by a fresh corps, drove the russians out of the bukovina with his right wing, while his left wing reached in succession kolomea, nadworna, and finally, on feb. 20, stanislau. he now purposed to wheel to the left, to come in on the flank and rear of the russian forces facing lingsingen. this move was checked by the assembly to the north and west of stanislav of lechitski’s ix. army, which had been transferred from the russian-front in poland. dlitempt to relieve preemysl—during the first half of feb. the austrians transferred the i]. army (bohm-ermolli) from the polish to the carpathian front, with the intention of making a last attempt to relieve przemysl. by the end of february, when this ji. army was ready to advance, the situation of the austrian forces in the carpathians seemed critical, in spite of their numer- ical superiority. the left of boroevich’s iii. army had almost reached breaking point under the continual pressure of brusilov’s forces, which had captured meze laborcz and the lupkow pass; linsingen’s army held its ground, but could make no headway; ptlanzer-baltin’s army was threatened by lechitski’s concen- tration; and przemysl was in sore straits. the offensive of the ii. army, if it was to restore the situation, required a rapid and striking success. the principal offensive was made in the direc- tion of baligrod, astride the shortest road to przemysl. at no time did the attack meet with any great measure of success; and by the middle of march it was stopped as hopeless, the austrians being completely exhausted by the weather and their heavy 544 losses. the formations which had borne the brunt of the assaults had lost over 50% of their strength. przemysl was now aban- doned to its fate. meanwhile, during the first fortnight in march, lechitski’s forces had driven pilanzer-baltin some 20 m. back from stanislau and had reached the line of the prut in northern bukovina. an opportune reinforcement enabled pflanzer-baltin to check the russian advance. there was some further fighting; but little material change took place in this eastern portion of the battle- field up to the end of april. russian offensive-—on march 20 the russians, now sure of the fortress of przemysl (it actually fell on march 22) launched a final great offensive against the austrian iii. and il. armies. the attack was made by the left wing of radko-dimitriev’s iii. army, which had been extended eastwards, and by brusi- lov’s viii. army. for a month their effort lasted. both the austrian armies were driven over the crest of the main ridge. but both managed to maintain their positions on the other side of it, though it was only the arrival of fresh german divisions (the beskiden corps) which saved the iii. army from breaking. linsingen’s southern army obstinately withstood all shocks and indeed made some ground forward. it held fast to the important uzsok pass. by april 20 the russians paused, breathless. they had appreciably enlarged their gains south of the dukla pass, but their effort to break through the austrian front had failed. conclusions.—it is a little difficult to arrive at a just balance of profit and loss between the two antagonists in this long drawn- out struggle. the austrians seem to have attached undue im- portance to their fortress of przemysl; their obstinate efforis to relieve it brought them to the verge of collapse and cost them heavier losses in men than did the eventual surrender of the garrison. the russians, though they secured a ‘ bridge-head ” over the barrier of the carpathians, did not succeed in forcing the obstacle, and squandered valuable resources in. men and munitions by their persistence. the result showed in fact that both commanders had been ill-advised to embark on this winter battle. on the whole the consequences were more disastrous for the russians, whose ob- session with this carpathian struggle induced them to withdraw two corps from the right wing of their iit. army, and was thus a direct cause of its crushing defeat by mackensen at the beginning of may (see dunajec-san). no special lessons of tactics can be drawn from the fighting. the conditions of weather and ground were against elaboration of manoeuvre. ilill fighting requires a cegree of individual skill and of tactical leadership which neither side possessed. bintrocrrapriy,—c. menckeberg, unier linsingen in den kar- pulthen (1917); b. gourko, afemortes and in:pressions of war and revolution in russia (1918); sir a. knox, with the russtan army 1914-17 (1921); m. schwarte, der grosse krieg 1914-8 (1921 ctc.): j. e. edmonds, history of the great war (1922 etc.); see also world war: bibliography, (a. p. w.) carpenter, john alden (1876- ), american composer, was born at park ridge, ill., feb. 28 1876. tle was educated at harvard university, graduating in 1897, and joined his father in business in chicago. subsequently he studied music in europe under elgar, and in chicago under ziehn. his compositions in- clude gifanjali, a song-cycle with words by tagore (1914); adventures in a perambulator (1915); a symphony (1917); the birthday of the infants, a ballet pantomime, produced by the chicago opera co., dec. 23 1919; and arazy-aat, a ballet, pro- duced dec. 23 1921. his published works also include a sonata for violin and piano and a number of songs. as a composer he became distinguished by his adherence to modern tendencies, and «displayed great skill and variety in his handling of the orchestra. carrel, alexis (1873- ), franco-american surgeon, was born at sainte-foy-les-lyon, france, june 28 1873. he grad- uated at the university of lyons in 1890, and for two years was prosecteur @ la faculte de medecine. he went to the united states in 1905, and worked at the university of chicago. in 1906 he was appointed to the staff of the rockefeller institute for carpenter—m—carson medical research in new york, becoming a member in rg12. he developed a new method for suturing blood-vessels, which made it possible to perform blood transfusion safely, and to transplant arteries, veins and organs. he also studied the preservation of tissues outside the body and its application to surgery. ‘this work led him in rg1i to investigate the conditions of tissues when they are living actively outside the organism. ife was awarded the nobel prize in physiology and medicine in 1912 for his contributions to the surgery of blood-vessels. on the outbreak of the world war he returned to france and devised the carrel-dakin treatment for wounds, by means of which many lives were saved and countless amputations were avoided. at the same time, with dr. du noiiy and other collaborators he studied the laws of the cicatrisation of wounds. in 1919 he resumed his work at the rockefeller institute for medical research. carson, edward henry carson, baron (1854- 1; british politician and lawyer, son of edward henry carson, a civil engineer of dublin, was born feb. 9 1854 and educated at portarlington school and trinity college, dublin. he became an irish barrister and made his reputation as crown prosecutor in the difficult years when mr. a. j. balfour was chief secretary for ireland. his pluck, readiness, wit and skill in cross-examina- tion soon brought him to the front, both in legal and in political circles. he became a q.c. at the irish bar in 1889; but his am- bitions could not be satisfied with legal eminence in dublin. he was called to the english bar, and took silk there in 1894. meanwhile he had been returned to parliament in 1892 in the unionist interest as member for his own university of dublin and was for a few months solicitor-gencral for ireland. ie en- tered parliament just when gladstone was about to make a second effort to pass a home rule bill, and he helped to defeat the measure. but during the next 20 years he was mainly occupied with his professional work. having risen to a leading place at the bar in ireland, he achieved an even more striking success at the english bar and in 1900 became solicitor-general, a post which he held till the fall of mr. balfour’s government in dec. 190s. it was not until r9r1, when another home rule bill was im- minent, that sir edward carson, who had gradually become the spokesman of the irish unionists in parliament, emerged as a political figure of importance. he strenuously resisted the parlia- ment bill, which was to curtail the power of the lords and enable a measure of hlome rule to be passed without a direct appeal to the people. ile was one of the ‘‘ die-hards” who urged the peers to take the responsibility of throwing out the bill in spite of the ministerial threat to swamp their llouse with sufficient new creations to make its passage secure. he told the house of commons that home rule, if carried by force, would be resisted by force and that the resisters would be constitutionally right. feeling against the home rule policy was most bitter in ui- ster, which, protestant and loyal, would be placed thereby at the mercy of the roman catholic, and largely disloyal, majority of the other three irish provinces. he went to ulster in the autumn, and at an enormous unionist demonstration at craigavon, near belfast, endorsed the threats of rebellion against home rule which previous speakers had made. belfast, he said was the key of the situation; ulster would never submit to a parliament in dublin. they must be prepared, if necessary, to take over the administration of those districts which they were entitled to control. practical measures were immediately taken in this di- rection, though liberals and nationalists scoffed. his position was that he and his ulster friends were loval to the constitution as it existed; they were only rebels, he said, in the sense that they desired to remain under the king and the imperial parliament. in anticipation of the introduction of the home rule bill in the spring of 1912, he presided over a gigantic gathering in belfast in easter week, which mr. bonar law, the newly appointed union- ist leader, came to address; and he made those present repeat after him, “ we will never, in any circumstances, submit to home rule.” he himself, in a speech instinct with passion, moved the rejection of the bill on its introduction, and took a leading part in opposition during its subsequent stages. but his activity was mainly outside parliament. he made frequent cartel speeches in the next two years in different parts of england and scotland, particularly at a great demonstration at blenheim in july r912, at which mr. bonar law pledged the support of the unionist party to ulster. his principal work, however, was in the organisation of resist- ance in ulster itself, including the formation of a local volunteer force, which speedily assumed large proportions. in sept. 1912 he was the chief figure at a series of demonstrations in all parts of the province, culminating in an enormous assemblage at bel- fast on sept. 28. there he took the lead in signing a solemn covenant, by which the men of ulster bound themselves to stand by one another in defending their position of equal citizenship in the united kingdom, and in using all necessary means to defeat the proposal to set up home rule, and further pledged themselves to refuse to recognise a home rule parliament. he followed this up by moving (unsuccessfully) in parliament on new year’s day 1913 the exclusion of ulster from the bill. in the autumn of 1913 the ulster unionist council organised itself, under his supervision, into a provisional government, of which he was the leading member, and a guarantee fund of {1,000,000 was initiated to which he himself contributed £10,000. he reviewed the volunteers, who were rapidly becoming a for- midable military force, approaching in number 100,000 men. but when ministers who had refused to prosecute him or to in- terfere with his activities began to realise the determination of the six northeastern protestant counties he did not repulse their overtures for a settlement by consent, but said that it must not establish a basis for separation. his advice during the following winter to his ulster friends was “ peace but preparation.” he entirely declined to accept mr. asquith’s offer, in the early spring of 1914, of a county option of exclusion for six years. that was “‘ sentence of death with a stay of execution.”” there was only one policy possible, he told the house of commons: “‘ leave ulster out until you have won her consent to come in.” fe be- came a member of the abortive buckingham palace conference convened by the king, and when that broke down, at the end of july, it looked as if he and his ulster friends would have to make good in action their policy of force. the world war intervened and switched off his activity into another direction. though he resented, as a breach of the polit- ical truce between parties, mr. asquith’s determination to pass the home rule bill into law, while suspending its operation and promising some form of special treatment for ulster, he went to belfast in order to stimulate ulstermen and especially ulster volunteers to join the british army, and had a considerable suc- cess. he was eager for a thorough prosecution of the war, and accordingly joined mr. asquith’s coalition ministry of 1915 as attorney-general, resigning however in october because he thought that the policy of the cabinet, after the defection of greece, involved the desertion of serbia, a small country in whose fate he took a profound interest. he was strongly in favour of the compulsory service bill in 1916, and regretted that mr. red- mond should insist on exempting ireland from its provisions. he looked favourably upon mr. lloyd george’s efforts that summer to arrange an agreed settlement of the irish question; and when that statesman formed a new government in december for the more efficient conduct of the war, he accepted office as first lord of the admiralty. at this period the board of admi- ralty were mainly engaged in devising means to counter the ger- man submarine attack, which was steadily increasing in intensity; and he devoted all his energies to the pursuit of this vitally impor- tant aim. outside his departmental duties he warmly promoted the irish convention which the govt. assembled in 1917. in july he quitted the admiralty to become a member of the war cabinet without portfolio, a position which he resigned at the beginning of 1918. but, in or out of office, his activity was di- rected wholeheartedly to the vigorous prosecution of hostilities. after the war was over ulster and ireland regained the first place in his thoughts. at the general election of 1918 he left dublin university in order to represent one of the divisions of ulster’s capital, belfast. on the anniversary in july 1019, of the battle of the boyne, he restated, speaking near belfast, 545 ulster’s position and claims, and threatened to call out the volunteers if any attempt were made to change her status. when, however, mr. lloyd george proposed in the winter his bill for the reform of the government of ireland, establishing parliaments and executives both in dublin and in belfast, and a vederal council for all ireland, he modified his attitude. though he would have preferred no change, yet, as this bill gave the six protestant counties of ulster a parliament of their own, besides representation in the imperial parliament, he would not oppose it. after it had passed, he exerted himself with success to secure a strong unionist majority in the elections in may 1921 for the first parliament of northern ircland. he had thus achieved his main political object of saving protestant ulster from domination by the roman catholic majority of the south and west. through- out the past ten exhausting years he had, save while in office, combined with his political work an immense practice in the law courts; and after the ulster elections he accepted a lordship of appeal and a life peerage as baron carson of duncairn. but, though he had become a judge, he did not hesitate to avail him- self of his opportunities as a member of the house of lords to continue to give his countrymen the benefit of his counsel at critical moments of the irish question. thus, he bitterly de- nounced the treaty which constituted the free state, both at the time of its conclusion and when the bill to carry it into effect was before his house. he also protested in 1924 against the bill which empowered the british govt. to appoint, owing to ulster’s default, a third commissioner on the irish boundary commis- sion. but he cordially welcomed the agreement, made at the close of 1925, between the british govt., the govt. of the irish free state, and that of northern ireland, which finally settled this question. he was twice married—in 1879 to sarah a. i. kirwan, who died in 1913, and in 1914 to ruby frewen. (g. e: b.)