Pressure of Pure Substances ORGANIC COMPOUNDS DASIEL R. STLLL
T h e increasiug importance of yapor pressures iii the forw-ard march of technology prompted the author to assemble as much of this information as h e could locate. Data on oVer 1200 organic compounds from the literature and private sources were collected and weighed, and are presented in the accompanying tables.
P
ROB.iBI,T the method most generally uaed for the purifica-
tion of organic compounds is t h a t of distillation. For thousands of yenrs distillation vas regarded as a n a r t , b u t the development of the technology of this process has removed it from the realm of a r t and has placed it on a rational scientific basis. One of the cornrrstones in t h e structure of technical distillation is a knov-led,;e of t h e vapor pressures of t h e components being separated. 111 a number of other portions of tlie fields of chemical and physical technology t h e story is t h e same. K h e t h e r t h e problem a t hand deals \r.ith estraction, absorption, m a s action reaction rates, or a host of others, the vapor pressure of the constituents i. required knowledge for the solution of the problem. Vapor pressure information is scattered throughout the chemical literature in countless places, many of 17-hich are not available t o the avernge technical mnn. It would be desirable and helpful if t1ie.e d:ita were collected and tematically arranged within convenient reach of all. Such a project induced t,lie interest of t h e writer some six years ago; conseque:itly a n effort was made t o exhaust methodically the sources of such iiiformation. Chernicul A b s f m c t s w a i searched through 1942: since t h a t time so many d a t a have heen restricted or t h e periodical file has heen broken, t h a t onll- inconiplete coverage has been effected. I n the vast majority of cases t’he original documents n-ere consulted. Considerable help was derived from esi;ting collectionc of vapor pressure d a t a (11, 191. 208, 2$6a, 356) in locating and checking information which wanot :ivailahle i n the original publication. Each group of d a t a K:IS copied onto a card n-ith the formula and name of tlie conipound and t h e source of tlie information. After several years it became apparent t h a t one could continue collecting d a t a v i t h o u t ever having a complete collection ; consequently the deci5ion IYZIS reached t o start norking u p the information. The method of trenting the d a t a grew out of n desire t o pre-ent the informatioil in tematic tabular form \Tliich would allow easy comparison of different compounds. The prohlem of accurately reviorking the originnl information is coniplicated by tliP fact t h a t the experimenter did his investigation under a myriad of conditions a’ t o temperature and pressure. analyticnl method seemed to present t h e be-t ~ a ofy accomplishing t h e desired result. h 56 X 35 inch Cox chart (95, 106, 107. 108) n-az used together with a set of m a p tacks of different colors. A411the information on a given compound was plotted using different colors to represent the \Tork of different individuals. With com-
The D o u Chemical Company, .?!Zidlartd, Mich.
pounds t h a t had been much worked on, it as easy to see which of the points did not fall on t h e median line. This median line wis actually a t a u t thread placed so thnt it touched the d a t a in which one had the most confidence. Deciding n-hich information to p u t confidence in required much ingenuity. If confidence J T ~ S engendered through experience with the work of a given individual, i t was extended t o his other I\-ork. If the measurements tT-ere made a long time ago when apparatus wa? poor hy present standards or t h e science was too young t o appreciate the \Torth of pure compounds, and if t h e d a t a did not agree \Tit11 mole recent data, they n-ere relegated t o a place of lesser importnnce. By choice and elimination t h e thread was placed (under slight tension) so t h a t i t fit t h e points consistently, and temperature values were “read back” at, predetermined pressures and copied onto yellox cards. These yellow cards carvy also the empirical formula, the name of the compound, and, on t h e back, 2111 the references related t o t h a t compound. So t h a t ambiguity rould be minimized, the name recognized by Chemical Abstracts was used. T h e arrangement in the tables is also t h a t folloir-ed by Chemical .ibstracts for organic compounds so t h a t they m a y be quickly locnted by empirical formula. Table I contains pressures (in niillimeters of mercury) under one atmosphere, whereas Table I1 contains pressures (in atmospheres) over one atmosphere. All temperatures are in C. Since there is a discontinuity in a vapor pressure curve :It the melting point of the compound, it is listed in Table I where knon-n. Since t h e vapor pressure curve ends a t the critical point, Table 11 lists the critical temperature and pressure. It is difficult t o assemble results from a Iargc: number of ~ ~ o r k e r s tvorkiiig in all parts of t h e v-orld v i t h all kinds of equipment over t h e last hundred odd years, and assign accuracy to this data. Since t h e method of interpolation is a graphical one, the personal error is also a n unknon-n factor. In a number of cases t h e same d a t a n-ere plotted and “read hack” a t times .,Tell separated from each other. T h e agreement \vas a l n a y s within half a degree; therefore tlie 11-riter feels certain t h a t t,he values presented in these tables are correct t o the nearest degree (assuming t h a t the origiiinl iiiformation is accurate). T h e writer further feels t h a t in the majority of cases, the agreement n-ill be of the order of a few tenths of a degree. XOMEKCLATURE
d tl dl
e
i
= = = = =
dccomposes dextrorotatory inactive (50% d a n d 50% I ) explodes levorotatory
ALP. = melting point P o = critical pressure p
s
T,
= polymerizes = solid =
critical temperature
Tables I and 11, pages 518-536 Literature citations, pages 337-540
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I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY ACKNOWLEDGMENT
Many hand3 Thi-. 5 ia ’. not solely t h e work of one individual. have helped with the task, and it is a pleasure to t h a n k all ivho have helped make this cooperative project a reality.
LITERATURE CITED (1) -%lien,J . Chem. Soc., 77, 400-16 (1900). ESG.CHEM.ANAL.ED.,16, 605-6 (2) Althouse and Triebold, IND. (1944). (3) Altschul, 2. p h y s i k . Chem., 11, 577-97 (1893). (4) Amagat, Compt.rend., 114, 1093-8 (1892). ( 5 ) Amagat. J . Phys.. ( 3 ) 1, 297 (1892). (6) Am. Petroleum Inst. Research Project 44, Natl. Bur. Standards, tables endingwithletter K (June 30, 1946). (7) Andri., Compt. reiid., 126, 1105-7 (1898). ( 8 ) .Indrews, J . Phys. Chem., 30, 1497-1500 (1926). (9) .InschiitZ, Ann., 221, 133-57 (1883). (10) -4nschiitz and Berns, Ber., 20, 1389-93 (1887). (11) .Inschiita and Keitter, “Die Destillation unter verniindertem Druck irn Laboratorium”, 2nd ed., Bonn, Cohen, 1895. (12) Ansdell, C h e m . S e w s , 40, 136-8 (1879). (13) Arbusow. Chem. Zentr., 1909, 11,684-5. (14) drbusoiv, J . Russ. Phys.-Chem. Soc., 41,429-46 (1909). (15) ;Iston, Kennedy, and Messerly, J . Am. Chem. Soc., 63, 2343-8 (1941). (16) +%ston,Kennedy, and Schumann, I b i d . , 62, 2059-63 (1940). (17) d s t o n and hlesserly, Ibid., 58, 2354-61 (1936). (18) Aston, Sagenkahn, Saass, Moessen, and Zuhr, I t i d . , 66, 1171-7 (1944). (19) Aston, Siller. and hlesseriy, I b i d . , 59, 1743-51 (1937). (20) .Itkillson, Heycock, and Pope, J . Chem. Soc., 117, 1410-26 (1920). (21) .%uwersand Lange, Ann., 409, 149-52 (1915). (22) Babasinian and Jackson, J . -4m. Chem. Soc., 51, 2147-51 (1929). (23) Baly and Donnsn, J . Chem. Soc., 81, 907-23 (1902). (24) Barker, 2 . phyaik. Chem., 71, 235-53 (1910). (25) Bauer and Burschkies, Ber., 68B, 1238-43 (193.5). (26) Baxter, Bezzenberger, and Wilson, J . Am. C‘hem. SOC., 42, 1386-98 ‘(1920). (27) Beale and Docksey, J . Inst. Petroleum Tech., 21, 860-70 (1935). (28) Beall, Re.tiner -\-atural Gasoline Mi?., 14, 586-9 (1935). (29) Beare, JlcYicar. and Ferguson, J . Phys. C‘hem., 34, 1310-8 (1930), (30) Beartie, H d l o c k , and Poffenberger, J . Chem. Phys.. 3, 93-6 (1935). (31) Beckmann. Fuchs, and Gernhardt, 2 . p h y s i k . C‘hem.. 18, 473513 (1895j. (32) Beckmann and Liesche, Ibid., 88, 13-34 (1914). (33) Ibid., 88, 419-27 (1914). (34) I b i d . , 89, 111-24, (1915). ( 3 5 ) Berliner and l l a y , J . Am. Chem. SOC.,47, 2350-6 (1925). (36) Ibid., 48, 2630-4 (1926). (37) Ibid., 49, 1007-11 (1927). (38) Berthoud, J . chim. p h y s . , 15,3-29 (1917). Berthoud and Bruin, Ibid., 21, 143-60 (1924). Bertram and Gildemeister, J . prakt. Chem., 11, 39, 349-55 (1889). I b i d . , 49, 185-96 (1894). Bertram and Helle, I b i d . , 11,61, 293-306 (1900). Beyer and Claisen, Ber., 20, 2178-88 (1887). Biltz, Ann., 296, 263-78 (1897). Blaise and Luttringer, Bull. soc. chim. Jfdm.,111, 33, 761-83 (1905). Blasekowska and Zakrzewska, Chem. Zentr., 1929, 11,3076. Blaszkowska and Zakrzewska, Roczniki Chem., 8,210-18 (1928). Bolas and Groves, J . Chem. Soc., 24, 773-85 (1871). Booth, Burchfield, Bixby, and McKelvey, J . Am. Chem. Soc., 55, 2231-5 (1933). Booth and Swinehart, Ibid., 57, 1337-42 (1935). Bouveault, Bu!l. soc. chim., 111, 17, 363-72 (1897). Brickwedde, Bekkedahl, Meyers, Rands, and Scott, J . Research N a t l . Bur. Standards, 35,39-87 (1945). Bridgeman, J . A m . Chem. Soc., 49, 1174-83 (1927). Brinkman, Thesis, Amsterdam. Briner and Cardoso, J . chim. phys., 6 , 663 (1908). Bri.woe aiid Peel, J . Chem. Soc.. 131, 1741-7 (1928). Britton. T r a n s . Faraday Soc., 55, 520-5 (1929). Bruckner, 2 . anorg.allgem. Chem., 199,91-2 (1931). Bruhl, Ber.. 32, 1222-36 (1899). Brunner, Ibid.. 19. 2224-8 (1886). Buckler and Norrish, J . Chem. Soc., 139, 1567-9 (1936).
(62) (63) (64) (65) (66) (67)
531
Bullard and Haussmann, J . P h y s . Chem., 34, 743-7 (1930). Burchfield, J . Am. Chem. Soc., 64, 2501 (1942). Burg and Schleainger, I b i d . , 59, 780-7 (1937). Burrell and Robertson, Ibid., 37, 1893-1902 (1915). I b i d . , 37, 2188-93 (1915). Burrell and Robertson, U. 9. Bur. Mines, Tech. Paper 142, (1916). (68) Butler et al., J . Chem. Soc., 138, 280-5 (1935). (69) Cailletet, Compt. rend., 85, 851-4 (1877). (70) Cailendar and Griffiths, Chem. .&‘em, 63, 1--2 (1891). (71) Carbide and Carbon Cheniicals Corp. ulletins (1945). (72) Cardoso, J . chim. p h y s . , 13, 312-50 (1915). . (73) I b i d . , 13, 332 (1915). (74) Cardoso and Bruno, Ibid., 20, 347-51 (1923). (75) Carpmael, British Patent 469,421 (1937). (76) Cavalier, Ann. chim. phys., 18,449-507 (1899). (77) Cavalier, BdZ. soc. chim., 19, 883-7 (1698). (78) Chamuieau and Noyous, Acta Brel;ia -Veerland. Physiol. Phurmacol. Microbial., 2, 94-5 (1932). (79) Chappuis and Rivigre, Compt.rend., 104, 1,504-5 (1887). (80) Chipman and Peltier, ISD. EKG.CHmr.. 21, 1106-8 (1929). (81) Ciarnician and Silber, Ber., 29, 1799-1811 (1896). (82) Clayton and Giauque, J . Am. Chem. Soc., 54,2610-26 (1932). (83) Clusius and Teske, Z . physilt. Chem., 6B,135-51 (1929). (84) Coffin and Maass, J . Am. Chem. Soc., 50,1427-37 (1926). (85) Coffin and Maass, Chem. Zentr., 1928, I , 1643. (86) Coffin and Maass, T r a n s . Roy. Soc. Can., 131 21, 33-40 (1927). (87) Coffin, Sutherland, and Maass, C a n . J . Re?earch, 2, 267-78 (1930). ( 8 8 ) Cole, Philippine J . Sci., 40,499-502 (1929). (89) Collie, J . Chem. Soc., 55, 110-13 (1859). (90) Commercial Solvents Corp. hull. (1944). (91) Coolidge, J . -4m. Chem. Soc., 52, 1874-87 (1930). 192) Coolidge and Coolidge, I bid., 49, 100-4 (1!327). ENG.CHEM.,21,1116-7 (1929). (93) Copson and Frolich, IXD. 194) Cosslett, 2 . anorg. allgem. Chem., 201, 7 5 4 0 (1931). (95) Courtot and Rletzger, Compt. rend., 219,487-90 (1944). (96’Cox, IND.ESG. CHEM.,15, 592 (1923). (97) Crafts, Ber., 20, 709-16 (1887). (98) Crafts, J chim. phys.. 11,429-77 (1913). (99) I b i d . , 13, 105-81 (1915). (100) Crater, IKD.EKO.CHmt., 21, 674-6 (19291, (101) Crommelin, Proc. “Konink.” .%kad. We~enschappenAmsterdam (1913). (102) Crommelin, Bijleved, and Brown, Proc. -4 cad. Sci. Amsterdam, 34, 1314 (1931). (103) Cunninghain, P o w ? . 72, 374-7 (1930). (104) Dana. Burdick, and Jenkins, J . Am. Chem. Soc., 49, 2801-6 (1927). (105) Datin, Ann. Physilt., 191 5, 218-40 (1916). . (100) Davis. ISD.ESG.C H E h I . , 17, 735 (1925). (107) I h i d . , 22,380-1 (1930). (108) Davis and Calingaert, Ibid., 17, 1287 (1925). (109) Dejardin, Ann. phys., [9] 11, 253-5 (1919). (110) Demjanoff, Ber., 28, 22-4 (1895). (111) Dittmar and Fa- referrcd t,o was used. So t1i:it nml,iqiiity nil1 be minimized, t h e nnme recogiii /ed liy ( ' h c m i d .Ibstracts has been used. T h e arrnngement i i i tlic: t:ililci i, :t~phabetic:d according t o the name of the ~ ~ J 1 l ~ ~ ) l i U l i t ~ . :iiid tlie furniuln is also added so t h a t there will be n o tlouiit a- t o the suhtniicc meant'. Table I contains pressures (in millimeters of mercury) under 1 Litiiwpliere, and T:ible I1 contains pressures (in atmo>plieres) over one atmosphere. All temperatures are in C. Since there is n discontinuity in a vapor pressure curve a t t h e melting point, t h e melting point of tlie substance, xliere knon-n, is listed in Table I. Since the vapor pressure curve ends a t t h e critical point, Tahle I1 li?ts the critical temperature arid pressure. Assembling the results of many workers, as has been clone here, 1e:idu to uncertainty as to t h e accuracy of t h e d a t a . T h e temperature range is virtually from absolute zero to the highest temperatures m a n has devised. The lower p a r t of t h e temperature scale is accurate, but as higher temperatures m e reached, the uncertainty gap widens. I n the opinion of the writer the figures giveu here represent t h e best experimental d a t a possible v i t h the graphic methods employed. Thp writer is certain t h a t , as more wliable experimental measurements are made, a few of the figure> given here should be revised.
HE foregoiiig report (441) discussed the n e d for accurate vapor pre.ssure d a t a n-hen certaiil physical lan-a are put into practical application. One of the constant cries ut' modern times is for more extensive aiid better d a t a . T o a fair e.cte:it, a new plant is no better tlinn t h e d a t a used in its design. Tliese tn-o reports are intended as a s t a r t toward the improvenlelit of this circumstance. The methodical exhaustion of the sources of vapor pressure d a t a was begun some six years ago. Chemical $bstracts was searclitd through 1942, b u t t h e coverage since then has been incomplete. t n tlie vast majority of cases t h e original documeiits were consulted. Existing collections of vapor pressure d a t a (9, 199, 249, 466) were of great help. I n this connection special attention should be focused on t,he excellent compilation of Iielley (229), which has holstered our work admirably. The treatment of d a t a follows t h e style, format, and ge11crd plan of t h e preceding paper. T h e analytical method n . ; i s retained and was based on semilogarithmic charts menzurilig 30 X 42 inches (where 1 mm. = 1 C.) aiid colored map tacks reprepenting the plotted points over which a t a u t thread n-as stretched. NOMENCLATURE This resulted i n t h e introduction of a gentle curvature t o tli? T:Id = decomposes p = polymerizes por pressure line, b u t sufficient tacks were inserted 50 th:rt tlie s = solid 1I.P. = melting point curve was virtually continuous and without angles. For t h e p r T, = critical temperature P , = critical pressure manent gases (those materials belom- -100" C.), the lines x e r e penciled in with t h e help of a French curve, but, in view of tlic uncertainties in temperature measurement above 500' C. (hTables I and 11, pages 541-546 coming less certain with increase of temperature), it n-a3 felt t h a t Literature citations, pages 547-550 t h e penciling of the curves \vas unnecessary. Where t h e tempera-
