A PROPOSED ENCYCLOPAEDIA of CHEMICAL REACTIONS C. A. JACOBSON Industrial Science Division, West Virginia University, Morsantown, West Virginia
EDITOR'SNOTE: Desfi'te the excellent abstracting sem'ces available to us and the reference comfi'lations to be found in all well-equipped chemical libraries, the labor of making a reasonably thorough search of the literature pertaining to even a very limitedfield of chemical subject matter is tremendous. A truly exhaustive search i s seldom attempted and probably represents i n reality only a n ideal to be approached as closely as possible. The usual literature search may be roughly divided into four stages: ( 1 ) accumulation from reference works of a summary of facts m'Ih corresponding references for subsequent checking and amplification by direct resort to the literature; (2) extension of the original summary by search of abstract indues; (3) examination of abstracts to determine which references are worthy of fuller investigation; (4) verification of facts and references already accepted as useful and supplementation of summaries by direct resort to the literature.
It i s obvious that if any of these processes could be performed more eficiently or i f any two of them could be combined, library research would be significantly facilitated. A work of the type proposed by Dr. Jacobson would combine the convenience of a n index with a considerable portion of the informational content of abstract and reference works. If it should be found economically feasible to issue such a work i n card-index form with prowision for periodical supplementation by card addition, the time-lag factor could be reduced to a minimum and ultimate obsolescence nztirely avoided. ( I n this event it would be necessary to devise some other system than simple consecutive numbering to indicate the proper sequence of cards.) The plan of the proposed encyclopadia i s here presented to the chemical public for the duel purpose of stimulating comment upon the general idea and of inviting criticism of specific details.
T
HE need of access to some work of reference which would provide easily located information regarding known reactions of elements and compounds, has doubtless been felt by all who have pursued research of a chemical nature. No reference book on chemical properties and reactions is complete. In fact, all such reference books, in toto, printed in any one language would be quite incomplete in supplying information about all known chemical transformations. Consequently, the loss of time and materials attributable to duplication of investigations is enormous. In short, if a digest of the world's chemical knowledge were available in easily accessible form, a greater impetus to productive research would be given than through ,any other single achievement in the realm of chemistry. The nature of the work and the plan for %ccomplishing such a momentous undertaking are outlined in the following pages. 1. All reactions are to be given under each element, the elements being arranged alphabetically with respect to their symbols. 2. The reacting substances are to be placed in alphabetical order with respect to their symbols or to the symbol of the most significant electropositive element present. 3. All reagents that effect some chemical transformation of the reacting substance in question are
614
4.
5.
6.
7. 8.
9.
alphabetically placed in a marginal space to the left, and are numbered consecutively under each element. The symbol or formula of the reacting substance is placed a t the head of each group of reactions, and the symbol or formula of the reagent, under its number in the marginal space. A signifies heat, e the electric current or spark, and P pressure. Opposite each reagent and n u d e r is to be given a brief statement of the salient condition governing the reaction between the substance and the reagent employed. Following the paragraph stating the conditions of reaction is a completely bal3nced equation, expressing by symbols and formulas the completed reaction. If the reaction proceeds by steps, then each step is to be represented by a separate equation, and lettered, (a), (bj, (cj, etc. If the resulting product 'of a reaction is known only by name, as in the case of No. 86 under iron, then the name should be substituted for the formula in the equation. If the reagent is complex in composition so that its nature cannot readily be recognized by its formula, as, for example, dimethylglyoxime in No. 280 under carbon, then the name should be given in the margin.
When precipitates are known to be formed, the formulas of these products are printed in boldface type. When probable compounds are formed in the reaction but not reported in the original paper, the formulas of such compounds are inclosed in parentheses. A question mark is introduced in the equations of reactions where a prediction of omitted products cannot be made, as for example No. 353 under arsenic. When the formation or decomposition of different hydrates or ammonates is involved, the varying conditions may be included in the same paragraph, and the formulas of the hydrates or ammonates follow one another in the equations below. If either the reacting substance or reagent is known only by its chemical formula, then it should be placed in alphabetical order with respect to the name of the most electropositive element. This work should cover completely the chemical transformations of all active elements and their compounds, with the exception of the compounds of carbon. The carbon compounds to be included may be given, provisionally, as follows: ( a ) all compounds containing carbon with one other element alone, excepting hydrogen; (b) all hydrocarbons up to and including six carbon atoms; (c) all compounds containing one or two carbon atoms together with hydrogen and oxygen; ( d ) compounds of carbon that are inherently inorganic in nature like the oxalates, carbonyls, cyanides, thiocyanates, etc.; (e) organic compounds that serve as reagents for inorganic processes. Formulas found in the older literature such as HO for water, CPHZfor acetylene, etc., should appear in quotation marks, but with the correct formulas in the equation as illustrated in No. 364 under antimony. Reactions that are apparently erroneous may be included with a question mark, when reported by famous chemists, as illustrated by No. 130, under carbon. 19. Following the equation, the name of t h z author and the literature reference, including date, are to be given. 20. The statement of conditions of a given reaction, together with its equation will appear but once in the work. When the same reaction is encountered under the other elements involved, then reference is made to the place where the reaction was first encountered. Exception to this rule will be made in the case of most of the compounds containing hydrogen, oxygen, sulfur, and the halogens. 21. No equations will be given under oxygen.
22. Under hydrogen only those reactions will be included that deal with compounds of hydrogen containing one other element, and when that element is carbon, the limitation is stated under (16b). 23. In reproducing or abstracting the conditions governing a given reaction, close adherence to the letter of the text, even though it is ambiguous or manifestly erroneous, must be maintained. This work is intended to be of historical as well as of practical value. 24. A large number of organic reactions could be expressed by graphic, or empirical formula equations but no attempt will be made a t present to cover the organic field in this way. The appended reactions have been selected to illustrate the plan of the work, with a view to eliciting aiticisms or suggestions as well as for the purpose of creating an interest in the undertaking. The work could never be completed without the help and cooperation of a large number of workers who would be willing to cover the chemical literature in the different languages. The intention is to secure a large number of associate editors representing the chemical literature of every country, each associate editor to be responsible for the abstracting of articles representing chemical reactions appearing in one journal or small group of journals, and for transmitting these records to a central office, where the tabulation and arranging of the data would take place. All data appearing in the publication will have been worked up by some one of the associate editors, whose names and addresses will appear in the work, as being iesponsible for all abstracts taken from a given journal. Suppose, for example, Mr. 0. Fioli of Rome, Italy, had abstracted No. 301 under lithium, and that someone desires more information concerning this reaction, which is only available in the Atti. est. Veneto Sci. let. arti. and cannot be procured or read by the person desiring the information. This work would show him a t once with whom to communicate. Other advantages of a complete and perpetuated work of this nature will doubtless appear as the plan is perused. ALUMINUM
5C
I.
Aluminum unites directly with carbon in a vicunm at e he reaction
650° forming yellow aluminum carbide.
[i. means with] proceeds rapidly at 1400'. 4AL 3C = AhCi I. N. PRIND, J . Chrm. Sor, 93%2103 (19081
No. 80 5 KAu(CN1. KOH
+
+
Metallic gold and aluminum oxide scparate while potassium cyanide is formed in solution when an alkaline solution of potassium auracyanide is treated with aluminum. ZAl BKAu(CN)z 6KOH = 6Au lZKCN Also1
+
+
+
+
. No. 355 5 K or N a
No. 375
NntFn
A solid hydride is formed when arnine reaetr with PC18
~ ~ t n l lpotassium ic reduces aivminum chloride to aiuminum when the two are heated together. AICb 3K = A1 3KCi warn.. popp. A S S . . 11,146 ( l a w ; AS".. 91, 252 (1854)
No. 187 E PClr
Cryolite is precipitated when a solution of sodium fluoride ia treated with a solution of aluminum chloride. 3Na~Fs= NarAlPa 3NaCl AiCb C. PISPE., D. P. 35.212; Bar.. 19, 325 (abdr.) (1886)
No. 192 FHgCI,
AlIa ~ ~ t r a e h l o r o e t h y i mise formed when aluminum iodide reacts with hexaehloroethane. 3 C C b = 3C2CI. 2AiCb 312 2Alh G. Gusr~vson,BIT.. 9, 1607 (1876)
...................................................................
+
+ ............
+
+
I in t h e absence of air at O'C. ~ A E &+ 2PCh = 2PCb
/ J. v.
e
+
ASP, Arsenic triduoride reacts vigorously with rilico chloroform a t ordinary temperatures to form elementary arsenic, ete.. as indicated below. 4Ash 3SiHCb = 2A. 3SiF4 2AsCh 3HCi
...................................................................
+
AIN ~ l u m i n u mhydroxide is formed when aluminum nitride No. 274 E 0,
+
As,%
................................................................... No. 530 F H,O
.. No. 843 cH a
Potamium metaroenite i.l formed when arsenic trisulfide reactr with potasium hypmulfite. 2As& 8-05 = 4KAsO. 8K*h01 3 s 7S01 R. BuNseN, Ann., 191, 310 (1878)
+
AdCNSIa Carbon disd6de is formed whm arnenie thiaeyannte ia hated. PAS(CNS)a A = 3Ch (?) P. M~QLW,,Ann. chim. phys., 11, 351 (1877)
_No. 353 c A
+
+
+
+
.
KAlO, Potassium peraluminate is formed when hydrogen peroxid= ~.idi%espotassium meta-aluminate in cold solution and is precipitated by alcohol. K A ~ G HIO. 5&0 = ISA~OVSHIO Turhlas, Bw., 36, 1893 (1903)
+
+
...................................................................
AiP ~hosphine is evolved quantitatively, and aluminum hydroxide is formed when aluminum phosphide r e d s with HnO in the presence of H.SOd. AIP 3H10 = ZPIL AI(0Hh L. PRANCE, 2. a n d Chrm., 37, 173 (1898)
+
+
+
+
No. 338 i &SO5
+
+
+
...................................................................
A1201 ~ b m i n u mnitride is formed when alvminum oxide and carbon are heated at 1500' in ao atmosphere of nitrosn. AhOa 3C N* = 2AiN 3C0 Fenew~e~ 2., Elc!#rochcm.. 19, 362 (1013)
+
+
An01 Arsmic trioxide is oxidized to arsenic pentoxide by ozone. AS08 20, = ARO. 20. Y ~ r r ~ n Am. a , C h m . J . , 49, 58 (1913)
~ ~ n i a ethyl r y amine is found in solution.
No. 488 F C N2
++
+
+
+
+
+ 4HCi
A yellow and 6nally blaek ppt. f o r m when arsine reacts with mercuric chloride in water solution. ( 0 ) ASH* 2HgCb = AsHHgzCh 2HCI 3HgCb = A a B g a 8HCl (6) 2AsHr Famcsocnz. L'Orori. IS. 289 (1890) P * s r ~ e rAND ~ AXOBT.BCI... 31, 594 (1898)
................................................................... No. 390 CaCh
ASH*
Bn., 8 . 1638 (1875) ............
JAWOVSSU.
KH?ArOd A eompler salt is obtained reacts with arsenate in state. 4K&AsO. KloWnO~~ 3H.O (2KOH) 3Ha0) W. Grees, Proc. Am. Acod. ArIt 50 (1888)
No. 402
e &.w,.o,,
+
+ +
+
when potasdum dindd potassium duodeeatung-
= 2(AaO$.6WO..3ICIOSci.. 18, 134; Ann., 148,
ANTIMONY CARBON No. 364 E 6H3
"CIHI"
...~ ~is p a r d~ into antimony t pentaehloride ~ l until~ saturated. Upon cmling, rhambie eryotais of aeetylenic antimony pmtechloride are obtained. CIH. SbCh = c*H~SbClh("C.HI'') BERTHBLOT AND JUNO~LBISCX. Ann., 7 (Suppl.), 252 (1870)
+
' ' "" " '
~
NO. 4 FNH'
~ I
-
At 30- sbohol mmpietely dehydrate. the hydrated lithium thioantimonnte. 2LiaSbSh 17HnO 2LiuSbS1.17H.O Chrm. Wcckblod. 7 , 211 (1910) F. A. H. Sc-msmrsas.
+
(SCSNd. Chiom-mido-dithi-carbonate is prepared by passing a moderate excess of Ch through a ehloraform solution of azido-carbon dirulfide a t -16'. the excess Clr being r c moved by dry air. On evaporating the solvent a white solid undergoing gradual transformation into a yellow v i s e o ! ~ail ~ is obtained. Ch PC~WSN. (SCSNs), W. H. GARDNBP.AND A. W. BROWNB, J . Am. Chem. Soc.. 49, 2781 (1927)
No. 14
"I"
+
ARSENIC C .................................................................. a mkture of tin and
4As
No. 153 6 HES
+ 3%
= SnaAa
~ r s e n i eacid is slowly but completely converted into thioaroenie aeid by hydrogen sulfide; thioarsenic aeid is unstable and breaks down into arsenic pentasulhde sod HS. (a) HaA.0. H a = HsAsOIS H,O Ha0 (6) HIASOIS H,S = HaAsO& ( r ) HaAsOISz H1S HdsOS. Hx0 (d) HIAIOSI H I = H~APS, Ha0 (4 2HxArS4 = Ass% 3 H P McC.%u,2. onorg. Chcm., 29. 36 (1902)
++ ++
-
+
++ ++
-
......................................................
AS ---
No. 24
+
+
................................................................... No. 530 i. 6 H s O H
Ammonia oassed over . alowina- earboo forms ammonium cyanide and methane. 4NHs = 2NILCN CR. 3C Ann., $8, 82 (1841). F. K-AX.
NO. 74 5 NaNHz
.........
I
CO, Carbon dioxide nets on nadamide t o form sodium cyanamide. (a) NaNH, CO, = OCNH3ONa HIO (b) OCNHaONa = NaOCN (0 NaOCN NaNHr = NaCNz HsO DXFSHSBL. J. D~akl.Chcm.. 16. 203 (1878)
+ +
+
+
CSI
No. 103 e
h
acts on an aqueous solution of potamium-triI nltnde .~ o.d im .n ethe orcoence of CSn to farm mtasrium iodide and ~~
~~
~
a precipitate bf a~ido-carbondisulhdi. (n) KNa CSI = KSCSNI (b) ZKSCSNI Is = ( S C S m r 2KI BROWN= AND HOBL,J . Am. Chcm. Soc.. 4 4 , 2110 (1922)
+
+
+
No. 130
E
A
I
NaCaNa ' o n adding silver nitrate to a solution of sodium dicyantmtde, the silver ~ a l tseparates ap a pure white, veqy bulky precipitate. AgNOa = AgClNa (NaNOd NaCaNa E. C. FEANZLIN. J. A m . Chrm. Soc.. 44. 500 (1922)
CClr?C.CId') =his chloride of carbon was p-sed through a gl-o tube filled with broken glass heated red hot. The resulting vapors were condenred and the free chlorine was removed by mercury. CCI. a = CCII (CId voa V. R e c n ~ u ~Ann.. r . . 80,. 350 (1839)
................................................................... HICINI On heating a liquid ammonia solation of dieyano-diamide at a temperature of 100" for several how., melamine in the fmm of beautiful crystals is obtained. A BHaCaNe 3HGNa E. C. FRANILIN, I. A m . Chcm. Sor., 44, 504 (19221
No. 152 < A
+
No. 530 E HsO
I
I
I
I 1
--..-.~. Perthloeyanic acid breaks down into thiourea earbonyl sulfide and sulfur when heated with water or strong sulfuric aeld (a), or into ammonium thioeyaoafe, carbon dioxide, hydrogen sulfide and sulfur when heated with water t o 200" in a .e&d tube (bl. (a) HzNKhS. Hz0 = CS[NH& COS S (b) HXN~CIS. 2HsO = NHICNS CO. Hd S C m n r r ~ w ~AND u S T W B NJ~. Chcm. Soc., TI', 009 (1897)
++ +
++
+
................................................................... No. I00 5 H,s
+
+
+
+
.CNT . A d u t i o n 01 cyanogen iodide reacts with hydrogen sulfide to form hydmeyanic acid, hydriodic h d . and sulfur. CN1 HI C S -..- + , ASS --. . = HCN ~. G. P. B ~ x r s n J. , A m . Chem. Soc., 26, 1580 (1904)
+
IRON
................................................................... ................................................................... FeCla A cold acid solution of ferric chloride, containing about No. 190 c cupfernon0.2 gram io 100 ee. is treated with a 0% solution of eupE Ch fenon, produdog a red, flaky precipitate of iron-nitrosopheoyl hydrorylamine (quantitative). FCCL C.HINONONHA= Cupferron-Iron salt+ (3HCI) R. Fmsmras. Z . e n d Chcm., SO. 36 (1911) 0. B ~ u m s c x Chrm.-Zlg, , 23. 1298 (19091 Bavorsca A N D KING,J. Ind. Eng. Chrm.. 8, 029 (19111 ................................................................... B r ~ r zAND H a o r r e , Z. anarp. Chcm., 66, 420 (1910) N ~ S S ~ S OZN , . mzm. them.. as, 969 (1911) PhlCNO). ~.~ Plumbic cyanate is hydrolyzed by hot H.0 to urea and No. 218 lead carbonate. This is a quick and simple method for 6 Hs0 obtanmg pure urea. LITHIUM pb(CN0). 2H2O I CON&L PbCOa A. C. CUMMINOS. J . Cham. SOC..as9. 1391 (1903) ................................................. ......... HCN 11 chlorine b conducted through a solution of alcohol with hydrogen cyanide, cyanogen chloride is formed. The cyanogvl chloride decomposer in the presence of water to yield ammonium chloride and carbon dioxide. (a) HCN CL = CNCI HCI (b) CNCI 2HzO = NHGI COz S r a ~ a o u sAnn., ~ , 83. 95 (1839)
+ +
+
+
+
solution of free thiocvanoaen may be made . by treating a plumbic thiocyanate suspension in ether with less than the calculated amount of bromine. Pb(SCN), Brr = (SCN), (PbBn) WILCOXON, MCKINNBY, AND BROWN% J . A m . Chcm. So
