ACTION OF HEAT UPON CERTAIN METALLIC SALTS.
135
A DICTIONARY O F T H E ACTION O F H E A T U P O N CERT A I N METALLIC SALTS, ISCLCDISG
AS
ISDEX
TO THE PRISCIPAL LITERATURE UPON T H E SCBJECT.
COMPILED ASD ARRANGED BT J. W. BAIRD, M. A., PH.C. CONTRIBUTED BY PROF. A. E. PRESCOFT.
-.INTRODUCTIOX.
I t has been the aim of the author, in compiling the present work, to place in convenient form a fairly complete, and yet a concise, statement of the effect of heat npon metallic salts. No original experiments were made, nor anything introduced except that which could be accompanied by good authority. The works constilted comprise t,he leading journals of the present century and such works of reference as Gmelin-Kraut, Watts’ Dictionary, etc., in all about 1200 volumes. Absolute completeness cannot be claimed, for such a claim could only be based upon exhaustive research through all the scientific works extant, a thing which in this case was utterly impossible ; but comprising as it does a review of so many volumes, that represent the majority of experiments performed in the scientific world, it cannot be othcrwise than practically complete. Brevity has always been one of the objectsheld in view, and if in any case a more minute statement is desired, the authority itself can then be consulted, which in every instance accompanies the subject matter. Not only is reference to the original article given, which is always placed first, but also references to the briefs or abstracts of that article, care being taken t o give accurately the volume and page. There will be found given the melting and boiling points of the salts, the temperature at which disassociation takes place, the products of decomposition, both volatile and residual, and such other facts as fall within the scope of the subject, only just so far as these things are stated by the authorities consulted. T o all those who may have occasion to refer to this work, either for practical, chemical, or in short for any scientific purpose wbatever, it is respectfully submitted.
J. W. BAIRD, University, Ann Arbor, Mich., 1883.
13G
ACTION OF UEAT L-I’OS
CERTAIN YETALLIL SALTS.
ACTION OF HEAT UPON CEETAIIN METALLIC SALTS.
137
The temperatures are given on the Centigrade scale, excepting when the contrary is expressly stated. The following is the list of the most important abbreviations : Abstracts Phil. Trans. of Roy. Soc.-Abstractsof the Philosophical Transactions of the Royal Society, Amer. Chem.-American Chemist. Amer. J. Pharm.-American Journal of Pharmacy. Amer. J. Sci.-Amcricnn Journal of Science. Anna1en.-Annalen der Chemie und Pharmacie. Ann. Chim. Phys.-Annales de Chimie et de Physique. Ann. Chim.-Annales d e chimie. Arch. der Pharm.-&chiv der Pharmacie. Arch. ne’-er1and.-Archives ne’-erlandaises des Sciences. Bcr.-Eerichte der deutschen chemischen Gesellschaft zu Berlin. Bcrzelius J3hrcsb.-Jahresbericht uber die Fortschritte der p h y sichen Wissenschaften, oder der Chemie und Mineralogie. Jacob Eerzelius. Bull SOC.chim.-Bulletin de la socibti! chimique de Paris. Er. Arch.-Archiv des Apothekervereins im niirdlichen Deutschland. Chern. Centr.-Chemisch-Pharmaceutisches, since 1857 Chemisclics Ccntralblatt. Chcm. Gnz.-Chemical Gazette. Chcm. News.--Chemical Kews. Chem. SOC. J.-Journal of the Chemical Society. Compt. rend.-Comptes rendus hebdomadaires, des SQancesde 1’ Academic des Sciences. Paris. Crcll. Ann.-Chemische Annalen by Dr. Crell. Dingl. Pol. J.-Polytechnisches Journal. by E. M. Dingler. Ed. Phil. J.--Edinburgh Philosophical Journal. Gilb. Ann.-Annalen der Physik, afterwards der Physik und pliysikdischen Chemic, by L. IT.Gilbert. ~melin-I~rnnt.-Gnielin’s Handbuch by Kraut. Gmclin. Watts’ Trans1.-Gnielin’s Handbuch, translated by TT nt ts. Institnt.--Z’ Institut, Paris. Jn1ivesb.-Jaliresbericht f tir die Fortschritte der Chemie, Physik, IIincralogie und Gcologie. Jahresb. Ph. Tox.-Jnliresbericht iiber Fortschritte der Pharmacognosie, Pharmacie und Toxicologie. J. Chim. m&d.-Journal de chimie m6dicale de pharmacie.
138
ACTION OF HEAT UPOX CERTAIS M E T A L L I C SALTY.
J. P h . Chim.--Journal J. pr. Clieni.-Jouriinl
de Pharm2cie et tlc cliirnie. Climiiiv. Inorganic Cliciiiistry. ~Iiller.-~1ill~~r’s Nng. der PIiarni..-JI;ignzin dcai. 1 ’ I i ~ ~ i m a ~ ~ i ~ , illcin. ant1 Pro(*. Ciieiii. Si1c.--lIvinuirs nntl I‘rocecdings t ~ f the CL c’11i i c ;i1 S, )ci et y. 3Iiillii)ri~cdoc. I3i1~I.--Eiilletiii clc 1 : ~soci6ti. indnstriclle (le 11111horise. N. Gclll.--JUnrnnl fiir die Cliciiiic unil Pliysik by A. F,Gcliliii. K, J:ihrb. Yhariii.-Seues Jalirbiicli f i i v Plinrmacie. 1’1 13. r;n. c‘c I 1 t I..-SCC c11c 111. C‘(>llt1’. Plinrin. .J. Ti.:uie.-Piiiiriiin~~,iitic;il ,Joiirnal and Tr:insnction>. Pliil. >In?.. J.--Philoso~~liical Jlagaeiiie n n ~Ju,iiriinl l of Science. I’liil. Ti~:iiis.-Pliiloso~~liic~l Trnnsnctions. 1’11. (’11. Eer.-Pliilo.s. der Clicniic. Ecrliii, I’ogg. Aliin.-Aniialen t7cr Pliysik u i i t l Clicmie. J. C ’ . Poggcntlorff. P r o c Ahnw. A l c : d , - I’rocecdings of tlic ilinerican Acnclciiiy of A r t s : i i i d ScicBnces. T’roca. Roy. Sue.--Proccediiigs of the Royal Society. IZcll). (‘11. al)l)li.-Rel~crtoirc dc C’iiirriic :~lj1)licl11f~. Itel).(111. 1)iirc.-Rclicrtoire d e Cliimie 1111rc‘. Ro 5, ai i (1 Scli.-Rosco ( 2 a11cl Selli, rl cmni er’s c‘l 1c m ist r p. Scli~y.--.Joi~i~naIfiir Cheniie i i n d Pliysik 1))- Dr. S.c‘. Scliwciggcr. Tccli. J:ilir.-Jahrcs)Jericht iibcr Jic Fortschrittc cicr cliemischen Tecllllologic~. Trans. Roy. SOC.EL-Transactions of tlie Royal Society of Edinbnrgli. Watts’ Dict.-lyatts’ Dictionary of Clieniistry. der k. k.Akademie der W i 5 Wiss. Acad. 13er.-Sitzuiigsberichte sensclinften. Zcitschr. Anal. Chem.-Zeitschrift fiir analytische Chemie. Ze i t sch r , C 11ern, -Z eit schri f t f iir Chem ie . Zcitsclir. Chem. Pharm.-Zeitschrift f itr Chemie und Phmmscic. f i i i * pr:lktiscllc
ACTION OP HEAT CPON CEPTAIN METALLIC SALTS.
139
THE BROMIDES. Alumiizittm Bromide. AI,&,. Aluminium bromide melts at go", Rud. Weber (1) o r a t 93O, Deville and Troost (2), to a clear mobile liquid, which boils at 265270°,Rud. Weber (I), or a t 260°, Deville and Troost (2). When heated in sealed tubes it sublimes, forming colorless glittering lamin=, Rud. Weber (3) ; b u t when heated in the air it decomposes into hydro-bromic acid and alnmininm oxide, Beithemot, (4)or into vapor of bromine and oxide of aluminium, Rud. Weber (5). Amizoiaium Bronzic7e. iVKBr. Ammonium bromide vaporizes in the lieat without previous fusions (6). Antimonous Bromide. SbBr,. Antimonous bromide melts at go", Kopp (I), R. W. Emerson MacIvor (2), at 93O, J. P. Cook (3), a t 94", H. Serullas (4), or at 95" (5) to a pale greenish-yellow colored liquid, which boils a t or near 283", R. W. Emerson MacIvor (2), a t 270O. H Serullas (6), at 275.4", Kopp ('i'),or a t 280", J. P. Cook (3). When heated in a closed vessel it sublimes unchanged, H. Serullas (8). Arsenious Broniicle. AsBr,. Arsenious bromide melts a t 20-25" to a pale yellow liquid which boils at 220°, H. Serullas (9), and on cooling congeals in long prisms. W h e n heated in closed vessels it sublimes unchanged, 8. SerullaR (10). (1) Pogg. Ann. 103. 259. J. pr. Clieiu. 74. 105. Chem. Gnz. 10. 209. Chem. Centr. 1858. 365. Jnhresb. 10. 157. Ginelin-Kraut. 2. 1. 042. Watts Dict. 1. 150. Ros. and Sch. 2. 1. 417. (2) Jalircsb. 12. 2ti. (3) Pogg. Ann. 108. 259. J. pr. Chem. 74. 105. Clicrn. Gnz. 10. 209. Ros. andScli. 2. 1. 447. (4) Ann. Chim. Pliys. 44.394. (5) Pogg. Ann. 103. 200, Chem. Gaz. 16. 209. Chem. Centr. 1958. 305. Jnliresb. 10. 157. Gmclin-Kraut. 2. 1. 042. Watts Dict. 1, 150. (0) Gmelin. TT'ntts Trtiuslntion, 2. 409. (1) Annnlen 05. 307. Pliarm. Ceutr. 1855. 771. Jahresb. 8. 37. (2) Cliem. News 29. 179. (3) Proceed. Amer. Acad. Kern Series 8. Ber. 11. 255. Jaliresb. Ph. Tox. 1878. 259. Jaliresb. 30. 284. (4) Pogg. Ann. 14. 111. Ann. Cliim. Phys. 38. 322. (5) Ros. and Scli. 2. 2. 319. (6) Pogg. Ann. 14. 111. Ann, Cliim. Pliys. 38. 322. Gmelin, Watts Translation, 4. 304. Watts Dict., 1. 317. (7) Annnlcn. 95. 307. Plinrm. Centr. 1855. 771. Jahresb. 8. 37. Ros. and Sch. Y. 2. 319. (8) Pogg. Ann. 14. 111. Ann. Cliim. Pllys. 38. 322. Ros. and Sch.2. 2. 319. (9)Pogg. Ann. 14. 111. Ann. Chim. Phys. 38. 320. Gmelin, Watts Transl. 4. 283. Watts Dict., 1. 371. Ros. nud Sch. 1. 523. ALiller 585. (10) Poggq Ann. 14. 111. Ann. Chim. Phys. 38. 320. Gmelin. Watts Transl. 4. 283.
140
ACTIOX O F IIEAT UPON CERTAIN METALLIC SALTS.
Bctrizim Bromide. UuBr,. A n h y d r o u s b a r i u m b r o m i d e m e l t s a~ 812”, T. Carnclley (1). The s a l t crystallized w i t h 2 mol. water riiclts when heated, I3alard ( 2 ) . and loses i t s water, C’. Ratnmelsberg (:j). Uism iith U r o i ~ i i d e . BiBr,. B i s m u t h b r o m i d e m e l t s ac 1!~S-2W3, R. \V. E. MacIvor (A‘,, at 200”, €1. Serullau ( 5 ) , 01- at 210-215”, 31. 1’. J I n i r ( G ) , t o :L 1ij.ac i n t h r e d liquid, which boil?;a t a dark red heat., 11. Seru!!:i; ( 5 ) , 11. I\-. E. 3facIvor (4) or at 4s&&$M’ ‘1’. (’nlmeliey aiict \V. (’. IViIIiaiii3 ( 7 ) . The salt, znn be snlilinicvl iiric.lianget1, IT. Swulla:; (S1. ( . h t b l L i c o l L l I I . O U ~ i d P # ( YlI??ill? 0.
-4
Crystallized c a d m i u n i broniitlc ioscs its war t’r a t ~ O O ’ a n d the at loiP w i t l i o i i t n i i d e l y i i i g fusi(ori, C’. Raii~iii(,lhi)eig(‘3) ; b u t w h e n r a p i d l y lieated, i t iiieits i i i its \ r a t e r cjf cr!,st:tIliz:itioii, Lecomes anliyclroiis : t i l t 1 if the teiiipeixturc be now i.aistx1 tv nlmost redness i t entirely srtblirncs i i i tlic f01.m of r o u n d p e a r l y wliite scales, B e r t h e m o t (1). The a n i i y d r ~ u ssalt melt3 att. 5:lL), 1’.C:trilelle! :9,.
otlier
a-
~ . ‘ ~ ! ~ ~ ‘ ; l l~l j! li
‘ O i l l ~ ~ / f .‘ ( I I j J ’ p
C a l c i u m b r o m i d e nielt,s a t lj;~;‘, ‘1’. CnrrieIlcxy (ij), at i ; W ’ , ‘1’. O)is decomposed when heated in tlie air into liydro-broniic acid nn(l osiclc of ni:ignesiiini, Balnrd (4). Xa)ign)iotcu BromitZc. ;IhtBi*,. Crystallized manganous bromide (MnGr, ?H20), wheii carefully heated i n a closed vessel, gives off its water of crystnliizntion and l e n i e s tlw nnliydrous bromide ;3), 2nd this w h i igiiited in contact n-it11 t h e nir, gives off bromine vnpurs and lenves ni~nganoso-mangniiic osidi. (6). The salt containing iiiiol. of water (l\lnlZr, &H,O) ~ n e l t sin its water of ci*~stallizntion \r.lien l t c a t ~ d and , then becoines m l i y d r u u ~ melting , ngnin s t a wliite Iicnt, at wliicli ternpernturc it deconipo,ses completely i i i coiit:ict with tlie air into bromine and oside of ~iiniiganesc. Eci*tli(~iiiot t (1 'r. X m ~ t i / -U i ~ ~ -id^. u ~I ~~ ~ I l l ~ , . JIcrcriric 1,iumidc melts :it 222-2?3", Oppenlicini ( 2 ) or at 2&i0, 1'. Carncllcy ( 3 ) , ant1 snbliincs, I h k x r i l (A', Luvig ( 5 ) ( G ) , boiling a t 319@,T. C'nrnellcy n l i ( l I\-,(', \ViIliaiiis ( 7 ) .
14/?
,lfeI'r'/l/'i,t,S. TI-. b'ischer ( l ) t , some nitrate remaining even after long heating, J. Imig (2), and finally a mixt u r e of protoxide and peroxide of potassium (SI.
Siluer. Yitratc. i1!jSO3. Silver nitrate melts 1'38O, Pohl (1),at 2111" ( 3 , at 217418," T. Cnrnelley ( G ) , or at 233', T. ('nrnellcy, ( 7 ) ? rcisolidifying at 212", Carnelley (S), and decomposes at an incipicnt red-heat into oxygen, peroxide of nitrogen, nitrogen a n d inetal!ic silvcr (9). When the - - - . ... .~____ * (1)Amer. J . Sci. LL] 27. 14. ,J;ihresl). 12. 114. Giuelin.Iiraut 3 556. c2) Watts Dict. 4. 97. (3) Watts Dict. 4. 99, (4) A u n . Cliini. Pliys. 21. 295. Pogg. Ann. 74. 523. 70. 301. C'ompt. rend 28. lG2. Aiiiinlcn G4, 179. Jaliresb. 1. 73. Ginelin-Kraut 2. 1. 91. Ros. :iud Sch. 2 . 1. 80. Miller 340. (5) Pogg. Auo. 135. G12. Jahresb. 21. 20. Ginelin-Kraut 2. 1. 91. (6) Chem. SOC.J. 33. 273. ( 7 ) Pogg. Ann. 154. 190. (8) Clieiii. Eoc. *J. iJ1. 381. Zeitschr. Anal. Cliem. 19. 175. (9)Pogg Aiin. 102. 293. .Jtiliresl\. 10. 18. Giiielin Kraut 2. 1. 91. (10) Chem. SOC. ,J. 29, 499. (11) PII. Ch. Ber. 1813. 377. GmelinKraut 2. 1. 92.
t (1) Pogg. Aun. 74. 115. Annalen G8. 224. J. pr. Chem. 46. 318. Pharm. Ceutr. 1845. 401. Chem. Gaz. 6. 281. Jahresb. 1. 383. ( 2 ) Pogg. Ann. 118. 282. ,J. pr. Chem. 86. 295. J. P1i. Chim. [:I 42. 341. Rep. Chim. pure. 5. 77. Jahresb. 13. 99. Gmelin-Iirniit 2 . 1. 92. (3) Gmelin-Kraut 2. 1. 91. Watts Dict. 4.99. Miller 340. (4) Wien. Alraci. Der. 0. 587. Gmelin-Kraut 3. 953. Jahresb. 4. 59. Ros. aurl S(.li. 2 . 1. 377. (5) Watts Dict. 4. 104. Miller 686. (6) Cliem. SOC. J . 38. 918. ( 7 ) Chem. SOC.J. 31. 381. Zeitschr. Anal. Chein. 19. 175. (8) Cliem. Soc. J. 33. 273. (9)Ginelin-Kraut 3. 954.
ACTION OF HEAT UPON CERTAIN METALLIC BUTS.
169
salt is heated in a small retort until gas bubbles are evolved and red vapors begin t o appear, oxygen gas is given off, and the residue consists of t h e nitrite, undecomposed nitrate, and a little metallic silver, J. Persoz (10). Sodium Nitrate.
NaNO,.
Sodium nitrate melts at 310.5', C. Person (l),* a t 314O, Braun (2). at 316", T. Carnelley (3), or at 330°, T. Carnelley (4), solidifying again at 3139, Schaffgotsch (5). Sodium nitrate, when subjected t o a red heat, evolves at first oxygen under t h e formation of the nitrite, Mitscherlich ( G ) , then a mixture of oxygen, nitrogen and some peroxide of nitrogen (7), or protoxide of nitrogen, H. Deville and H. Debrny (8), and finally forms a mixture of protoxide and peroxide of sodium (9). T h e nitrite that is formed by mbjecting t h e nitrate of sodium to a red heat is always contaminated with some undecomposed nitrate and some free alkali, N. W, Fischer (lo), J. Lang (11).
Strontium Nitrate.
Sr( LVO,) I.
Strontium nitrate crystallized with 4 mol. of water (Sr(NO,),. 4H,O) melts when heated under t h e separation of the anhydrous salt, Ordway (l),t losing its water at looo, A. Souchay and E.
Lensen (a), Brooke (3). T h e anhydrous salt decrepitates when heated (4),melts at 645", T. Carnelley (5), decomposes and leaves a residue oE strontia (6), Ros. and Scli. 2. 1. 377. (10)Ann. Chin. Phys. [3] 23. 48. Chern. SOC.J. 1. 189. Annalen 65. 177.
* (1) Ann. Chim. Phys. 21. 295. Pogg. Ann. 70. 300. 74. 522. Annalen 64. 179. Jahresb. 1. 73. Gmelin-Kraut 2. 1. 218. Watts Dict. 4.106. Ros. and Sch. 2. 1. 80. Miller 361. (2)Pogp. Ann. 154. 190. (3)Cliem. SOC. J. 33. 273. (4)Chem. SOC.J. 29. 489 Zeitsclir. Aoal. Chem. 17. 469. Ros. and Scli. 2. 1. 80. (5) Pogg. Ann. 102. 293. Jnliresb. 10. 18. Umelin-Kraut 2. 1. 218. (6)Gmelin-Kraut. 1. 2,459. 2. 1. 218. (7) Gmelin.Kraut 2. 1. 218. (8) Ann. C h i n Phys. [3] 61. 117. (9)Watts Dict 4.106. (10) Pogg. Ann. 74, 115. Annnlen 68. 224. J. pr. Chem. 46. 318. Pliarm. Ceutr. 1848. 401. Chem. cfaz. 6. 281. Jahresb. 1. 383. (11) Pogg. Ann. 74.118. 281. J . pr. Chem. 86. 595. J. Ph. Chim. [3] 42. 341. Rep Chim. pure. 5. 77. Jahresb. 15. 100. t (1)Amer. J. Sci. [2]27. 14. Jahresb. 12. 113. Gmelin-Kraut 2. 1.339. (2) Annalen 99.45. J. pr. Chem. 69. 384. Cimelin-Kraut 2. 1. 339. (3)GmelinKraut 2. 1. 339. (4) Gmelin-Kraut 2. 1. 339. Watts Dict. 4. 106. Ros. and Bch. 2. 1. 216. Miller 406. (5)Chem. SOC. J. 33. 273. (6) Gmelin-Kraut 2. 1.
170
ACTION O F HEAT UPON CERTAIN METALLIC SALTS.
under the evolution of oxygen and nitrogen ( 7 ) . The nitrite is formed by the ignition of the nitrate, but is always contaminated with some free strontia, N. W.Fischer (8), and some undecomposed nitrate, J. Lang ( 9 ) . The nitrite is formed by keeping the nitrate at its melting point, IIampe 110).
z i i\?trate. ~
z1~,~\~'0,);6N~ 0.
Zinc nitrate crystallized with 6 mol. of water melts at 36.4O, boils at 131", and on long boiling remains clear until 42 per cent. of its weight has been lofit ; the residue on cooling consisting of 4Zn0.3S,0;3IIz0, Ordway (l).* TVllen t h e salt is heated for some time a t looo it loses nitric acid and water and a basic salt remains, 9 Z n 0 . 2 S 2 0 , , A. Vogel and C . Reischauer (a) ; there is also evolved peroxide of nitrogen and oxygen, Schiitdler (3) ; and at log0 in a stream of air i t lose8 nearly all its water, Pierre (4) After the salt is boiled and cooled t h e rejidue consists of ZnO.3Zri(S0,);3€1,0, Gerhardt (j),and if the heat be continued until the fialt becomes nearly solid, the residue contains 8ZnO~N1O;2H,O, Grouvelle (6 ,.
THE KITRITES. AmnLoiLium X t r i t e . XIT,LVO,, Ammonium nitrite detonates when heated between 60 and YO", Berthelot (l),!and is decomposed by a gentle heat, N. W.Fischer (2), into nitrogen and water, K€1,NOZ=N,+2H,O (3), or into water, nitrous oxide and ammonia (4). 339. Watts Dict. 4. 106. (7) Miller 40G. (8) Pogg. Ann. 74. 115. Annalen BE.224. J . pr. Chem. 46. 318. Pharm. Centr. 1848. 401. Chem. Gaz. 6. 2Y1. Jahresb. 1. 383. Gmelin-Kraut 2. 1. 339. (9) Pogg. Ann. 118.282. J. pr. Chem. 86. 295. J. Ph. Chim. [3] 42. 341. Rep. Chim. pure. 5. 77. Jobresb. 15. 100. Gmelin-Kraut 2. 1. 339. (10) Annalen 125. 337. Jahresb. 1G. 160. Gmelin-Kraut 2. 1. 339.
"(1) Amer. J. Sci. [a] 27. 14. Jahresb. 12. 113. Gmelin-Kraut 3. 34. (2) N. Jahrb. Pharm. 11. 137. Jahresb. 12. 196. Qmelin-Kraut 3. 34. Ros. and Sch. 2. 1. 262. (3) Gmelin-Kraut 3.34. (4) Ann. C h i n Phys. [3] 16. 247. Gmelin-Kraut 3. 35. WattsDict. 4. 107. (5) J Ph. Chim. [3] 12. 61. Jahresb. 1. 436. Watts Dict. 4. 107. (6) Ann. Chim. Phys. 19. 137. Gmelin-Kraut 3. 34.
t (1) J. Ph. Chim. [4] 19.4%. Bull. Soc. Chim. [2] 21. 55. Chem. SOC.J. 27. 961. 1058. Ctiem. Centr. 1874. 245. Jahresb. Ph. Tox. 1877. 270. (2) P o g g Ann. 74. 119. Annalen 68.224. J. pr. Chem. 46.318. Pharm. Centr. 1848. 401. Jahresb. 1. 383. (3) Watts Dict. 1. 192. Ros. and Sch. 2. 1. 180. (4)
ACTION OB HEAT UPON CERTAIX METALLIC SALTS.
171
Cd(NO,),*H,0.
Cadmium Nitrite.
Cadmium nitrite is decomposed even by a gentle heat, N. TIr. Fischer (2), or is decomposed at looo, forming thereby a basic salt, J. Lang ( 5 ) .
C'obaltous Nitrite.
CoNO,.
Cobaltous nitrite is decomposed even by a gentle heat, N. W, Fischer (2).
Cupic ATtrite.
Cu(NO,),.
Cupric nitrite is decomposed even by a gentle heat, N. W. Fischer, (6). A solution of the salt evolves nitric oxide even a t an ordinary temperature , W. Hampe ( 7 ) .
Lead Nitrite.
Pb(NO,),H,0.
Lead nitrite is easily decomposed, N. W. Fischer (l),* Peligot (2), and when heated at 100" evolves nitric oxide and leaves a basic salt behind, J. Lang (3).
Xagnesium Nitrite. Mg(NOa);2H,0. Magnesium nitrite is easily decomposed by heat, N. W, Fischer loo", S. Lang (a), and after being heated to redness leaves 26.14 per cent. of magnesium oxide, W. Hampe ( 5 ) .
(I), evolving nitric oxide even at
Xercurous Nitrite. Hg,(NO,),. Mercurous nitrite, when exposed to the action of heat, resists a temperature of 280," but a 890" it begins t o give off red vapors, J. Lefort (6). Gmelin. Wnlta Transl. 2. 490. (5) Pogg. Ann. 98. 291. J. pr. Cliein. 86. 295. J. P. Cliim. [3] 42.341. Rep. Chim. pure. 5. 77. Jahresb. 15. 100. GmelinKraut 3. 73. Watts Dict. 4. 72. (0) Pogg. Ann. 74. 121. Annalen 68. 224. J. pr. Chem. 46. 318. Pharm. Centr. 1848. 401. Jaliresb. 1. 383. Gmelin-Kraut 3. GOO. (7) Anualen 125. 343. Jahresb. 16. 162. Gmelin-Kraut 3. 650. * ( l j Pogg. Ann. 74. 121. Annalen 68. 224. J. pr. Cliem. 46. 318. Pharm. Centr. 1848. 401. Jahresb. 1. 383. (2) Ann. Cliiin. Pliys. [3] 2. 87. Annalen 39. 338. (3) Pogg. Ann. 118. 282. J. pr. Cliem. 86. 295. J. P. Chim. [3] 4.2. 341. Rep. Chim. pure. 5. 77. Jahresb. 15. 100. Gmelin-Kraut 3. 257. (4) Pogg. Ann. 118. 289. J. pr. Chem.86. 295. J. P. Chini. [3] 42. 341. Rep. Ch. pure. 5. 77. Jahresb. 16. 100. amelin-Kraut 2. 1. 473. (5) Annalen 125. 341. Jaliresb. 16. 160. (6) Compt. rend. 1943. July 7. Chem. Gaz., 3. 343.
172
ACTION O F H E a T UPON CERTAIN UETALLIC SALTS,
LVi(~VOz)s
Nickeloiis ,\?trite.
Nickelous nitrite is not decomposed at loo", J. Lang ( 7 ) , but when heated to redness it loses its acid, and leaves behind the oxide of nickel, J. Lang (1 * TV IIampe ( 2 )
Silver X i t r i t t
,
dgiX0,
Silver nitrite does not lose in weight at looo, but begins to decompose a t 140-150°, J. Lang (3) When gently heated in a glass tube it decomposes into metallic silver and nitrous acid (4), or evolves hyponitric acid, which converts the residue into silver nitrate, Peligot (5). W h e n silver nitrite is heated in an open dish over a lamp, or in an air bath, between 85 and 140°, i t decomposes into metallic silver, tri-oxide of nitrogen and silver nitrate, a little of the nitrite remaining undecomposwl, 3AgX0,=XT,0,+ Ag3+ A g NO,. When a closely covered crucible is used, there is fornied nitric oxide instead of the tri-oxide of nitrogen, 2AgSO,=XO + A g + A g KO,. When heated in a test tube, accurately stopped with a glass rob, red fumes appear at i l 5 O ; the crystal? begin to shrink and fuse a t 1 3 4 O , and the salt is decomposed into metallic silver, nitric oxide and oxigen, Ed. Divers (ti),
+
Zinc ,?-itrite.
Zn(1;02),314 0.
Zinc nitrite is decomposed even by a gentle heat, N. W,Fischer (l),t and when heated a t 100" evolves nitric oxide and leaves a basic salt, which a t 5 higher temperature loses its acid and IS converted into the oxide, J. Lnng (2). W h e n Zinc nitrite is heated t o redness the oxide remains, W.Hampe (3). (7) Pogg. Ann. 118.282. J. pr. Chem. 86. 293. J . P. Chim. [3] 4.2.341. Rep. Ch. pure. 5 . 7 7 . Jiihresb. 15. 100. Gmelin-Kraut 3. 555. "(1) Pogg. Ann. 118.282. J. pr. Cliem. 86. 295.,J. P. Chim. [3] 42. 341. Rep. Ch. pura. 5.. 7. Jahresb. 15. 100. (2) Annalen 125. Jahresb. 16. 160. (3) Pogg. Ann. 118. 118. 292. J. pr. Chem. 86. 295. J. P. Chim. [3J 42. 341. Rep., Ch. pure. 5. 77. Jahresb. 15. 100. Gmelin-Kraut 3. 952. (4) Gmelin-Kraut 3. 952. 1. 2. 459. (5) Ann. Cliim. Phys, [3] 0. 68. Gnielin-Kraut 1. 2. 459. (G) Chem. SOC. J. 24. 85. Bull. SOC. Chim. [2] 15. 178. Iber. 4. 282. Amer. Chem. 2. 71. Jahresb. 24. 343.
t (1) Pogg. Ann. 74. 121. Annalen 68. 224. J.'pr. Chem. 46. 318. Pharm. Chem. 1848. 401. Jahresb. 1. 383. (2) Pogr. Ann. 118. 289. J. pr. Chem. 86. 296. J . P. Cliim. [3] 42. 541. Rep. Ch. pure. 5 . 7 7 . Jahresb. 15. 100. Gmelin-Eraut 3.34. (3) Annalen 125, 344. Jallresb. 1G 160.
ACTION OF HEAT UPON CERTAIN METALLIC SALTS.
173
THE PHOSPHATES. Alzinainiuin Phosphate. A l 2 ( P 0 J 2 .
Aluminium phosphate does not melt at a red heat, Ludwig (I).*
Anzmonium Phosphate.
(LVH,),PO,.
Ammonium phosphate cannot be dried without losing ammonia and being converted into diammonic phosphate (2), which when heated first andergoes fusion, then dries up, and at a red heat is converted with slow and imperfect expulsion of ammonia into hydrated phosphoric acid (3), or into meta phosphoric acid, (SH,), HPO,=HPO, +2NH, +H,O (2).
Barium Phosphate. Xono-basic phosphate of barium (BaH,(PO,),), Then heated, melts t o a colorless glass, Erlenmeyer (A), or b~ melting forms a white, spongy mass, similar to alum, and at a red heat leaves behind meta-phosphate of barium, Berzelius ( 5 ) . Di-basic phosphate of barium (BaHP0,j melts in the heat, Berzelius ( 6 ) , loses no water at 300°, and becomes anhydrous only at n red heat, A. Chodnew ( 7 ) .
Ccichium Phosphate.
Cc7,(P04),.
Cadmium phosphate melts at an incipient white heat forming a transparent vitreous mass, Stromeyer (I).+
Ccilcium Phosph cite.
Ca, ( P0,),.
Normal phosphate of calcium can be melted at a very high red heat to a porcelain-like mass, Saussaure ( 2 ) . The precipitated salt retains 1 mol. of water at loo”, becomes anhydrous at 2000, and is not decomposed by simple ignition (3). Mono-basic phosphate of calcium (CaH,(PO,),) melts when heated, giving off all its water and leaving an insoluble meta-phosphate (4), Cn€I,(PO,),=CaP,O, + 2H?O ( 5 ) . The same with 1 mol. of water of crystallization (CaH,(PO,),€I,O) loses 17.2 per cent. of its water
-
++ (1) Arch. Pliarm. [2] 59. 10. Pliarm. Centr. 1880. 109. Gmeliu-Kraut 2. 1. 632. (2)Watts Dict. 1. 193. (3) Gmelin. Watts Transl. 2. 448. (4)Jalirosb. 10. 145. Gmelin-Kraut 2. 1. 273. (5)Ann. Chiin. Pliys. 2. 153. GmelinKraut 2. 1. 274. (G) Gmelin-Kraut 2. 1. 272. (7)J. yr. Cliem. 29.201.
f (1)Ann. Chim. Phys. 11. 81. Gmelin-Eraut 3. 6G. Watts Dict. 4. 584. (2) Gmelin-Kraut 2. 1. 366. (3) Watts Dict. 4. 536. (4)Watts Dict. 4. 555. (5)
at 200°, and is converted into pyro-phosphate of calcium and meta+ II,P-O, + X , O , phosphoric acid, 2CaH,(PO,);II,O=Ca,P,O, which by further heating swellr up, melts, lows t h e rest of tlic ttc water, n i i d at a red hcat is converted into ~ n ( ~ t a - ~ ) I i o ~ pofh : cnlcium, IC. I3irubaum C ) . lli-babic. pliosplinte of calcium (CaIIPO,), when subjected t o a red lieat, lows u :iter ntid is clianged iiito a pyrophosphate, Debray (1).* ‘fltc canw \I it11 2 mol. of water of crystallization (Ca1IPO4*2H,O) lows the 2 niol. at lW’, Pcrcy (2), or :it 130°, and the last tracw of nters n t n recl Iicat, Biitleker (3), Ion\ ing behind a some\\ lint porou$, M hitc, opaque mass, Erlcnmeycr (4).
Phosphate of chromium with 1 2 mol. of water Ioscu, when heated, 7 mol. of water and is converted into the green phosphate, A. Etard ( 5 ) .
Cobaltous Plmpliate. Cobaltous phosphate is of a pink color, and Then licatecl loses its water and becomes bluish-pink, Alvaro Reyiiow ( C ) .
Cipric PfmpIultt~. ( r t i 3 ( P O + ) 2 3 1 T o . Cupric phospliate changes in tlie heat f r o m a bluish-green t o a dark brown powder under loss of \vatcr ( 7 ) .
Fe w i c Ph osph n t c.
f7e2( I-’ OIj 41Z20.
Ferric phosphate, when heated, lxcornes yellow and melts at a red heat, Bergman (l),t becoming :~nliyclrous,Nillot ( 2 ) ) . __
~
..
.
Wutts Dict. 4. 500. ( 0 ) Zeitschi.. Clieiti. IS71. 137. Kraut. 2 . 1. 373.
.
.J~lhresli.2 1. 2Sl.
.. .-
- -.
Gmelin-
*(1) Ann. Cliim. Phys. [3] 61. 484. Gmeliu.Kraut 2. 1. 3;l. (0)Waits Ilict. 4.555. (3) Annalen 69. 206. P1i;u.m. Ccutr. 5849. 288. Clieiii. G : u . 7. 138. Jsliicsb. 2. 229. (4) N . Jahrli. Pliariii. 7 . 295. Jshresb. 10. 115. ( 5 ) Compt.
rend. 84. 1089. Ginelin-Kraut 9 . 2 . 301. Jahresb. 30. 261. ( G ) h u . Chim. Phys. [:I] 45. 110. ( 7 ) Gmeliu-Rr:iut 3. 615.
t (1) Opnsc. 3. 118. Gmcliii g m u t 3. 327. Watts Dict. 4. 563. ( 2 ) Compt. r e d . 82. 89. P1i:crtn. J . TI.nii4. [:{I 7. 118. Jahresb. 29. 244. Ros. and Sch.
ACTION O F H E A T UPON CERTAIN METALLIC SALTS.
175
Lead Phosphade. Di-basic phosphate of lead (PbHPO,), when heated to redness, remains white, gives off water, and changes into the anhydrous pyrophosphate, Pb,P,O, (3).
Magnesizrnz Phosphate. Mg,(P04),*5B,0. Normal magnesium phosphate with 5 mol. of water melts a t a white heat to a clear glass, Graham (4), Gregory ( 6 ) , and becomes anhydrous on ignition (6). Di-basic phosphate of magnesium with 14 mol. of water (MgHPO;14H,O) loses 8 mol. of water at 100' ; 6 more at l76", and yields its basic water at a stronger heat under the formation of the pyrophosphate, Graham (7).
il-lngnnous Phosphate. J f i ~ ~ ( P 0 , ) , * 70. fl~ Normal manganous phosphate with 7 mol. of water loses 4 mol. a t looo, Erlenmeyer and Heinrich (8),or at 11Oo-12O0, and the last 3 only at a red heat, Heintz (9). Mono-basic phosphate of manganese (MnH4(PO4);2K,O), when heated at 10Qo,not only loses water, Erlenmeyer and Heinrich (l),* but also a part undergoes decomposition with the separation of phosphoric acid, which at a higher temperature volatilizes, E. Erlenmeyer and 0. Heinrich (2). The salt loses at 110-120° on an average 13.15 p,er cent. of water, and at a red heat 12.910 per cent,, Heintz (3). Di-basic phosphate of manganese with 6 mol. of water (Mn,H,(PO,);GK,O), when heated at 1000, loses 22.24 per cent. of water, Erlenmeyer and Heinrich (4); at 110", 23.27 per cent., Bodeker ( 5 ) ; at 110-120°, 22.47 per cent., Heintz (6) ; at 200" the 6 mol. are evolved, Heintz (6), and a t a red heat pyrophosphate of marigaiiese (Mn,P,O,) is left, Bijdeker (7), Debray (8). 2. 2. 102. (3)Gmelin-Kraut 3. 227. (4) Gmelin-Kraut 2.1.445. (5) Annalen 54. 98. Gmalin-Kraut 2. 1. 455. (6) Watts Dict. 4 569. (7) Gmelin-Kraut 2. 1. 447. (8)Aunalen 190.208. Jahresb. 30. 255. (9) Pogg. h n u . 74. 449. 75. 174. Annalcn 48, 257. Pharm. Centr. 1848. 657. J. Ph. Chim. [3] 14. 397. Chem. Gaz. 6.458. Jahresb. 1. 342. * (1) Annalen 190. 195. Chem. SOC.J. 33. 270. Jahresb. 30. 255. GmelinKraut 2. 2. 474. (2) Annalen 190. 191. (3)Pogg. Ann. 74. 450. GmelinKraut 2. 2. 474. (4)Annalen 190. 191. Gmelin-Kraut 2. 2. 474. (5)Annalen 69. 208. Pharm. Centr. 1849. 283. Gmelin-Kraut 2. 2. 474. (6)Pogg. Ann. 74. 450. Gmelin-Kraut 2. 2. 474. (7) Annalen 69. 208. Gmelin-Kraut 2. 2. 474. (8) Ann. Chin. Pliys. [3] 0'. 453. Gmelin-Kraut 2. 2. 474.
116
ACTION O F HEAT UPON CERTAIN METALLIC SALTS.
Xercuric Phosphate. Hg3(P0,) *. Mercuric phosphate, when heated, cakes up and melts t o a dark yellow liquid, opaque when cold ; a t a stronger heat metallic mercury, oxygen and phosphoroii~ ouidc are wolved and a residue is left behind, which ih not 0111)- RUJ iri rwction and inw1al)lt. i r i water, but alw coiitaiiii mercuric o\itit>, 15 liich l ~ y'1 qtill longer heating is completely volatilized, Trommdorff (I)* Tlie dry salt melts, when heated, t o 3, dark yellow class ( 2 ) . -&?'C
20'0
r / 5 1%USlJli LI [ e .
2'((/
(
.?' 0,)1.
Mercurous phosphate, wlien gently lieated in a tube, evolveo ~ mercuric phosphate as a residue, metallic mercury and l c a es Gerhardt (3). Xickelo u s Phosphate.
A7i3(f' 04)9*7ZA 0.
Sickelous phosphate with 7 mol. of water gii es off water at a low red heat and becomes yellow, Rarnmelsberg (4) ; but after a long continued heat it becomes brown without loss in weight, Struve (5).
Potassium Phosphate. ICPO,. Normal phosphate of potassium, when strongly heated, melts to an enamel-like mais (6). Mono-basic phosphate of potassium (KEI,PO,) undergoes no change at 200" ; but whcn heated nearly t o redness is converted without melting into the metaphosphatcl, Graham (;), or melts to a clear glass, which on cooling consists of mono-metaphosphate of potassium, KPO, (1)t. Di-basic phosphate of potassium (K2HP0,)is converted into the pyro.phosphatc b y ignition, Graham (2). ,Yil L' L P Phosphate. rl g
P 0,.
Silver phosphate melts at a strong red heat, Berzelius (3), to a dark brown fluid, which on cooling becomes yellow, and which a porion b y longer melting is transformed into pyrophosphate of __ ___________ ________ . ___ l. * (1) Gmelin-Kraut 3. 754. (3) Watts Dict. 4. 573. (3) Compt. ~ c i ~ t1849. 225. Jaliresb. 2. 288. Gmeli~i-I
