[COSTRIBUTION FROM THE JOHS
HARRISON LABORATORY OF
CHE3lISTRT,
S o . 76.1
T H E BEHAVIOR OF CERIUM, LANTHANUI1, NEODYfIIUI7, PRASEODYiIIUM, THORIUM A N D ZlRCONlUil TOWARD ORGANIC BASES.' B\- n V R T
LATVS
HARTWELL.
Keceived A u j J s t IS. 1903.
AN IWESTIGATIO~X along these lines seemed to promise well because of the success which Jefferson' met while prosecuting a similar study with a limited number of aromatic bases. I t was hoped that some organic base would be found, among the large niimber to be tried, 11hich would lead to the separation of thorium and zirconium, or, failing i n this, that a method would be disclosed by which these tiyo elements could be separated from cerium, lanthanum, neodymium and praseodymium. Large quantities of thorium and zirconium nitrates \\.ere prepared from the mineral thorite a i d zircon. Kumerous yualitative tests were macle and the solvents for the bases n.ere, in most cases, water and alcohol, or mixtures of these two, depenc!ing upon the solubility of the base. I n some instances ether was added to advantage. Alcohol, above a certain strength, precipitated the thorium anc! z i r c o ~ i u mnitrate solutions, so that this point had to be coi1stailtl~considered during the testing. T h e salt solution \vas usually added in small quantities at a time to the solution containing a liberal amount of the organic base. Heat was applied, if precipitation did not occur in the cold. T h e solutions were not permitted to stand for long periods, as it \vas thought that differences Ivhich did not manifest themselves readily, under ordinary conditions, n~ouldscarcely indicate the probability of practical quantitative separations. The bases studied in this investigation were obtained from Kahlbaum. Those rmployed by Jefferson3 were usually omitted here. REAGESTS \VH IC13 I'RCjDTrEL3 S 3 PRECII'IT.\TE
\\'IT11 S.\LTS O F ASS
O N E O F T H E SIX E L E M E S T S .
Benzylaniline. Dimethylnitrosamine.
#-Sitraniline. fi-Sitrophenylhpdraziiie.
From author's thesis for the P h . D . de,cree. This Journal, a4, j40. .i L O C . Ionopropylamine. Xeurine. Normal butylamine. Sormaldibutylamine. Propylenedianiine. Tetrethylammonium hydroxide. Tetramethylammonium hydroxide. Triethylamine. Trimethylamine. Tripropylamine.
W H I C H C.4’JSED
Allylamine. Benzylmethylamine. Bornylamine. Camphylamine. Diamylamine. Dibenzylamine. Diethylamine. Dimethylamine. Dipropylamine. Ethylenediamine. Heptylamine. Hexylamine. Isobutylamine. Isotributylaniine.
REAGESTS \ V H I C H PRECIPITATED O S L S T H O R I U M A N D ZIRCONIUM.
Benzidine. m-Bromaniline. p-Bromaniline. p-Bromphenylhydrazine. 9-Chloraniline. REAGENTS
Isoquinoline. a-Picoline. p-Toluidine. Iit-Toluylenediamine. Tribenzylaniine.
KOT I S C L I J D E D I N T H E PRECEDIKG GROUPS A N D WHOSE
REACTIONS ARE M E N T I O N E D UPON SUCCEEDING PAGES.
m-Chloraniline. Diethylaniline. Hexamethylenetetramine. Monethylaniline. Monomethylaniline. a-Naphthylamine.
9-N aphth y lamine. Tetrahydroquinoline. 112-Toluidine. o-X ylidine. $-Xylidine.
The bases of the first and second groups were manifestly unsuited for the purpose in mind. Those of the third and fourth groups showing differences in deportment with the several elements under consideration were given more particular attention, while those which were insoluble in dilute alcoholic solutions were placed to one side. The following paragraphs record the observations made with the several bodies which seemed best adapted for quantitative separations. 1
Lac. c i l .
1130
BURT L A K S H;PKTWELL.
Tlioriiiiiz and Zirioiiiiirri nrith the Chioi,iliiiliries.-The different behaviors of the chlorani1ii:es substantiate the vieys held regarding their relative basicity.' o-Chloraniline did not precipitate thoriiini or zirconium. m-Chloraniline precipitated zirconium in tlic coltl. liut with thorium, heat was required to produce precipitatioii, irliile k-chloraniline Precipitated the solutions of both elements. even in the cold. Solutions of ceriLun, lanthanum, neodymium xi(! praseodymium salts \\.ere not affected by these reagents. Zircoiiiz/ui mid Thoririiii 'iilifh ~ i ~ - C ~ i l o ~ a i i i i i i i c . - ~ I ~work icli was done upon 9%-chloraniline to arrive at the proper conditions in the strength of alcohol and temperature favorable to the complete precipitation of the zirconium solutions, and at the sami' time to leave the thorium salt unprecipitated. A solution containing equal parts of water and commercial alcohol was found most satisfactory. -At a temperature of 60"-70", this solvent coiltaining uz-chloranilice occasioned no precipitation in solutions of thorium nitrate, while in zirconium nitrate solutions i t precipitated o q g j gram, 0.0988 gram? 0.0990 gram and 0.0988 gram of zirconium oxide, instead of o.og9j gram obtained b:!. ammonia or 0.0993 cram by direct evaporation and ignition. (.h repeating the experiment with a mixture of the thorium and zirconium nitrates, both elements were completely precipitated. TIiorit~uiaiid Zivcoriiiirii atif12 Hc.rniizeth~leiiefetl.uirliiic (Fori i i i i i ) .-Formin in the qualitative tests showed a marked difference in behavior. Thus a thorium solution, after its addition, stood forty-two hours at room temperature without the appearance of a precipitate. Upon adding the zirconium nitrate solution, both hydroxides were precipitated coinpletel!-. CY- and /3-Saphthylamine, iii-bromaniline and p-bromphenylhydrazine precipitated zirconium solutions much more conipletel!. than those of thorium, but separation5 could not be effected by mezns of them. The; reacted indifferently with the salts of cerium, lanthanum, neodymium and praseotlyinium. o-Bromaniline was not tried at all in this investigation. In a solution of the nitrates of zirconium and cerium. m-chloraniline precipitated o.oj32 grain of zirconium oxide, instead of 0.0539 gram obtained with ammollia ~ v a t e r . p-Chlorani!ine precipitated 0.0536 gram. 112-bromaiiiline 0 . 0 3 ~ gram, an(! P-nnph C!:e:lli
