1330
Vol. 64
SOTES
TABLE I11 CALCULATED VALUES
FOR
.4SSOCIATED
ACID
SITRIC
IS
DILVTEAQITEOIXSITRIC ACID SOLITTIOM Total acid hydrogen. -1.I
3.5 3 .0 2.8 2.0 1. 5 1.CI 0.5
T o t a l organic acidity.
31
2.28 2 04 1 .77 1.42 1 .o; 0 .i 5 0.48
TBP, 31
1.24
1.50 1.74 '1.10 '1.46 2 80 3 . O!l
Associated nitric acid, M . aq.
0.47 .35 .26
.I7 .I1 . 0; .04
The fact that the partition coefficient wab a wnstant is believed to be supporting evidence for considering the nitric acid which enters the TBP phase in exceqs of a 1 : 1 ratio as dissolved acid which does not enter into a complexation reaction with the 1 : 1 THP HKOa complex to yield higher complexes. Further data are being collected to show the role
which this complex has in metal extraction processes in which metals are extracted from acidic solutioiis with tri-n-butyl phosphate.
Summary Data are presented which show the values for t,he equilibrium distribution constant and the equilibrium reaction constant for the partition of associated nitric acid into T B P and the reaction of this acid in TBP to form a complex as 0.19 and 19.9 f 0.5, respectively. These constants were used to arrive at values for the concentration of associated nitric acid in dilute aqueous nitric acid solutions. These data are offered as indicating that oiily one complex forms between TBP and nitric acid in a two-phase TBP-H20-H?j03 system. Acknowledgment.-The authors wish t o acknowledge the helpful assistance of Dr. C. E. Crompton of the Division Staff and Dr. D. S. Arnold and W. C. 39anser of the Chemical Department.
NOTES THE SOLTJBIT,TTI' OF NITROGEK, ARGOS, METH-iNE, E T H Y L E S E ASD E T H A N 3 IK
XORIIAT, PRIMARY ALCOHOLS' B Y F R ~ ~ K IL. IBAO I E R4~h D LUII\ J BIRCHLR Furman
('hemistry
Laboratories 17anderbiIt T naiersily, Tennessee Receiied February 28 1969
Cashiille
was controlled a t 25" to f0.01" and at 35" to .tO.O5O. Materials.-All of the alcohols were purified by the rt'moval (if necessary) of the aldehydes and ketones, then dried and distilled. Known procedures for the purification of the alcohols were u ~ e d . ~ * 6We chose middle cuts with
A study of the solubility of nitrogen, argon, methane, ethylene and ethane in a series of normal primary alcohols at the temperature5 of 25 mid 35' was made using a modified E H.Sargent Conipany manometric T'an Slyke-Sei11 blood ga. apparatu5. The apparatus was equipped with a chamber similar to a volumetric T7an Slyke blood gas apparalu. A manometer w a y mounted at the waste w l x ent exit port, n hich w a y opened to the solution chamber during the wlution process so that the total prebsures of gai and vapor 111 the solution chamber (mild be adjuited to atmo+ pheric preqsure The procedures given by Van Slyke and Peters3 for extraction of gavh from the qolvent, and the measurement of the gas and solvent volume waz folloaed To avoid the corrections attendant with meaquring the ext racted gaa precsure ox cr the solvent the solvent na. transferred to the bulb below the 1011er .topcock of the extr:zction xewel and sealed off The gai aiid solvent vapor then \{a\ brought to volume o ~ e r mercury. This also enabled u5 to make repeated extractions of the solvent to assure complete removal of gas from the solvent. The temperature ( 1 ) 4dayted f r o m Ph D t h e m of F L Bnver Vanderbilt Vnlrersitv 1959 ( 2 ) h I d u F o n t de \ e m 0 irs and Co , Inc Circle\llle Ohio ('3) J P Peteis a n d D D \ a n $13 ke Quantitatixr Clinical Chern iitrx T 01 TI illiamc a n d TTilhin. Co Baltimoir \ I d 1012
10 11 12 13 1-1 15 Folritdit~yparamet er (rnl.t'ci:. '*. Fig. 1. ---Solvent capacity of alrohols for gmcs arid :tlcohd soliihilitj. parameters (5'mid TBO mni.).
Hept., 1'360
1331
XOTES
TABLE I 1 ATM. PRESSURE
OSTWALD COEFFICIENT O F sOLUBILITY AT 2? AND x3 Ar CH4
Gas -. Alcohol
Lit.
ObS.
Lit.
Obs.
Lit.
Obs.
C2H4 Lit.
Obs.
C3Hs ht.
Obs.
2.34 2.31h 2.63 .. , . 0.532 . .. 0.267$ 0.267 2.87 2.7Zb 2.56 , . . . ,539 , , . , .2& ,258 2.98 2 2.41 .. .. ,510 .,,., ,133 ,254 .25Ib 2.93 2.8jh 2.26 ... . ,122 ,240' ,509 . ,.. , ,246 9.95 2.76b 2.23 . ... ,483 , . , . , ,229 9046 ,116 CjHiiOH ,464 ..,.. 2.08 .. . . 2.84 . . . 114 ,224 . C~HI~OH C7HisOH. 105 ..... ,218 .. .. ,448 . ... . 2.05 2.76 . . ,436 , . , , 1.91 , , . . 2.66 .. ,102 , . , , . .213 ... . CXHI7OH C. B. Kretschnier, J. Xowakowskx and R. Wiebe, Ind. Eny. Chenl., 38,506 (1946). b J. C. Gjaldbaek and E L Niemarin, dcta Chenr. Sccrnd., 5 , 1'2, 1015 (1958). c G. Just, 2. physik. Chem., 37, 342 (1901). d A. Lannung, J . Am. Chen~.Soc., 5 2 , 68 (1930).
CH&H
0.167
C?HsOH CsH70H CgHsOH
0.164" .1489" .132* ,1225" ,1225" ..
,149
, ,
,
. I d
,
TABLE I1 31Ol.E 1~ktACl'IOK SOLUBILITY
