Table Of Contentstudies on the AmxoAixcnf o? Bxxtwmas mmom to
« m O A I- 0imi.3TRY
A Dissertation
Submitted to the Grad.us.te Faculty of the
Louisiana State University and
Agricultural and I'eohanieal College
in partial fulfillm ent of the
requirements for the degree of
Doctor of Philosophy
in
The Department of Chemistry
by
Jack Kenneth Carlton
B.3,# Centenary College, I9^2
!i*%, Louisiana State University, 1949
June, 1951
UMI Number: DP69352
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MANUSCRIPT THESES
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LOUISIAMl STATE UNIVERSITY LIBRARY
AOimowL^Dam’W
13*o author wishes to express his sincere appreciation to Hr*
Philip W. West for his advice and assistance as director of this
research*
Ho is very grateful to Or. J* L* !£., Erickson, Dr* Max Goodrich
and Dr-. Gunther Siohorn for their helpful suggestions in the prepar
ation of this manuscript*
So wishes to acknowledge the financial Sid provided by the
Office of Naval Research.
Ho also wishes to acknowledge the encouragement of his wife,
Mary 3&len9 to whom he la especially grateful for typing the dissert-
ation*
He would Ilk© to take this opportunity to express his deepest
appreciation to hia mother, Mrs* J* K. Oarlton, for her help and
inspiration.
table of ©ohtmps
CHAPTER PAOS
X * Introduction X
II* An Experimental Survey of the Extractiono f
M etallic Complexes with Organic Solvents 7
Experimental 8
Discussion of Results and Conclusions 12
Bibliography 26
XIX, The Extraction of head Iodide with Methyl
Isopropyl Ketone ^2
IV, Specific Spot Test for Gold IMploying
Par&roa&ni lino Hydrochloride y*>
V, Extraction Pi pot for Spot Teat Analysis *>4
VI, Summary ?5
VII, Vita ?6
ill
U3T OF TABLES
$A8&E PACE
X. Solvents Uaed in the Extraction itudy 15
IX* Conditioning Agents Used in the Extraction Study 16
XXX. Metal Ions Included in the Extraction Study 11
IV. Extractions Bnploying Potassium Iodide as
Conditioning Agent
V. Extractions Sftploying Assnonium Thlooyanate
ae Conditioning Agent m
vx. Extractions HJaploying Hydrochloric Acid as
Conditioning Agent 23
VII. Extractions Employing pyridine as Condition
ing Agent 25
iv
ABSTRACT?
A Bystem&tio investigation has boon mads of the extraction, of metal
lic salts and complex®© by organic solvents* The conditioning agents
employed in this survey included athylonedi a nine, ©thylcnodiaminet©tra&c©tia
sold, rcanr&tol, hydrochloric acid, potassium iodid©, ammonium thiecyamt®,
pyridins, perchloric acid, acetic acid and malonio acid* Th© solvents
used were n-butyl chloride, petroleum ether, benaene, n~arnyl alcohol, chloro
form, methyl isopropyl kotano, isopropyl ether, butyraldehyd©, carbon tetra
chloride and ethyl aoetate* .Methyl isopropyl koton© and butyr&ldehyd©
were found to be vory good solvents for the extraction of metallic complexes.
Only those solvents used which contained oxygen were found to extract the
complexes included in this study* Several extract!one war© discovered
which hold promise for application in qualitative and quantitative analysis*
The extraction of load iodide with methyl isopropyl fcoton© has boon
thoroughly investigated as a part of those studio©* It has boon found
that when lead solutions are treated with a large excess of potassium
iodide and adjusted to the proper acidity, lead iodide can bo extracted
with methyl isopropyl ketone * The extraction performed in this manner
was 91% complete in a single pace* Interferences wore kept at a minimum
through the use of a preliminary extraction which was applied after treat
ing the aqueous solution with ammonium tin.ocyanato and hydrochloric acid.
Hie perarosanilino hydrochloride teat for gold was rendered specific
for that metal by extracting an acidic aqueous solution of auric chloride
with ethyl acetate* In this manner, gold was separated from the platinum
metals, a group which constituted tho principal intorfaranc© in the
v
detection of gold* After the separation of phases the organ!o layer was
evaporated* taken up with a few drops of water and applied to the reagent
on Spot test paper* The teat was found to be sensitive to [3 ge^maa of gold*
A device was needed for the rapid extr&otlon of small volumes of
aqueous solutions with only a few drops of organic solvent. An extraction
pi pet was designed and prepared and hao carved quit© well in this capacity.
nrrRODUOTXon
The use of extract!on techniques as a moans of effecting analytical
separations has for many years provided the chemist with a very useful
tool, and especially in recent years have these techniques become general
ly popular* The increased interest in this field can be attributed in part
to the appearance of a considerable number of extraction devices, such m
the countercurrent extractors discussed annually In the review articles
of Orsig (6, 7, 8) f and the development of numerous colorimetric proced
ures based on the extraction of organic-metallic complexes (15, 35# 24,
27, 52)* The extraction of inorganic complexes also holds many interest
ing possibilities, and the applications of those extractions to analytical
separations, as well as to colorimetric procedures, are to be found
throughout the literature. It is with the extraction of inorganic complexes
that this investigation is primarily concerned.
Before embarking upon a discussion of the experimental work and the
results of this investigation I t night be well to discuss the various
classes of extractions and tho uses to which they have been put*
Generally, extractions can be classified according to the following
categories* liquid-liquid, liquid-solid, 11quid-gas and solid-gas* Be
cause this study was Gonflnod to liquid-11quid systems only brief mention
w ill be mado of tho other claosiflcntions.
Probably the most familiar type of liquid-liquid extraction being
employed In analytical chemistry is tin t in whioh a particular component
of an aqueous mixture is extracted into an organic solvent with tho form
ation of a highly colored organic phase which la then readily adapted to
(«
(2)
ft photometric analysis. In auoh ft iaann®r cobalt can bo rioter mined, after
treating I t with a.mmonium thiooyanata and extracting it with arsyl alcohol
(18, 19, 38)* the blu© color of the thlooyanatc complex is sufficiently
intense to provide an excellent means of do to raining cobalt colorimetric**
ally. Similarly, iron can be extracted as the thiooyanato complex by a
mixture of amyl alcohol and ethyl ether (55> 55) I the blood red color
of the organic phase ie then measured photometrically after the separation
of phases, The tMooy&nate of molybdenum can be extracted by normal butyl
acetate with the formation of & redd!sh-brovm color* A colorimetric do*
torrid.nation of molybdenum based on this extraction has boon reported by
James (15)* Oolorimotrio procedures have been developed for the dotorn&n-
ation of bismuth, both as the thioeyanato complex (5^) and as the iodide
complex (12), In the former procedure amyl alcohol was employed as solvent,
and in the latter a 5*1 mixture of amyl alcohol and ethyl acetate wm used.
One of the more outstanding examples of the use of extraction techniques
in colorimetric procedures is the determination of chromium by extract*
ing the blue per chromic acid and Treasuring the intensity of the blue extract.
Amyl acetate has been used in a procedure reported by Bishop and Dwyer (1)•
There are two principal advantages of employing an extraction procedure
in colorimetric analyses. First, in many oases tho desired component la
separated from 'color masking or reaction maoking interferences 5 and second,
small amounts of material can bo easily concentrated from relatively dilute
solutions, dxcept for the oilmlnation of color masking interferences, the
advantages listed above are manifest in all procedures employing extraction
techniques,
