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G a r y D. Christian2
Department of Chemistry, University of Kentucky, Lexington, Ky. 40506, and Department of Chemistry, University of Washington,
Seattle. Wash. 98795
Seventy-nine compounds have been investigated as pos- Unfortunately, acetone is water miscible, which normal-
sible salting-out agents for the separation of acetone ly prevents achieving maximum benefit of its effects. The
from aqueous solutions and its use for solvent extraction present study was undertaken to determine the feasibility
of metal chelates. Three of the compounds, calcium of separating acetone from aqeous solutions uia salting-out
chloride, magnesium chloride, and sucrose, were superi- techniques for possible use in solvent extractions. Sev-
or in that they were efficient salting-out agents, were not enty-nine probable salting-out agents have been exam-
strong complexing agents, their p H could be readily ad- ined. Phase separation was achieved in several cases and
justed, and they did not react with many commonly used solvent extraction has been successfully demonstrated
chelating agents. The solvent extraction of the cobalt-l- using radiotracers. This system should offer advantage
pyrrolidinecarbodithioate chelate using calcium chloride over other water-immiscible solvents for those elements
as the salting-out agent has been demonstrated using ra- exhibiting maximum flame spectrometry sensitivity with
diotracers. Acetone separated from saturated calcium
acetone as the solvent.
chloride solution contained 0.321 *
0.01 1 % water (v/v)
EXPERIMENTAL
and 212 ppm salt (wt/v) at equilibrium. Equilibrium was
achieved in 2 hr, but could be reached rapidly by centri- Saturated aqueous salt solutions a t room temperature were pre-
fuging for 3 min. pared with ACS reagent grade chemicals. The saturated solutions
containing excess solid phase were allowed to sit with intermittent
agitation for a t least 7 days a t room temperature before being used
in an experiment. Reagent grade acetone was used throughout.
Addition of water miscible organic solvents to aqueous Karl Fischer titrations were used to determine the amount of
solutions has been used for decades as a means of enhanc- water present in acetone. Because acetone will react with methanol
ing the sensitivity of flame emission and atomic absorp- to form a ketal and water ( 6 ) , a modified Karl Fischer reagent was
tion spectrometry measurements ( I , 2). This practice, used with pyridine replacing most of the methanol, thus inhibiting
the unwanted side reaction (7, 8). The modified reagent consisted
however, has two disadvantages. First, it dilutes the sam- of 84.7 g of iodine, 920 ml of pyridine, 30 ml of methanol, and 45
ple, thereby partially or wholly offsetting the advantage of ml of sulfur dioxide. This is reported to give stable end points when
the organic solvent effect. Second, the maximum benefit titrating water in acetone ( 7 ) .A second modified Karl Fischer re-
of the organic solvent effect is not achieved since the solu- agent consisting of 84.7 g of iodine, 45 ml of sulfur dioxide, 260 ml
tion contains a mixture of the solvent and water. Therefore, of dioxane, and 690 ml of pyridine gave results similar to those ob-
tained with the first modified reagent.
a frequently preferred practice is to perform solvent extrac-
Atomic absorption spectrometry measurements were made with
tion of the test element(s) into a water immiscible organic an Instrumentation Laboratory Model 153 atomic absorption/
solvent as a chelate or ion-association complex. In this flame emission spectrophotometer using an air-acetylene flame
way, the element can actually be concentrated in a pure and Boling burner head. Radioactivity measurements were made
organic solvent. Methyl isobutyl ketone (MIBK) is a widely with a 1.5-in. Harshaw sodium iodide well type scintillation crystal
used solvent for this purpose. connected to a Radiation Instrument Development Laboratory
Several studies have indicated that acetone is one of the Model 2005 scaler and Model 115 pulse height analyzer.
solvents of choice for maximum sensitivity in atomic ab-
sorption analysis. Robinson ( 3 ) , for example, found this RESULTS AND DISCUSSION
solvent gave the best sensitivity for nickel determinations.
Feldman et al. ( 4 ) found that acetone gave the best detec- Salting-Out Agents. Equal volumes of acetone and
tion limit for manganese, and Feldman and Christian (5) saturated aqueous salt solution were added in a 50-ml
found similar results for cobalt. Indications are that ace- buret. The mixture was then thoroughly agitated and al-
tone might be the best solvent for a number of elements, lowed to sit 30 min and the volumes of the resulting phas-
es were measured.
Present address, Crompton & Knowles, Dyes and Chemicals The compounds tested as salting-out agents can be sep-
Division, Reading, Pa. 19508. arated into three classes. 1) Those compounds that caused
2 Present address, Department of Chemistry, University of
Washington, Seattle, Wash. no phase separation. Phase separation was not effected by
varying the acetone/aqueous solution volume ratio for
J. A . Dean, "Flame Photometry," McGraw-Hill, New York, N . Y . , these compounds. The agents in this category include:
1960.
G. D. Christian and F. J. Feldman, "Atomic Absorption Spectrosco-
p y , Applications in Agriculture, Biology, and Medicine," Wiley-lnter- (6) D. J. Cram and G . S. Harnmond, "Organic Chemistry." McGraw-
science, N e w York. N . Y . , 1970. Hill, New York, N . Y . . 1964.
J. W . Robinson, Anal. Chirn. Acta, 23, 479 (1960). (7) J. Mitchell and D. M. Smith, "Aquametry." Interscience, New York.
F . J. Feldman, R. E. Bosshart, and G. D. Christian, Anal. Chem., N.Y.. 1948.
39, 1175 (1967). (8) "Moisture Determination by the Karl Fischer Reagent," 2nd ed, The
F. J. Feldman and G . D. Christian,Can. Specfrosc.. 14, SO (1969). British Drug Houses Ltd., London, 1966.
:/
h
ume of acetone taken. This was due to the water in the results are listed in Table 111. NO measurement was made
acetone phase (see below). The mixtures of acetone and in those cases where there is no entry.
MnS04 solution below 30 vol % MnS04 solution showed The observed amount of salting-out agent in the ace-
no phase separation and a precipitate was observed. tone phase was always higher than the amount predicted
Water in the Acetone Phase. Appreciable quantities of from the solubility of that compound in acetone. This is
water in the acetone phase could affect aspiration rates not surprising and was probably due to the small amount
and atomization efficiency in flame spectrometric mea- of water present in the acetone phase, causing an increase
surements. The water content, after shaking equal volumes in the solubility of the salting-out agent in the acetone
of the aqueous solution and acetone, was determined in phase. The amounts of salts that could be carried into the
the acetone phase immediately after separation and after acetone phases if the water were saturated with respect to
allowing the phases to sit together for 24 hr. In the latter the salts equalled or exceeded the observed amounts of
case, samples were sealed from the atmosphere until anal- salts found in the acetone phases. Hence, salts present in
ysis. KOH and NaOH solutions were unstable and could the water could account for the majority of the salts in the
only be analyzed right after mixing. The results are listed acetone phases. When larger amounts of water were pres-
in Table 11. Absence of an entry indicates those cases where ent in the acetone phases, increased quantities of salts
no measurement was made. The average deviation is list- were generally found.
ed where at least three analyses were performed. Hieftje and Malmstadt (26) observed that the presence
The results indicate that equilibrium was not achieved of 100 ppm of NaCl had little effect on solvent evapora-
immediately after mixing. The water content of the ace- tion rates or on droplet size in flames. The effect of 1000
tone phase decreased with time. This observation is sup- ppm of 27 different elements on the absorption of 5 ppm
ported by solvent extraction experiments (below) which of zinc was examined and only Si and Au interfered (27).
demonstrated that up to 2 hr duration is required for Of the salts listed in Table 111, AlC13, CaC12, and MgC12
equilibration. Usually, 90% equilibration is reached in 15 are the most potentially useful ones for solvent extractions
min. with acetone (see below). Three hundred parts per million
All those salting-out agents that showed precipitation or less of the salt in the acetone phase should not have se-
upon mixing with acetone resulted in greater than 1% rious effects on most flame spectrometric determinations.
water in the acetone phase at equilibrium (NaBr, NaCl, Molecular emission by the salt should, however, be cor-
NaC~H302,NazC03, and SrC12). Salts that yielded great- rected for in flame emission determinations.
er than 100% acetone "recovery" resulted in greater than Trace metal impurities in the salting-out agent would
2% water in the acetone phase a t equilibrium (Ka(citrate), be expected to be extracted into the acetone phase by
NazH(citrate), and MnS04). With the exception of chelating agents. Reagent grade CaC12, for example, has
NH4C2H302, all the other salts resulted in less than 0.5% been found to contain appreciable quantities of Cu, Cd,
water in the acetone phase. Note that KOH and NaOH, Zn, and Ag. If an analysis for any of these metals is de-
which were very efficient phase separating agents, had sired, a presolvent extraction step on the calcium chloride
very little water in the separated acetone. Less than 1% solution would have to be performed to remove the trace
water in the acetone did not appreciably affect flame impurities before the calcium chloride is used as a salting-
spectrometric results. Under certain conditions, there is a out agent.
linear relationship between atomic absorption signals and P h a s e Diagram of the Ternary System Acetone,
per cent water in acetone ( 2 5 ) . Water, and Calcium Chloride. Although all of the com-
Salting-Out Agent in the Acetone Phase. Equal vol- pounds in Table I are efficient salting-out agents for ace-
umes of both acetone and saturated aqueous salt solution tone, most would be rather limited in their application to
were thoroughly mixed and allowed to sit for either 30 solvent extraction because they are either not neutral,
min (except KOH and NaOH solutions) or 24 hr. Aliquots possess strong complexing anions (F-), or possess a
of the acetone phases were pipetted into preweighed strongly chelating cation (Mn2+) that would interfere in
weighing bottles, evaporated under reduced pressure, and many solvent extractions. CaC12, MgClz, and AlC13 are
dried at 125 "C for approximately 12 hr. The bottles were potentially the most useful salting-out agents for solvent
reweighed and the amounts of residues determined. The extractions with a number of chelating agents. AlC13
(26) G.M. Hieftjeand H. V. Malmstadt.Anal. Chem.. 40, 1860 (1968)
(25) C. E. Matkovich and G. D. Christian, Can. Spectrosc., in press (27) J. A . F. Gidley and J. T. Jones, Analysf (London), 85, 249 (1960).
(35) L. M. Gindin, I. F . Kopp. A. M. Rozen, P. I. Bobikov, E. F. Kouba, (37) G. H. Morrison and H. Freiser, "Solvent Extraction in Analytical
and N. A. fer-Oganesov, Russ. J. Inorg. Chern., 5 , 71 (1960). Chemistry," Wiley, New York, N.Y., 1957.
(36) L. M. Gindin, I. F. Kopp. A . M. Rozen. and E. F . Kouba, Russ. J. (38) "Solubilities of Organic Compounds," Vol. 2, 3rd ed. A . Seidell, Ed.,
Inorg. Chern.. 5, 66 (1960). Van Nostrand, New York, N.Y., 1941, p 176.
Sources of errors are discussed of the unique method of where y is the ratio of the net gravitational forces acting
density measurement of a solid sample by comparing its on the body j in the two liquids,
fall time to that of a reference sample in two different liq-
uids. Equations are derived for computing the quantitative
effect of the various experimental parameters on the final
density result, indicating that the accuracy of the method and p is the gross fall time ratio,
can be increased by using a reference body of density,
size, and shape close to those of the tested body, and (3)
liquids of wide density difference, and high, approximate-
ly equal viscosities. The self-correcting features of the This results from 4 times use of Stokes' law, extended
method make it insensitive to some lack of control on for bodies of arbitrary shape and constant fall orientation
experimental conditions. Comparison with experimental (2-4):
results is presented.
(4)
A novel method has previously been reported for mea- where u, g, F , and D are, respectively, the fall velocity
suring density of an individual small, solid sample of high (cm/sec) of the body, the acceleration due to gravity (980
density and arbitrary shape ( I ) . In the study of isotopes cm/sec2 at sea level), viscosity (poise), and the diameter
and solid state imperfections and when the sample avail- or characteristic dimension of the body (cm), while k is a
able for investigation is smaller than a millimeter in size, shape-orientation factor which is a numerical constant
the method becomes invaluable for densities above 4 or 5. (unity for a sphere) typical of the geometry and particular
For obtaining accuracies of 0.1 to 0.3% a simple procedure fall orientation of the body. Applying Equation 4 twice to
with a limited attention to the choice of materials has the same body i in the two different liquids of viscosities
been found adequate ( I ) . The present work deals with the and p' (and densities c and u'), respectively, and then di-
error analysis of the method aimed to indicate the steps viding one of these equations by the other, results in
required for attaining higher accuracies. It will be shown
that prudent choice of materials, specifically a standard (5)
body of density, size, and shape close to those of the test-
ed body, and liquids of wide density difference and high, Similarly, with the reference body j
approximately equal viscosities, will permit the measure-
ment of densities with additional one or more significant
P P, - -a t,
figures.
pf - p, - -a/ t,'
The method consists of separate fall time measurements Dividing Equation 5 by Equation 6 results in
of two bodies between arbitrary marks on two cylinders. P,--a P,--a
The two cylinders are each filled with a different Newto-
Pi- fJJ - P, - fJJ
@
nian viscous liquid; one of density u and the other of 0'
(gram/cm3). Two of the fall times, ti and t,' (sec), are from which Equation 1is obtainable by rearrangement.
taken for the tested body i in the two liquids, respectively, The method requires thermostating of the liquid-filled
and similarly, t , and t,', for the reference b o d y j having a cylinders in order to keep the liquid viscosities and densi-
known density p , (gram/cm3) acting as a standard. The ties constant and uniform during the fall runs. Care is
density p r of the tested body is obtained from the equation also needed to prevent convection, air bubbles, or con-
specifically derived for this method ( I ) :
(2) G. Barr, "A Monograph of Viscometry," Oxford University Press,
?@af - -a 1931, Chap. V I I I .
= (1)
PI
rp - 1 (3) J. F. Heiss and J. Coul, Chern. Eng. Progr., 48. 132 ( 1 9 5 2 ) .
(4) H. Lamb, "Hydrodynamics," 6th ed., Dover Publication, New York.
(1) A. S. Roy,Ana/. Chern., 33, 1426 ( 1 9 6 1 ) N . Y . , 1945. pp 597-605.