Salting-Out of Acetone from Water-
Basis of a New Solvent Extraction System
Charles E. Matkovich'
Department of Chemistry, University of Kentucky, Lexington, Ky. 40506.
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-
sible salting-out agents for the separation of acetone
from aqueous solutions and its use for solvent extraction
of metal chelates. Three of the compounds, calcium
chloride, magnesium chloride, and sucrose, were superi-
or in that they were efficient salting-out agents, were not
strong complexing agents, their p H could be readily ad-
justed, and they did not react with many commonly used
chelating agents. The solvent extraction of the cobalt-l-
pyrrolidinecarbodithioate chelate using calcium chloride
as the salting-out agent has been demonstrated using ra-
diotracers. Acetone separated from saturated calcium
chloride solution contained 0.321 *
0.01 1 % water (v/v)
and 212 ppm salt (wt/v) at equilibrium. Equilibrium was
achieved in 2 hr, but could be reached rapidly by centri-
fuging for 3 min.
Addition of water miscible organic solvents to aqueous
solutions has been used for decades as a means of enhanc-
ing the sensitivity of flame emission and atomic absorp-
tion spectrometry measurements ( I , 2). This practice,
however, has two disadvantages. First, it dilutes the sam-
ple, thereby partially or wholly offsetting the advantage of
the organic solvent effect. Second, the maximum benefit
of the organic solvent effect is not achieved since the solu-
tion contains a mixture of the solvent and water. Therefore,
a frequently preferred practice is to perform solvent extrac-
tion of the test element(s) into a water immiscible organic
solvent as a chelate or ion-association complex. In this
way, the element can actually be concentrated in a pure
organic solvent. Methyl isobutyl ketone (MIBK) is a widely
used solvent for this purpose.
Several studies have indicated that acetone is one of the
solvents of choice for maximum sensitivity in atomic ab-
sorption analysis. Robinson ( 3 ) , for example, found this
solvent gave the best sensitivity for nickel determinations.
Feldman et al. ( 4 ) found that acetone gave the best detec-
tion limit for manganese, and Feldman and Christian (5)
found similar results for cobalt. Indications are that ace-
tone might be the best solvent for a number of elements,
Present address, Crompton & Knowles, Dyes and Chemicals
Division, Reading, Pa. 19508.
2 Present address, Department of Chemistry, University of
Washington, Seattle, Wash.
J. A . Dean, "Flame Photometry," McGraw-Hill, New York, N . Y . ,
1960.
G. D. Christian and F. J. Feldman, "Atomic Absorption Spectrosco-
p y , Applications in Agriculture, Biology, and Medicine," Wiley-lnter-
science, N e w York. N . Y . , 1970.
J. W . Robinson, Anal. Chirn. Acta, 23, 479 (1960).
F . J. Feldman, R. E. Bosshart, and G. D. Christian, Anal. Chem.,
39, 1175 (1967).
F. J. Feldman and G . D. Christian,Can. Specfrosc.. 14, SO (1969).
ANALYTICAL CHEMISTRY, VOL. 45, NO. 11, SEPTEMBER 1973
Unfortunately, acetone is water miscible, which normal-
ly prevents achieving maximum benefit of its effects. The
present study was undertaken to determine the feasibility
of separating acetone from aqeous solutions uia salting-out
techniques for possible use in solvent extractions. Sev-
enty-nine probable salting-out agents have been exam-
ined. Phase separation was achieved in several cases and
solvent extraction has been successfully demonstrated
using radiotracers. This system should offer advantage
over other water-immiscible solvents for those elements
exhibiting maximum flame spectrometry sensitivity with
acetone as the solvent.
EXPERIMENTAL
Saturated aqueous salt solutions a t room temperature were pre-
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.
Karl Fischer titrations were used to determine the amount of
water present in acetone. Because acetone will react with methanol
to form a ketal and water ( 6 ) , a modified Karl Fischer reagent was
used with pyridine replacing most of the methanol, thus inhibiting
the unwanted side reaction (7, 8). The modified reagent consisted
of 84.7 g of iodine, 920 ml of pyridine, 30 ml of methanol, and 45
ml of sulfur dioxide. This is reported to give stable end points when
titrating water in acetone ( 7 ) .A second modified Karl Fischer re-
agent consisting of 84.7 g of iodine, 45 ml of sulfur dioxide, 260 ml
of dioxane, and 690 ml of pyridine gave results similar to those ob-
tained with the first modified reagent.
Atomic absorption spectrometry measurements were made with
an Instrumentation Laboratory Model 153 atomic absorption/
flame emission spectrophotometer using an air-acetylene flame
and Boling burner head. Radioactivity measurements were made
with a 1.5-in. Harshaw sodium iodide well type scintillation crystal
connected to a Radiation Instrument Development Laboratory
Model 2005 scaler and Model 115 pulse height analyzer.
RESULTS AND DISCUSSION
Salting-Out Agents. Equal volumes of acetone and
saturated aqueous salt solution were added in a 50-ml
buret. The mixture was then thoroughly agitated and al-
lowed to sit 30 min and the volumes of the resulting phas-
es were measured.
The compounds tested as salting-out agents can be sep-
arated into three classes. 1) Those compounds that caused
no phase separation. Phase separation was not effected by
varying the acetone/aqueous solution volume ratio for
these compounds. The agents in this category include:
(6) D. J. Cram and G . S. Harnmond, "Organic Chemistry." McGraw-
Hill, New York, N . Y . . 1964.
(7) J. Mitchell and D. M. Smith, "Aquametry." Interscience, New York.
N.Y.. 1948.
(8) "Moisture Determination by the Karl Fischer Reagent," 2nd ed, The
British Drug Houses Ltd., London, 1966.
1915
Table I. Summary of Salting-Out Data for Those Compounds Causing Phase Separation without Precipitationa
ml of Av vol
aqueousphase acetone phase Molarity of sat Molarity of sat
Compound recovered recovered soin in H 2 0 (9-1 7 ) s o h in acetone (9-13)
AIC13 33.20f 0.36 59.6 5.25 (15')
CaClz 34.42f 0.44 56.5 6.7 (20") 1.1 x 10-3 (250)
KOH 24.68f 0.27 95.6 19.2 (15') lnsol
KF 24.70f 0.10 99.2 15.9 (18") lnsol
KCzH30z 25.05f 0.20 92.4 26.0 (20') Insol
KJ (citrate) 22.10f 0.50 105.0 5.1 (15')
LiC2H30~ 26.6 f 0.2 88.0 29.2 (15')
MgCh 31.73f 0.14 64.0 5.7 (20O) Insol
Mg(CzH30z)z 25.10f 0.50 91.2 4.5 (25')
MnCI2 30.9 f 0.7 74.0 5.7 (25')
MnS04 22.0 f 0.20 108.8 3.9 (25')
NaOH 24.69 f 0.47 93.2 24.5 (25') I nSOl
Na2H(citrate) 19.72f 0.10 118.0 2.4 (25'j
NH4F 23.70f 0.33 99.2 22.1 (25")
"4CzH30z 26.68 f 0.53 95.6 19.2(4') 3.5 x 10-2 (20")
( N H 4 ) 3 (citrate) 22.42f 0.60 105.2 sol. lnsol
0 Twenty-five milliliters of each phase were initially taken. All resuits were taken at ambient temperature (ca. 25 "C).

AI(OH)3, AlBr3, A U C Z H ~ O ZAlz(S04)3,

)~, Ba(OH)z, BaFz,
BaClZ, BaIz, Ba(C104)~, Ca(OH)z, CaFz, CaBrz,
Ca(N03)2, CaC03, CaS04, Ca(CzH302)2, CuSO4, KC1,
KBr, KI, KN03, KzS04, LiOH, LiF, LiC1, LiBr, LiI,
LizS04, Mg(OH)z, MgBrz, MgIz, MgS04, Mg(C104)z,
MgH(citrate), Mn(OH)z, NaF, NaI, N a ~ S 0 4 ,NazHP04,
NaN03, "3, NH4Br, "41, NH4N03, Sr(OH)z, SrBr2,
SrIz, Sr(CzH302)2, Zn(OH)z, ZnC12, ZnBrz, and ZnIz.
Partial precipitation occurred with 20 of these agents. 2)
Those compounds that caused phase separation accompa-
nied by partial precipitation of the salting-out agent in
the aqueous phase. These compounds include the fol-
lowing with the volume per cent acetone phase recovery in
parentheses: NaCl (76.4), NaBr (21.6), NaCzH302 (86.0),
Na2C03 (131.6), NaHzP04 (110.4), NaK(tartrate) (126.0),
NH4Cl (48.0), (NH4)zS04 (117.6), and SnClz (73.3). 3)
Those compounds that caused phase separation with no
precipitate formation. Results for these are listed in Table
I. The average deviation of three to nine measurements is
listed.
The per cent acetone phase recovered was, as expected,
independent of the total volume of acetone and aqueous
solution but was dependent on the ratio of the volumes
(see below). There was a slight volume contraction, usual-
ly 1-470, when equal volumes of the two phases were
mixed, as apparent from the data in Table I. Any precipi-
tate occurring during an extraction procedure would have
a probability of coprecipitating test elements and there-
fore render the extraction process quantitatively useless.
There is reason to believe that at lower concentrations the
second class of compounds could effect phase separation
without precipitation (24-16).
(9) "Handbook of Chemistry and Physics," 50th ed. Chemicai Rubber
Publishing Co., Cleveland, Ohio, 1969.
(10) "Solubilities of Inorganic and Metal Organic Compounds," Vol. 1,
4th ed, W. F. Linke, ed., Van Nostrand, Princeton, N.J., 1958;
(11) "Solubilities of Inorganic and Metal Organic Compounds, Vol. 1,
3rd ed, A. Seidell, Ed.. Van Nostrand. New York, N.Y., 1940.
(12) "Solubilities of Inorganic and Organic Compounds," Vol. 1. H. Ste-
phen and T. Stephen, Ed., Macmillan. New York. N.Y., 1963.
(13) M. F. Altaba. Rev. Real Acad. Cienc. Exactas. Fis. N a l u r . Madrid,
44, 271 (1951).
(14) J. Timmermans and J. Lewin, Discuss. Faraday SOC.. 15, 195
(1953).
(15) R. J. Mertslin. N. I. Nikurashina, and G. M. Ostapenko, Russ. J.
Phys. Chem., 43, 169 (1969).
(16) N. I . Nikurashina, G. M . Ostapenko, and T. G . Kalyuzhnaya, Russ.
J. Phys. Chem., 43, 225 (1969).
The acetone phases recovered from those salt solutions
that showed greater than 100% atetone phase recovery
were all cloudy at the time of measurement and contained
appreciable amounts of water (see below). Equilibrium
was probably not attained during the allotted 30-min sep-
aration period. Long phase separation times are inconve-
nient and therefore salts in this category are of question-
able value. Also, appreciable water in the acetone phase is
undesirable because of the inconvenience of preparing cal-
ibration curves with mixed water-acetone solutions.
Two relatively simple and similar theories have been
used to explain salting-out phenomena, one postulatng
decreased mutual solubility of the solvents and the other
postulating removal of one solvent uia solvation processes.
These are the medium effect theory and the salt effect
theory, respectively (17). The former assumes that com-
pounds, not necessarily ionic in nature, are preferentially
solvated by one of the solvents, making this solvent un-
available for dissolving the second. Sucrose presumably
lowers the solubility of alcohol in water by this means
(18). The latter theory, which applies only to ionic com-
pounds, assumes that the more polar of the two solvents
( e . g . , water) preferentially congregates around the salt be-
cause of electrostatic attraction, leading to nonideal be-
havior and positive deviation from Raoult's law (18).
Thus, the vapor pressure above the aqueous phase is in-
creased and the escaping tendency of the second solvent is
increased with the result that its solubility in the first sol-
vent is decreased (19). A combination of these two pro-
cesses is obviously possible, but the salt effect will proba-
bly predominate with ionic salting-out compounds.
Samoilov and Tikhomirov (20) have presented a modi-
fied hydration theory and similar theories have been de-
scribed by several other investigators. Long and McDevit
( 2 2 ) have reviewed several other approaches to the theory
and mechanisms of salting-out processes, including the in-
ternal pressure, van der Waals, hydration energy, and
electrostatic approaches. Quantitative description of the
theories is generally not possible for the relatively high
salt concentrations used in this study.
(17) R. G. Bates, "The Chemistry of Non-Aqueous Solutions," Vol. 1, J.
J. Lagowski, Ed., Academic Press, New York. N.Y.. 1966.
(18) S. Glasstone, "Textbook of Physical Chemistry," Van Nostrand.
New York. N.Y., 1940.
(19) A. Dobry-Duclaux, Chem. Ztg., 76, 805 (1952).
(20) 0.Ya. Samoilov and V. I. Tikhomirov, Ekstraksiya. 2, 34 (1962).
(21) F. A . Long and W. F. McDevit, Chem. Rev., 51, 119 (1952).

1916 ANALYTICAL CHEMISTRY, VOL. 45, NO. 1 1 , SEPTEMBER 1973

 Three factors should be considered when evaluating a c/v I
salt and its potential salting-out effect on acetone. First,
-
h

the solubility in acetone must be negligible. Salts such as

the lithium halides, which might be expected to cause
phase separation based on the other parameters, showed
-
E
40
30
20
no separation because they were soluble in acetone. The
lithium halides, according to Glasstone (It?), are soluble in IO
w
both phases and show a negative deviation from Raoult's
' 0
law, or salting-in effect.
Second, the solubility of the salt in water must be large 40
in order to have maximum interaction with the water
molecules. All of the salts that caused phase separation c ,3 0
were a t least 1.5M when saturated in water. g 20
Finally, the lyotropic series should be considered. This
is an empirical order of ions based on their ability to pre-
g IO
cipitate water loving substances (gels). Glasstone (18) lists
the series as Mg2+ > Ca2+ > Sr2+ > Ba2+ > Li+ > Na+
80
> K + > Rb+ > Cs+ for cations and as citrate > tartrate a
Y-
40
0
> so42- > C2H302- > c1- > NOS- > c l o 3 - > 1- > 30
CNS- for anions. Dobry-Duclaux (19) reports a slightly
different order for the cations, Mg2+ > Sr2+ > Ca2+ >
2 20
Ba2+ > K + > Na+ > NH4+ > Li+, but a similar order 3 IO
for the anions, S042- > C2H302- > C1- > NO3- > Br-
> I- > CNS. The important role of the anion in deter-
9 0-
0 5 IO 1 5 2 0 2 5 3 0 3 5 4 0 4 5
mining lyotropic behavior is supported by the work of
Mille (22) who observed that the solubility of many salts INITIAL VOLUME of ACETONE (ml.)
in acetone is markedly dependent on the anion. The anion Figure 1. Recovery of the acetone phase as a function of the
F- is usually considered more extensively hydrated than initial volume of acetone
the other common anions. Therefore, salts containing this
Total initial volume, 50 m l
anion ought to be efficient salting-out agents. This as-
sumption was supported by the present results.
Saturated aqueous KC1 solution effected no phase sepa- 50 I

:/
h

ration in the present investigation at room temperature. 40

Timmermans and Lewin (14) studied the salting-out of
acetone from water with KCl. The water and acetone were 30
added such that the weight per cent of acetone was 47.65. 20 MnSO,
With 6.84 g of KC1 in 100 g of the binary mixture, phase
separation was observed over the temperature range of 123 IO
to over 200 "C. With 9.25 g of KC1 in 100 g of the binary
0
mixture, the temperature range for phase separation was 0
from 37 to over 200 "C. Phase separation at room temper- w 40
ature was not mentioned. The solubility of acetone in a
aqueous solutions of Na2C03, NaC1, NaOH, and KOH has 30
W
been studied at low solute concentrations (23). z 20
Effect of Volume Ratio on P h a s e Separation. To ob-
tain maximum sensitivity in flame spectrometric meth- Pw IO
ods, small volumes of organic solvents are used when I -

employing solvent extraction in order to concentrate the g o

desired species. However, in the present system, a de- cc 40
crease in the initial acetone volume was accompanied by a 0
decrease in the per cent acetone recovered. If the chelate W
30
has any appreciable solubility in the aqueous phase, it 5 20
could distribute more toward the aqueous phase, thus re-
ducing extraction efficiency. 6 10
Saturated aqueous salt solutions and acetone were ' 0-
mixed in various proportions, keeping the total combined 0 5 IO I5 2 0 2 5 3 0 3 5 40 45
volumes constant at 50 ml. The volumes of the two phases
were measured approximately 30 min after thorough mix- INITIAL VOLUME of ACETONE (ml.)
ing. The phases for NaOH and KOH were measured Figure 2. Recovery of the acetone phase as a function of the
shortly after mixing to minimize aldol condensation of the initial volume of acetone
acetone (24). The results are graphed in Figures 1 and 2.
Total initial volume, 50 ml
In all cases, a recovery which was linearly dependent on
the initial volume of acetone was obtained, once the solu-
bility of acetone in the aqueous phase was exceeded, Le., solubility in the aqueous phase appears to be the primary
all the acetone was recovered above this amount. Initial consideration in acetone recovery. The initial portions of
the graphs represent complete dissolution of the acetone
(22) L. M. Mille.Anal. Fis. Quim. (Madrid). 41, 120 ( 1 9 4 5 ) . in the aqueous phase, with the intersection of the rising
(23) "Solubilities of Inorganic and Organic Compounds," Vol. 2. H . Ste-
phen and T. Stephen, Ed.. Macmillan, New York, N.Y., 1964
portions representing the solubility of the acetone.
(24) J. D. Roberts and M. C. Caserio. "Basic Principles of Organic The volume of the acetone phase recovered from satu-
Chemistry," W . A . Benjamin, New York, N.Y.. 1964. rated MnS04 solutions was greater than the initial vol-

ANALYTICAL CHEMISTRY, VOL. 45, NO. 11, SEPTEMBER 1973 1917

 Table II. Amount of Water in Acetone Phase Table 1 1 1 . Amount of Salting-Out Agent in Acetone Phase
% water, v l v After 30 min After 24 hr
Salting-out
agent Right after mixing After 24 hrs Weight of
None-acetone Weight of residue, Ppm, residue, Ppm,
Compound g j 2 5 ml wt/v g/50ml wt/v
only 0.027 0.0212f 0.005
NaOH 0.052 f 0.001 Acetone 0.0000 0.0000
KOH 0.067f 0.005 KO H 0.0030& 0.0010 120
MgCb 0.304 NaOH 0.0073 290
CaCI2 0.665 0.321 f 0.011 CaCI2 0.0065f 0.0018 260 0.0106 212
AIC13 0.635 0.470 f 0.005 MgCb 0.0118 f 0.0020 472 0.0146 292
SrCI2 1.410f 0.051 1.030 f 0.047 AIC13 0.0076 f 0.0010 300 0.0172 344
NaBr 1.580f 0.040 Na2C03 0.0197f 0.0015 7.88 '0.0156 312
"4CzH30z 2.190 f 0.087 1.590 f 0.034 SrC12 0.0272 544
NaCl 1.650f 0.074 "4CzH30z 0.0458 916
NaC2H302 1.810 f 0.040 NaC2H302 0.0366 1.460 0.0740 1,480
K 3 (citrate) 4.220 f 0.101 2.100 f0.081 MnS04 0.1582 3,164
NazC03 18.40 f 0.98 2.150f 0.037 NaCl 0.1480f 0.0025 5,920 0.1746 3,492
Mils04 6.130f 0.810 2.480 NaH2P04 0.5160 10,320
Na2H (citrate) 13.5 f 1.2 4.209f 0.063 NaBr 0.4962 9,920
~

ume of acetone taken. This was due to the water in the
acetone phase (see below). The mixtures of acetone and
MnS04 solution below 30 vol % MnS04 solution showed
no phase separation and a precipitate was observed.
Water in the Acetone Phase. Appreciable quantities of
water in the acetone phase could affect aspiration rates
and atomization efficiency in flame spectrometric mea-
surements. The water content, after shaking equal volumes
of the aqueous solution and acetone, was determined in
the acetone phase immediately after separation and after
allowing the phases to sit together for 24 hr. In the latter
case, samples were sealed from the atmosphere until anal-
ysis. KOH and NaOH solutions were unstable and could
only be analyzed right after mixing. The results are listed
in Table 11. Absence of an entry indicates those cases where
no measurement was made. The average deviation is list-
ed where at least three analyses were performed.
The results indicate that equilibrium was not achieved
immediately after mixing. The water content of the ace-
tone phase decreased with time. This observation is sup-
ported by solvent extraction experiments (below) which
demonstrated that up to 2 hr duration is required for
equilibration. Usually, 90% equilibration is reached in 15
min.
All those salting-out agents that showed precipitation
upon mixing with acetone resulted in greater than 1%
water in the acetone phase at equilibrium (NaBr, NaCl,
NaC~H302,NazC03, and SrC12). Salts that yielded great-
er than 100% acetone "recovery" resulted in greater than
2% water in the acetone phase a t equilibrium (Ka(citrate),
NazH(citrate), and MnS04). With the exception of
NH4C2H302, all the other salts resulted in less than 0.5%
water in the acetone phase. Note that KOH and NaOH,
which were very efficient phase separating agents, had
very little water in the separated acetone. Less than 1%
water in the acetone did not appreciably affect flame
spectrometric results. Under certain conditions, there is a
linear relationship between atomic absorption signals and
per cent water in acetone ( 2 5 ) .
Salting-Out Agent in the Acetone Phase. Equal vol-
umes of both acetone and saturated aqueous salt solution
were thoroughly mixed and allowed to sit for either 30
min (except KOH and NaOH solutions) or 24 hr. Aliquots
of the acetone phases were pipetted into preweighed
weighing bottles, evaporated under reduced pressure, and
dried at 125 "C for approximately 12 hr. The bottles were
reweighed and the amounts of residues determined. The
(25) C. E. Matkovich and G. D. Christian, Can. Spectrosc., in press
results are listed in Table 111. NO measurement was made
in those cases where there is no entry.
The observed amount of salting-out agent in the ace-
tone phase was always higher than the amount predicted
from the solubility of that compound in acetone. This is
not surprising and was probably due to the small amount
of water present in the acetone phase, causing an increase
in the solubility of the salting-out agent in the acetone
phase. The amounts of salts that could be carried into the
acetone phases if the water were saturated with respect to
the salts equalled or exceeded the observed amounts of
salts found in the acetone phases. Hence, salts present in
the water could account for the majority of the salts in the
acetone phases. When larger amounts of water were pres-
ent in the acetone phases, increased quantities of salts
were generally found.
Hieftje and Malmstadt (26) observed that the presence
of 100 ppm of NaCl had little effect on solvent evapora-
tion rates or on droplet size in flames. The effect of 1000
ppm of 27 different elements on the absorption of 5 ppm
of zinc was examined and only Si and Au interfered (27).
Of the salts listed in Table 111, AlC13, CaC12, and MgC12
are the most potentially useful ones for solvent extractions
with acetone (see below). Three hundred parts per million
or less of the salt in the acetone phase should not have se-
rious effects on most flame spectrometric determinations.
Molecular emission by the salt should, however, be cor-
rected for in flame emission determinations.
Trace metal impurities in the salting-out agent would
be expected to be extracted into the acetone phase by
chelating agents. Reagent grade CaC12, for example, has
been found to contain appreciable quantities of Cu, Cd,
Zn, and Ag. If an analysis for any of these metals is de-
sired, a presolvent extraction step on the calcium chloride
solution would have to be performed to remove the trace
impurities before the calcium chloride is used as a salting-
out agent.
P h a s e Diagram of the Ternary System Acetone,
Water, and Calcium Chloride. Although all of the com-
pounds in Table I are efficient salting-out agents for ace-
tone, most would be rather limited in their application to
solvent extraction because they are either not neutral,
possess strong complexing anions (F-), or possess a
strongly chelating cation (Mn2+) that would interfere in
many solvent extractions. CaC12, MgClz, and AlC13 are
potentially the most useful salting-out agents for solvent
extractions with a number of chelating agents. AlC13
(26) G.M. Hieftjeand H. V. Malmstadt.Anal. Chem.. 40, 1860 (1968)
(27) J. A . F. Gidley and J. T. Jones, Analysf (London), 85, 249 (1960).

1918 ANALYTICAL CHEMISTRY, VOL. 45, NO. 1 1 , SEPTEMBER 1973

reacts vigorously with water, making it inconvenient to
prepare saturated solutions. CaCl2 was arbitrarily selected
over MgC12 for further study.
The phase diagram of the ternary system acetone,
water, and calcium chloride was useful for predicting the
concentration of CaClz for maximum acetone phase recov-
ery. Some studies of this ternary system were done in 1914
at 20 "C (IO).
The density of an aqueous saturated CaCl2 solution at
room temperature was determined to be 1.428 f 0.008
g/ml and that of a similar solution which was also satu-
rated with acetone a t room temperature was determined
to be 1.311 f: 0.006 g/ml. Measured volumes of acetone
were added to known concentrations of aqueous CaCl2 so-
lutions. The volume of acetone added was chosen so that
an acetone phase always existed. Measurement of the vol-
ume of the acetone phase in equilibrium with the denser
aqueous phase permitted the calculations necessary to
construct the phase diagram. The results are graphed in
Figure 3.
Maximum acetone phase recovery occurred at a CaCl2
concentration of 34.24 g/100 g of solution. Hence, dilution
of saturated calcium chloride solution (45 g/100 g) with
small amounts of an aqueous sample would increase the
acetone recovery. This is indeed fortunate. Also, the curve
is relatively flat in the vicinity of the maximum so that
acetone recovery is not greatly dependent on the salt con-
centration.
Increasing the temperature to 50 "C resulted in in-
creased acetone phase recovery and a shifting of maxi-
mum recovery to occur at slightly higher CaCl2 concentra-
tions (26.1 wt %). Mixing of the ternary system was exo-
thermic and so it was not surprising that decreased mix-
ing of the phases occurred a t higher temperatures. A pre-
cipitate was observed at 0 "C when a CaCl2 concentration
of 41.67 g/100 g of solution was exceeded. The solubility of
CaCI2 in water a t o "C is 37.3 g/1OO g of solution ( I O ) .
Yashkichev (28) has observed that isotopic effects (HzO
us. D20) on physical constants decrease markedly a t high
( L 8 N CaC12) salt concentrations. He postulated that the
limit of complete solvation was surpassed a t these high
salt concentrations and that this surpassing of the solva-
tion limit was responsible for the sharp changes in the iso-
topic effects.
Evidence has been obtained in the present study of a
limit in the water available for solvation of high concen-
trations of CaC12. Anhydrous CoClz is blue whereas hy-
drated CoCl2 is pink. As the concentration of CaCl2 in an
aqueous CoCl2 solution was increased above approximate-
ly 4.2m, the CoCl2 reverted to its blue color, indicating
unavailability of free water for solvation of the cobalt and/
or formation of cobalt chloride complexes. Evidence
below suggests the former. The CoClz concentration
ranged between 5 and 100 ppm with no observable effect
on the point where the blue color appeared. The number
of water molecules associated with each CaC12 molecule
can be roughly estimated from these data. The blue color
appeared at CaCl2 concentrations in excess of 4.2 mol/per
55 mol of water. This concentration corresponds to a value
of 13 molecules of water per molecule of CaC12. This
agrees with the hydration number of 12.0 for CaClz as de-
termined by Robinson and Stokes (29) from experimental
activity coefficient values in 0.01-1.4m solutions. The hy-
dration number for chloride ion has been estimated a t 0 to
0.9 (30-33) and so the bulk of the water is taken up by the
(28) Y. I. Yashkichev, Radiokhimiya, 10, 418 (1968).
(29) R. H. Stokes and R . A. Robinson, J. Amer. Chem. SOC., 70, 1870
(1 948)
(30) J. D. Bernal and R. H. Fowler, J. Chem. Phys., 1, 515 (1933).
(31) E. Glueckauf, Trans. FaradaySoc., 51, 1235 (1955).
ANALYTICAL CHEMISTRY, VOL. 45, NO. 11, SEPTEMBER 1973
0 bo
A
0 10 20 30 40 50 60 70 80 90 100
WEIGHT PER CENT WATER
Figure 3.Ternary phase diagram of CaCle-Acetone-He0
(-m-)0
(0)
"C; ( - O - ) 25 "C; (-A-)
50 "C)
34.2 g CaC12/100 g of solution at 25 "C
(a)
saturated CaCI2 at 25 "C;
calcium ion. The concentration of CaC12 at which maxi-
mum recovery of acetone occurs corresponds to 11.7 mole-
cules of water per molecule of CaC12.
The 4.2m concentration corresponds to 31.8 g of CaCl2
per 100 g of solution, which is near the point of maximum
acetone phase recovery. Hence, it appears that at CaCl2
concentrations up to the maximum recovery, the phase
separation increases as a result of removal of available
water by solvation and/or electrostatic interactions (medi-
um effect and/or salt effect). At concentrations exceeding
this, all the water has been removed in solvating the
CaCl2 and so the excess salt is solvated with acetone,
causing an increase in the mutual solubility of the two
phases.
The decrease in the water available for solvation in con-
centrated CaC12 solutions has been used to explain the
formation of thermodynamically less stable chloro com-
plexes of chromium in concentrated salt solutions ( 3 4 ) .
The chromium polarographic half-wave potential shifted
to less negative potentials in solutions containing greater
than 1M CaC12.
Calcium Extraction into Acetone by APCD. Before
solvent extraction studies using calcium chloride as the
salting-out agent could be performed, it was necessary to
determine the amount of calcium that extracts into ace-
tone in the presence of a chelating agent. Twenty-five-
milliliter portions of acetone and saturated aqueous CaCl2
were mixed. One milliliter of freshly prepared aqueous 1%
ammonium 1-pyrrolidinecarbodithioate (APCD) solution
was added to the CaClz solution as chelating agent, and
the apparent pH was adjusted to from 7 to 1 using either
acetic acid or hydrochloric acid. After equilibration, the
acetone phase was analyzed for calcium using atomic ab-
sorption spectrometry,
The addition of APCD had negligible effect on the dis-
tribution of calcium into the acetone phase. Similar re-
sults were obtained using methyl isobutyl ketone as the
organic solvent. Calcium chloride is a good choice as a
salting-out agent for acetone because only a small amount
of the calcium ion is soluble in the acetone. Experiments
(32) I . M. Maksimova and N. N. Zatsepina, Russ. J. Phys. Chem., 43,
570 (1969).
(33) R. G. Bates, B. R. Staples, and R. A . Robinson, Anal. Chem., 42,
867 (1970).
(34) V. M. Tsokalo. P. I . Zabotin. and G. 2 . Kiryakov, Tr. Insf. Khim.
Nauk, Akad. Nauk Kaz. SSR., 24, 62 (1969).
1919
 Table I V . Per Cent Extraction of Cobalt into Acetone Table V. Effect of pH on Phase Separation with 65 Wt%
from Saturated CaC12 as the APCD Chelate Sucrose Solutiona
Initial concn After 2 After 15 Vol of aqueous YOacetone Total vol,
of cobalr, ppm min After 5 min min After 2 hr phase recovered, recovered. final,
PH ml v/v ml
100 85.4 91.1 99.5
84.Za 100.9a 1 .o 27.0 84.8 48.2
10 93.Zb 84.8 92.6 99.5 2.0 27.0 84.8 48.2
1 59.0" 84.6 94.2 99.7 3.0 26.8 86.0 48.3
85.0a 10o.oa 4.0 26.5 88.0 48.5
0.1 84.9 95.1 99.8 5.0 26.0 90.0 48.5
AV 59.0 84.8 93.2 99.9 5.5 26.0 90.0 48.5
Measured by atomic absorption spectrometry. All others measured 6.0 26.5 86.8 48.2
*
with radiotracers. Centrifuqed for 3 min after sittina for 2 min. 7.0 26.5 06.8 48.2
8.0 26.5 86.8 48.2
are under way in which solvent extractions using this sys- 9.0 26.8 85.6 48.2
tem are successfully being applied to APCD and dithizone 10.0 27.1 84.8 48.3
chelates. Extractions with oxine chelates are not possible Initial volumes of aqueous sucrose and acetone were 25 mi each.
because of the formation of the calcium oxinate chelate.
Gindin and coworkers (35) studied the extraction of sev-
eral metal chlorides from aqueous solution into various or- solvent extraction theory (37). Atomic absorption results
ganic solvents using the salting-out agents hydrochloric agreed with radiotracer results.
acid and CaC12. They found a distribution coefficient of The time for equilibration can be shortened by centri-
0.106 for cobalt between an aqueous solution of 500 g/l. fuging (see data for 10 ppm cobalt). It is recommended
CaC12 and acetone, but no extraction of nickel. Their either that samples be centrifuged or else that the phases
data, as well as data obtained in this investigation with be separated after sitting for 15 min to obtain sufficiently
radioactive cobalt tracers (below), indicate that calcium efficient and reproducible extraction in a reasonable time.
chloride can act as a salting-out agent and force apprecia- Solubility of Acetone in Aqueous Sucrose Solutions.
ble amounts of elements such as cobalt into solvents such Calcium chloride has two disadvantages as a salting-out
as acetone in the absence of a chelating agent. These agent for solvent extraction. It cannot be used in the pres-
same workers have proposed that CaC12 is hydrated in the ence of chelating agents with which it forms stable che-
organic phase ( 3 6 ) . This might explain, in part, some of lates and it contains appreciable trace metal impurities.
the water present in the acetone phase in the present The latter problem can be easily remedied by preextrac-
study. tion. These two disadvantages would be minimized if an
Solvent Extraction of Cobalt. The feasibility of solvent organic "salting-out'' agent were available. Hence, sucrose
extraction with the saturated CaClz-acetone system was was investigated as a possible salting-out agent for ace-
studied using radiotracer cobaltous chloride and APCD as tone and other water miscible organic solvents.
the chelating agent. A constant volume of radioactive Attempts to create phase separation of methanol and/or
6OCo solution (0.25 ml) was added as a tracer to samples ethanol from aqueous solutions of either sucrose or CaC12
of various cobalt concentrations in aqueous saturated were unsuccessful. However, acetone could be separated
CaC12. To effect complete recovery of the added acetone, from sucrose solution. The solubility of acetone in sucrose
the cobalt samples were prepared in saturated CaC12 solu- solution at 25 "C was determined to be 150, 92, 49, 23, 13,
tions which had been pretreated (saturated) with acetone. 12, and 11 g/100 g of solution at 30, 40, 50, 60, 70, 80, and
The various colbalt concentrations were prepared by di- 90 wt % sugar, respectively. These data agree very well
luting a 1000 ppm stock solution of cobaltous chloride. with previous data for 20 to 70 wt % sugar (38).The per
The 6OCo solution had a high enough specific activity (10 cent recovery of the acetone phase increased exponentially
Ci/g) that its addition to samples had less than 1% effect with increasing sucrose concentrations. The viscosity also
on both the total cobalt content and the sample volume. increased and the ease of handling decreased. Therefore, a
Concentrated hydrochloric acid was added to the samples balance between per cent acetone phase recovery and ease
to adjust the apparent pH to 2.5. of handling was preferred. A concentration of 5.8m or 65
A 1% APCD aqueous solution (0.5 ml), freshly pre- wt % sucrose, with a 90% acetone phase recovery a t equal
pared, and 25 ml of acetone were added to 25 ml of the initial aqueous and acetone volumes, was chosen for fur-
acetone-saturated aqueous solutions. The samples were ther studies.
thoroughly shaken, allowed to sit for various time periods The effect of pH on phase separation was determined.
between 5 min and 2 hr before separating the phases, and The pH of a 65 wt 70 aqueous sucrose solution was the
then the count rates of 2-ml aliquots of the acetone phase same as the pH of distilled water and rose to 6.8 when
were measured. Results are summarized in Table IV. Ex- boiled for 10 rnin to drive off Con. Concentrated hydro-
periments were also performed without radiotracers for chloric acid and ammonia were used to adjust the pH in
comparison, using atomic absorption spectrometry for order to keep volume changes to a minimum. Table V
measurements. summarizes the results; precision of the measurements
The data in this experiment confirm that equilibrium was about 1% relative. The volume of the acetone phase
between the two phases is not established very rapidly. recovered was somewhat dependent on the pH.
The per cent cobalt extracted was about 59% after 2 min, Sucrose was not as convenient for general extraction
85% after 5 min, 94% after 15 min, and 100% after 2 hr. studies as was CaC12 because of the high viscosity of its
The per cent extracted was independent of the initial col- solutions and because reproducible recovery of acetone re-
balt concentration from 0.1 to 100 ppm, as expected from quired careful control of the sucrose concentration. With

(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.

1920 ANALYTICAL CHEMISTRY, VOL. 45, NO. 11, SEPTEMBER 1973

CaC12 salting-out agent, the per cent acetone phase recov-
ery was almost independent of the salt concentration in
the region of maximum separation.
The solubility of acetone in sucrose was very dependent
on the temperature. Hence, it is important to control the
temperature, pH, and concentration of sucrose for repro-
ducible acetone recoveries.
Error Analysis of Density Determination by a Unique Falling
Body Method
A. s.Roy
Department of Chemical Engineering, University of the Negev, Beer-Sheva, lsrael
Sources of errors are discussed of the unique method of
density measurement of a solid sample by comparing its
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
can be increased by using a reference body of density,
size, and shape close to those of the tested body, and
liquids of wide density difference, and high, approximate-
ly equal viscosities. The self-correcting features of the
method make it insensitive to some lack of control on
experimental conditions. Comparison with experimental
results is presented.
A novel method has previously been reported for mea-
suring density of an individual small, solid sample of high
density and arbitrary shape ( I ) . In the study of isotopes
and solid state imperfections and when the sample avail-
able for investigation is smaller than a millimeter in size,
the method becomes invaluable for densities above 4 or 5.
For obtaining accuracies of 0.1 to 0.3% a simple procedure
with a limited attention to the choice of materials has
been found adequate ( I ) . The present work deals with the
error analysis of the method aimed to indicate the steps
required for attaining higher accuracies. It will be shown
that prudent choice of materials, specifically a standard
body of density, size, and shape close to those of the test-
ed body, and liquids of wide density difference and high,
approximately equal viscosities, will permit the measure-
ment of densities with additional one or more significant
figures.
The method consists of separate fall time measurements
of two bodies between arbitrary marks on two cylinders.
The two cylinders are each filled with a different Newto-
nian viscous liquid; one of density u and the other of 0'
(gram/cm3). Two of the fall times, ti and t,' (sec), are
taken for the tested body i in the two liquids, respectively,
and similarly, t , and t,', for the reference b o d y j having a
known density p , (gram/cm3) acting as a standard. The
density p r of the tested body is obtained from the equation
specifically derived for this method ( I ) :
?@af - -a
= (1)
PI
rp - 1
(1) A. S. Roy,Ana/. Chern., 33, 1426 ( 1 9 6 1 )
ANALYTICAL CHEMISTRY, VOL. 45, NO. 11, SEPTEMBER 1973
Studies are currently under way in which solvent ex-
traction of oxine chelates with acetone are successfully
being performed using sucrose as the salting-out agent.
Received for review October 12, 1972. Accepted March 16,
1973.
where y is the ratio of the net gravitational forces acting
on the body j in the two liquids,
and p is the gross fall time ratio,
(3)
This results from 4 times use of Stokes' law, extended
for bodies of arbitrary shape and constant fall orientation
(2-4):
(4)
where u, g, F , and D are, respectively, the fall velocity
(cm/sec) of the body, the acceleration due to gravity (980
cm/sec2 at sea level), viscosity (poise), and the diameter
or characteristic dimension of the body (cm), while k is a
shape-orientation factor which is a numerical constant
(unity for a sphere) typical of the geometry and particular
fall orientation of the body. Applying Equation 4 twice to
the same body i in the two different liquids of viscosities
and p' (and densities c and u'), respectively, and then di-
viding one of these equations by the other, results in
(5)
Similarly, with the reference body j
P P, - -a t,
pf - p, - -a/ t,'
Dividing Equation 5 by Equation 6 results in
P,--a P,--a
Pi- fJJ - P, - fJJ
@
from which Equation 1is obtainable by rearrangement.
The method requires thermostating of the liquid-filled
cylinders in order to keep the liquid viscosities and densi-
ties constant and uniform during the fall runs. Care is
also needed to prevent convection, air bubbles, or con-
(2) G. Barr, "A Monograph of Viscometry," Oxford University Press,
1931, Chap. V I I I .
(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.
N . Y . , 1945. pp 597-605.
1921