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1514 J. Chem. SOC. (A), 1971

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Solutions of Soaps in Organic Solvents

By Wahid U. Malik," Ajay. K. Jain, and 0 . P. Jhamb, Chemical Laboratories, University of Roorkee, Roorkee,
U.P. India

The solubilities of silver and chromium soaps in nonaqueous solvents have been determined by a radiotracer
technique. The metal soaps are sparingly soluble in nonaqueous solvents but more soluble in alcohols. The
solubility data at different temperatures in benzene, toluene, and m-xylene has been used to determine the critical
micelle concentration (c.m.c.) of these soaps. Small amounts of methanol enhance the solubility of the metal
soaps in benzene and the viscosity of soap solutions in methanol-benzene (1 5% methanol) showed the existence
of micelles a t high soap concentrations. The solubility of silver laurate in aqueous solutions of dioctyl sodium
sulphosuccinate and Nonidet-P40 has been determined and the data was used to calculate the c.m.c. of aqueous
surfactants.

WE have investigated the solubilities of heavy-metal
soaps in order (i) to find mixtures of solvents in which
they are very soluble and (ii) to compare their behaviour
with aqueous soap systems. A radiotrace technique
was used to determine the solubilities of silver and
chromium soaps in nonaqueous solvents and in aqueous
dioctyl sodium sulphosuccinate and poly(ethy1ene oxide)
condensate. Our results are compared with those of
earlier ~tudies.l-~
EXPERIMENTAL
Reagents and Materials.-Dioctyl sodium sulphosuccinate
(97.8% purity) and Nonidet-P40 (designated as 100%
polyethylene oxide condensate by the manufacturers) were
B.D.H. products and used without further purification.
1 W. U. Malik, B. P. Singh, and A. K. Jain. Exfierientia,
1967, 23, 346.
Lauric (m.p. 43.9") and stearic (m.p. 69.4") acids (B.D.H.
reagent grade) were repeatedly crystallized from alcohol.
The solvents employed were purified by standard methods.
Water redistilled over alkaline potassium permanganate
was used throughout.
Sodizcm Laurate and Stearate.-Sodium soaps were pre-
pared by heating equimolar proportions of fatty acids and
sodium hydroxide in refluxing alcohol for 10 to 12 h.
Excess of acid was removed from the products by Soxhlet
extraction with acetone, and the soaps were recrystallized
from ethanol.
Preparation of the Labelled Silver S~aps.-[~l~Ag] Silver
nitrate in dilute nitric acid (from Bhabha Atomic Research
Centre, Bombay) was neutralized and added to unlabelled
2 W. U. Malik and A. K. Jain, J. Inorg. Nuclear Chem.,
1967, 29, 2825.
3 W. U. Malik and A. I<. Jain, J . Colloid and Interface Sci.,
in the press.
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Inorg. Phys. Theor. 1515

silver nitrate in methanol; the mixture was stirred for ca.
1 h. A stoicheiometric amount of sodium soap solution in
methanol was added and precipitated silver soaps were
filtered off and dried in vacuo in the dark. The precipita-
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residue. As these soaps possess amphiphilic properties
their solubility in alcohols is enhanced due to favourable
solute-solvent interaction. Thus in this respect these
soaps differ from aqueous soaps which are soluble both

tion was carried out in 95% methanol, since in water the

precipitates had a tendency to pass into colloidal state.
The soaps during preparation were protected from carbon
dioxide. The activity of the products was ca. 1 & 0.1
mCi/g.
Preparation of the Labelled Chromium Soafis.-[Wr]
Chromium trichloride in dilute hydrochloric acid was used
to prepare the chromium soap in a similar way to that em-
ployed for the silver soaps. The activity of the products
was ca. 1 f mCi/g.
Solubility Measurements.-Excess of solid metal soap and
solvents were stirred a t different temperatures in a thermo-
statically controlled bath to within k0.5". Attainment
of true solubility equilibrium was indicated by the con-
stancy of the counting rate when portions were leached a t
different time intervals. Solutions in various solvents were
filtered (Whatman No. 42 paper) and evaporated to dry-
ness under an i.r. lamp. The activity of each sample was
measured for 5 min. with y-ray scintillation spectrometer.
Standard solutions of the silver and chromium soaps in
pyridine were used to determine their specific activity.
Appropriate corrections were made for the coincidence loss
and the decay of the isotope.
Viscosity Measurements.-The viscosities o f silver, cobalt,
and cadmium laurate were determined in methanol-
benzene (15%) ; 4-8 average values from several measure-
ments were adopted. Temperature was maintained with
&Ow05 "C in a water thermostat.
RESULTS AND DISCUSSION
Solubility Behaviour.-The solubility values of silver,
and chromium, cobalt,l and cadmium 8 soaps together
with standard deviations are given in Table 1.
TABLE1
Solubility of heavy-metal soaps a t 30"
Solubility x lo6 (mol 1-I)
in highly polar solvents as well as in moderately non-
polar solvents. It is difficult to draw conclusions as to
the effect of the metal on solubility behaviour; although
in general the solubility of cobalt and cadmium soaps
are higher than those of silver and chromium. In
methanol, the solubility is in the order Co > Cd > Ag >
Cr soap which indicates that cobalt has a greater affinity
for methanol; it is well established that cobalt forms
solvates with methanol.'*
As to the effect of the hydrophobic part on the
solubility, silver and chromium stearates are more
soluble than corresponding laurates in nonpolar solvents.
Efect of Temperature o n Silver Laurate and Chromium
Stearate Solubility in Benzene, Toluene and m-Xy1ene.-
The effect of temperature on the solubility of silver laurate
and chromium stearate in benzene, toluene, aiid m-xylem
is shown in Figures 1 and 2. At low temperatures the
solubility of the soap is quite small but this increases
slowly with increase in temperature. Within a narrow
temperature range, the solubility increases rapidly and
the temperature at which the abrupt change occurs is
known as Krafft point,lO the concentration at which this
occurs is the critical micelle concentration (c.m.c.). This
behaviour is the characteristic of miceile-forming sub-
stances and is explained in terms of the low solubility
of the soap molecule and the high solubility of the micelle.
Comparison of these results with reported ones for
aqueous soap systems U,l2 shows that their behaviour
is similar. The Krafft point and c.m.c. values are given
in Table 2.
A

Silver Cobalt Cadmium Chromium Silver Chromium

Solvent laurate laurate laurate laurate stearate stearate
Water 1.13 & 0.04 2-29 f 0.9 4.85 f 0.12 0.31 f 0.02 0-72 f 0.03 0.19 f 0.02
Benzene 0.93 f 0.03 7-98 f 0.08 2-75 f 0.09 0.75 f 0.04 1-53 f 0.06 0.93 f 0-03
Toluene 1-19 f 0.04 4-43 f 0-05 3-29 f 0.10 0.82 f 0.04 2.12 & 0.06 1.19 0.03
m-X ylene 0.56 f 0.02 3.71 f 0.10 0.51 f 0.02 1-02 f 0.03 0.72 f 0.02
Methanol 195.40 f 1.76 604.00 f 3-00 239.70 f 1.76 86-21 f 1.51 128.10 f 1-18 75.01 f 1.34
Ethanol 25-01 f 0.27 3.94 f 0.06 166.40 & 1.27 19-42 f 0.38 22-13 & 0.25 16-81 f 0.34
Propanol 124.30 f 1.14 480.10 f 3.42 37-83 f 0.65 90.03 & 0.92 31.35 f 0.59
Butanol 69-45 f 0.59 529.10 f 3-67 17.69 f 0.35 54.11 f 0.49 14.75 f 0.30
Isopropyl alcohol 10.38 f 0.14 126-30 f 1.00 7.72 f 0.19 9.81 f 0.12 6.44 f 0.15
Isobutyl alcohol 4-39 f 0-08 136-50 f 1.07 5.24 j= 0.13 3.21 f 0.07 3.53 f.0.10
Dimethylformamide 14-67 & 0.18 1-99 f 0.02 25-44 f 0.29 21.2 f 0.43 8-62 & 0.11 20.31 -J= 0.40
Acetone 2-16 f 0.06 2-39 f.0.02 4.29 f 0.11 3.62 0.10 2-91 & 0.07 4.36 f 0.12
Carbon tetrachloride 1.04 f 0-03 1.15 f 0.02 7.33 & 0.14 1-48 f 0.04 1.86 & 0.05 1.70 f 0.06

The results show that silver and chromium soaps are Solubility of Silver Laurate in Aqueous Dioctyl Sodium
sparingly soluble both in highly polar and highly non- Sulphosuccinate and Nonidet P40.-The solubility values
polar solvents although they are expected to show large of silver laurate lo in aqueous dioctyl sodium sulphosuc-
solubility in the latter because of the hydrophobic cinate and Nonidet-P40 is a function of aqueous soap
4 0. Scarpa, Gazzetta, 1910, 40, 271. 2. Luz and S. Meiboom, J . Chim. fihys.. 1964, 40, 1058.
5 J. Farrow, J . Chem. Soc., 1912, 101, 347. 10 P. Krafft and H. Wiglow, Berichte, 1895, 28, 2566.
6 M. Prasad, S. M. Mehta, and B. N. Desai, J . Phys. Chem., 11 R. C. Murray and G. S. Hartley, Trans. Faraday Soc.. 1935,
1932, 36, 1384. 31, 183.
2. Luz, J . Chim. phys., 1964, 41, 1748. l2 N. K. Adam and K. G. A. Pankhurst, Trans. Faraday SOC.,
2. Luz, J . Chim. phys., 1964, 41, 1756. 1946, 42, 523.
 View Article Online

1516 J. Chem. SOC. (A), 1971

concentration as shown in Figures 3 and 4. The initial
increase of solubility with increase in the concentration
of aqueous soap is probably due to the interaction of
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laurate due to solubilization. This latter factor does not
appear to be the simple phenomenon involving the
inclusion of silver laurate in the hydrophobic core of
micelle since silver laurate has been found to be sparingly

4C soluble in nonpolar solvents (cf. Table l),rather it seems

II that solubilization takes place through mixed micelle
formation.
The c.m.c. values calculated from the breaks are
found to be 6.31 x lo4 mol 1-1 for dioctyl sodium sul-
phosuccinate and 12-59 x g 1-1 for the poly(ethy1ene
oxide) condensate (Nonidet-P40) and compare favourably
with the values (643 x 10" mol 1-1 for dioctyl sodium
sulphosuccinate and 12.5 x g 1-2 for Nonidet-
P40) l4 .139

Solubility in MethanoCBenzene.-As expected the

solubility of heavy-metal soaps in benzene, toluene, and
m-xylene etc. was greatly enhanced by the presence of
methanol; we have investigated this phenomenon for
~

heavy-metal soaps in methanol-benzene by the evap-

30 L3 50 60
Temp. ('Cl oration method. Our results are given in Table 3.
FIGURE
1 Solubility of silver laurate in, A, benzene, B,
tolueix, and C . ?:c-xylene

c
d
0

-- 12 -
!-

-; l o -
d

Lo
=x a -
.-
2 6 -
.-
d

a
a 1- FIGURE3 Plot of log S (silver laurate solubility) vs. log C
(concentration of dioctyl sodium sulphosuccinate)

FIGURE
2 Solubility of chromium stearate in, A, benzene,
B, toluene, and C, m-xylene

TABLE2
Krafft point and c.m.c. values of silver and chromium
soaps
Silver laurate Chromium stearate
Krafft c.m.c. x lo5 Krafft c.m.c. x lo5
point . (moll-1) point (moll-1) 2.0 1.5 1.0 0.5 0.25
Benzene 47.5" 1.9 48.5" 1.2 -Log c [ m o t 1-11
Toluene 48.0 2.0 52.5 1.6 FIGURE
4 Plot of the solubility of silver laurate us. log
m-xylene 53.5 1-4 49.5 1.0 (Nonidet P40 concentration)

silver soap and aqueous soap molecules as a result of The cobalt soap is more soluble than the others in
van der Waals forces.
methanol-benzene; this parallels its behaviour in
Beyond the breaks in the curves (Figures 3 and 4)
methanol.
which may be taken as the c.m.c. of aqueous soaps, the Viscosity Behzaviour.-In contrast to aqueous soap
increase in the solubility is larger, and this may be due
systems where viscosity studies 15-18 have been extensive,
to (i) the absorption of silver soap molecules on the
micellar surface and (ii) the enhanced solubility of silver l5 N. Sata and K. Tyuzyo, Bull. Chem. SOC.Japan, 1953, 28,
177.
13 E. F. William, N. T. Woodbery, and J. I<. Dixon, J . Colloid 16 R. J. Vetter. J . Phys. and Colloid Chem., 1947, 51, 262.
Sci., 1957, 12, 452. 17 I<. Hess, W. Philippoff, and H. Kiessig, KoZZoid Z.,1939,
14 W. U. Malik, P. Chand, and S. M. Saleem, Talanta. 1968, 88, 40.
15, 133. 18 P. Ekwall and P. Solyom, Acta Chem. Scand., 1967,21, 1619.
 View Article Online

Inorg. Phys. Theor. 1517

similar studies with organic solutions of metal soaps
have been li1nited.1~ We have investigated solutions of
metal soaps in pyridine and in 15% methanol-benzene.
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difference in this behaviour and that for 15% methanol
in benzene mixture may be due to complex formation
with pyridine 20 which stops micelle formation.
In methanol-benzene at low concentrations there is a

TABLE3 linear relation between AqSp and soap concentration.

Solubility of heavy-metal soaps in methanol-benzene Micelle formation occurs a t higher concentrations as
at 30" evidenced by an increase in A?*. Since micelles have
Composition of Solubility x 10s (mol 1-l)
the mixture r L
>
(% of methanol Cobalt Cadmium Silver Chromium
by volume) laurate laurate laurate laurate
O* 0.0798 0.027 0.009 0.0075
10 87.1 3.0 6.2 10.5
20 84.1 6-2 11.54 174
30 74.7 7.7 10.3 16.6
40 64.4 6.0 9.3 14.8
50 54.4 5.8 8.3 12.7
60 38.9 5.0 5-9 11-2
70 27.9 4.9 5.5 9.9
80 18.4 4.3 3.6 8.3
90 10.5 3.9 2.5 3.6
100 * 6.04 2.38 1.95 0.86
* Data taken from Table 1. FIGURE6 Plot of specific increase in viscosity us. soap
concentration in pyridine
Figures 5 and 6 are the plots between specific increase in
viscosity, Aqsp = (qs - qp)/qo (ys = Viscosity of soap high affinity towards solvent as compared to single soap
solution and yo = viscosity of the solvent) and soap molecules they will be associated with large amounts of
concentration. solvent and thus the volume fraction 21 of the dispersed
phase (soap) will increase more rapidly upon micelle
100 r formation.
In order to ensure that the viscosity variations are due
to soap solutions and not simply t o the presence of
metallic content, viscosity experiments with simple salts
(viz. silver nitrate, cobalt chloride, and chromium nitrate)
solutions were carried out under strictly identical con-
ditions, with 50% alcoholic solutions (metal salts as
m such are insoluble in pure solvents). The nature of the
0
c

3 curves in case of metals is quite different from those of

a The c.m.c. values calculated from above breaks are
2 4 6 8 10 12 IS 16 18 20
Soap concn. x 1 o 3 ~ m o 11-t)
FIGURE5 Plot of specific increase in viscosity us. soap
concentration in 16% methanol-benzene
Variations in viscosity with concentration are de-
pendent on the solvent employed. Thus, with pyridine
there is a linear relation between the specific increase in
viscosity and concentration of soap solution. The
corresponding metal soap solutions.
4.6 x 1 0 - 3 ~ ,S.0 x 1 0 - 3 ~ ,and 10 x 1 0 - 3 ~for silver,
cobalt, and chromium laurate, respectively.
Estimation of Metal Content by Viscometric ikfethod-
The concentration us. Aqsp plots may be used to estimate
the concentration of an unknown sample. The results
compare favourably with those of spectrophotometry
and polarography.22-24
Thanks are due to C.S.I.R., New Delhi, for the award of
Junior Research Fellowship to one of us (0.P. J.).
[0/059 Received, Jaizuary 13tI2, 19701

T. S. McRoberts and J. H. Schulman, Nature, 1948, 162, 2 p W. U. Malik and S. I. Ahmad. Indian T . Chem., 1964, 2.
101. 168, 247.
2o A. S. C. Lawrence, Trans. Faraday SOC.,1937, 33, 815. 23 W. U. Malik and S. I. Ahmad, J. Amev. Oil Cheinists' SOC.,
81 H. R. Kruyt. ' Colloid Science,' Elsevier, Amsterdam, 1952, 1965, 42, 451.
vol. 1, p. 27. z4 W. U. Malik and R. 2. Haque, dnalyt. Chem., 1962,189, 179.