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On the Electric Resistance of Solid Soap

H E I H A C H I E Z A K I , K. O H W A D A , and S. N O G U C H I ,
Mitsuwa Soap Factory, Sumida-Ku, Tokyo, Japan

p REVIOUSLY We reported (1) that commercial soaps


show very complex physical changes above about
40~ The effects of impurities and conditions ,' "~k ' ~ /'-'"
of treatment on the electric resistance of solid soap
have been studied (2). I n the present paper we de- V'~-. V / , & . I- "%. ,.,--~
scribe measurements of electrical resistance in solid
soaps at various temperatures and with various water
contents.
F o u r crystalline forms of soaps are known (3), the
most important of which is the ~o-form of unmilled
soap and the fl-form found mostly in milled soap. The
formation and disappearance of these crystalline 37g
forms are known to be influenced to a large extent
by m a n u f a c t u r i n g conditions (3, 4). Therefore heat-
treated samples, which are presumed to be ~-form,
were first investigated. Later, samples made with and
without heat treatment were compared.
o' ~-'sb .... ~do' ' o 50 ioo
Experimental
Tempe ra t,r~('C ) Te~Fer ~t ure( ~ )
Fro. 2. Effects of temperature changes on the electrical re-
Figure 1 is a schematic diagram of the apparatus sistance of soaps containing various amounts of water. (Elec-
used. A glass sample tube 18 mm. in diameter was trical resistance is shown i~ arbitrary units.)
equipped with platinum electrodes (3 • 12 ram., 10
mm. apart) connected with an automatic resistance NaC1 ........................................................... 213.4
recorder (made by Yokogawa, E. W.). A tiny ther- Glycerine ............................................ about 2%
mometer was placed at the center of the tube. The
apparatus was immersed in an ice bath or an oil bath, Soap in the Sample tube was melted, deaerated as
as desired. completely as possible, cooled until solid (and left
overnight). D u r i n g measurement of the electrical re-
sistance the temperature was changed at a rate of
tterraorneter 0.5-1.0~ a minute.
W a t e r content was precisely determined for each
~. to Resistance samp]e removed from between the electrodes.
)~ecorder
/
Results
Effect of Heating (Figure 2)
/ S amp& Tube a) Less than 18% water in s o a p - - A t first, the elec-
trical resistance decreases slightly as the temperature
~S~ele increases, reaching a minimum at 40-50~ (point V).
As the temperature is raised farther, resistance in-
/ ~ ELectrode creases to a maximum at 60-65 ~ (point MI), then
decreases to a second shallow minimum at about 80 ~
and increases to a slight maximum at 86-90 ~ (point
O~ter Tu be Mn). Finally the rate of decrease becomes extremely
slow as the soap melts.
b) Between 18 and 30% w a t e r - - T h e resistance-
FIG. 1. Apparatus. temperature curve is similar to a) except that the
second minimum, and maximum are absent because the
melting point of the soap is below 80-85 ~.
Neat soap, containing 30% water, was air-cooled c) Above 30% w a t e r - - T h e r e is a fairly steady de-
and solidified at room temperature. Soap containing crease in electrical resistance as temperature is raised,
less than 30% water was obtained by air-drying soap with a slight increase as the soap begins to melt.
chips. F o r soaps containing more than 30% water,
the necessary amount of water was mixed with air- Effect of Cooling from Molten State (Figure 2)
dried soap by heating since water cannot be readily a) Below 30% w a t e r - - T h e temperatures of max-
mixed with neat soap. The soap was made from a ima and minima in the resistance curves during cool-
mixture of beef tallow, coconut oil, and some hard- ing are at the same points as during heating. However
ened oil. The constants were: the changes in resistance are m a n y times more pro-
Melting point ............................................ 40~ nounced d u r i n g cooling than d u r i n g heating.
Neutralization value ................................ 39.1 b) Above 30% w a t e r - - T h e cooling curves are prac-
Iodine value ............................................... 0.01% tically identical with heating curves but are slightly
N a O H ........................................................ 0.83% lower.
254
JUNE, 1959 EZAKI ET AL.: ELECTriC RESISTANCE OF SOLID SOAP 255

ing and cooling was 0.5-1.0~ F o r another


extreme case the temperature was brought to a given
point and kept constant for at least 30 rain. Figures
4-1 and 4-2 show measurements for heating and cool
/ \ ing, respectively, of a soap containing 17.3% water.
t
F r o m these curves it was concluded that, for all points
except C, resistance values were constant at a given
constant temperature. The relatively large values at
C may be attributed to hysteresis since the sample
f . . . . . .s . . . . . ..

i2 . ~' /,; ~ \ ,

I ,N.'. (t~'),',' ~., ~ I

,ool
i
I

" I I
I
.5 --,
'E6ec, Res;sT,~ce.

0 I I ] I I I t i
20 40 60 80 IOO
T~.~p~ra.t~re C%) o

Fro. 3. Hysteresis in electrical resistance vs. temperature


curves for soap of 20% moisture content. ,a

Hysteresis Effect (Figure 3)


50 \
I n the case of the soap containing 20% water (Fig-
ure 3), samples were heated and then cooled from
various temperatures below the melting point.
g tU

a) As is shown in curve (1), when the temperature


was decreased at the usual rate (0.5-1.0~ from
a temperature below t~,, electrical resistance values
during cooling and heating were practically identical.
oj .~o ,bo 2bo
b) Curve (2) shows that when the soap was heated -r,:,.,. (.,-,,~.)
.to a temperature slightly above a t~, and then cooled, FIG. 4-2. Electrical resistances of soap (17.3% moisture
there was a sharp increase in electrical resistance. content) during stepwise cooling.
A similar effect was observed at all temperatures
was accidentally overheated slightly and then cooled
between M~ and L (the melting point). I t seems
to the proper temperature.
that tMz is the critical point above which hysteresis
Whenever soap is held at a given temperature, its
effects appear.
electrical resistance is constant and the hysteresis
Effect of Stepwise Temperature Changes (Figure 4) effect appears independent of the rate of heating or
In the preceding experiments the rate of both heat- cooling.
Discussion
When logarithms of conductivity v s . 1/T curves for
various water content, where T is absolute tempera-
ture, are drawn from the relation in Figure 2, it may
be more clearly shown that those curves consist of
three parts. Both in the regions below 40~ (V') and
above L, all curves are practically parallel to each
other, showing that they are in the same state of
phase, independently of water content. I t is also
interesting to note that there appear maxima or min-
.~. I ~ T~p.~. / ima always at around the same temperature in the
third intermediate region between 40~ and L. I t
i \, b b would appear that these changes are caused by phase
transition.
sol ",/ ~ EL,~. ~,t~.~o~ ~ ~ F i g u r e 5 shows the curves connecting the points
where definite maxima and minima in electrical resist-
F X"..., o~ /" !! i ance were observed.
McBaiu (6) presented a phase diagram for soap
based on studies of vapor pressure, dilatometry, and
optical measurements. The melting line tL (Figure 3)
%'"""" i corresponds well with McBain's Tr curve. Similarly
~ sb k0 2}0 s00 the line connecting the points M, fo r various water con-
tents in Figure 3 fits the horizontal line at 60~ in
Fro. 4-1. Electrical resistances of soap (17.3% moisture con- McBain's diagram, and region between t ~ and tL was
tent) during stepwise heating. also found to be heterogeneous. Our data however
256 THE JOURNAL OF T H E A M E R I C A N 0IL CHEMISTS' SOCIETY VOL. 36

content. F o r the sodium soaps of laurie to stearie


acids, conductivity decreased to a m i n i m u m between
150
80 ~ and 90~ a f t e r which it started to increase again.
This effect was independent of the kind of f a t t y acid
x ...... L ( ;,,. fiqZ) or water content. I t a p p e a r s that these effects m a y
o ..... H~( , )
predonlinate at around MI~ of F i g u r e 2.
100 o .... 7%( , )
o V ( ~ ) Summary
~..~ z~ . . . . V' ( ~ )
Electrical resistance values are reported for soaps
of various moisture contents. Marked changes in re-
~so sistance were found at 40-50~ Below this temper-
ature the logarithm of conductivity is a linear func-
a_ tion of inverse temperature, and the slope of the curve
g is practically independent of water content. Above
40 ~ resistance is m a r k e d l y affected by the water con-
i I t i i ._
0 20--4'0 6'0 8'0 I%0 tent of the soap. F o r soaps containing 12--30% water,
WMer C o ~ e ~ [ ( % ) heating and cooling curves show definite m a x i m a and
FIG. 5. Phase transition points for soaps of various moisture minima in electrieal resistance values. This effect is
contents shown by electrical resistance vMues. (L, Mm etc., less obvious in soaps containing' more t h a n 30 % water.
refer to corresponding points in Figure 2.) The phase transition points estimated f r o m resistance
measurements are in good agreement with those de-
seem to indicate phase transitions at about 50 ~ and duced from other physical measurements.
40~ which were not found by McBain.
I%EFEI~ENCE S
Thiessen and Stauff (5) have noted t h a t there are
1. Ezaki, Heihachi, et al., J. Chem. Soe. J a p a n (Ind. Chem. Section),
phase changes near the melting point of the constitu- 60, 883 ( 1 9 5 7 ) .
ent f a t t y acids in a soap and have named this the 2. Ezaki, Heihachi, et tel., ibid., 60, 1133 ( 1 9 5 7 ) .
3. Ferguson, 1~. tt., et al., I n d . Eng. Chem., 35, 1003 ( 1 9 4 3 ) .
" g e n o t y p i e p o i n t . " Since f a t t y acids in cmnmercial 4. Mills, V., U. S. P a t e n t 2 , 2 9 5 , 5 9 4 - 9 6 ( 1 9 4 2 ) .
5. Thiessen, P. A., et al., J. Phys. Chem., A_174, 335 ( 1 9 3 5 ) ; Thies-
soap have a melting point around 40~ the hori- sen, P. A., Angew, Chem., 51, 318 (1938) ; Davidsohn, A., et al., "Soap
zontal line at this t e m p e r a t u r e in F i g u r e 5 m a y be ~r vol. 1, p. 49, Interscience Publishers Inc., New York
(1953).
the " g e n o t y p i c p o i n t . " 6. ~ c B a i n , J. W., et aL, OiI arLd Soap, 30, 17 (19&3).
7. Ezaki, Heihaehi, et al., unpublished.
Studies with single p u r e soaps (7) have shown t h a t
transition points are practically independent of water [ R e c e i v e d M a y 27, 1 9 5 7 ]

Flash Desolventizer Operation to Produce Soybean


Protein Flakes
O. L. BREKKE, G. C. MUSTAKAS, M. C. RAETHER, and E. L. GRIFFIN,
Northern Regional Research Laboratory, 2 Peoria, Illinois

OYBEAN PROTEIN FLAKES are useful for m a n y in- vide the heat required for vaporization of solvent and
S dustrial applications, for example, in p r e p a r i n g
pIywood or paper-coating adhesives. However
to convey solids through the desolventizing tube to a
eycl(me separator. A m a j o r portion of these vapors
flaked, hexane-extraeted soybeans are not suitable un- is reheated and recycled, and the r e m a i n d e r is sent
less precautions are taken to minimize denaturation to a condenser. This desolventizing process combines
because of heat t r e a t m e n t incurred in the desolventiz- certain features of a horizontal, v a p o r t y p e of desol-
ing operation. Previous results obtained b y Belter ventizer (4) with those of a flash or pneumatic con-
et al. with a flash desolventizer indicated t h a t such a veying drier.
unit is well suited to hexane removal without exten- The performance of a flash deso.lventizer is deter-
sive protein denaturation (2). However the effects mined by several factors that control the heat t r a n s f e r
of process variables were not studied; moreover aged rate and consequently the rate at which ~ntrained sol-
soybeans with p a r t i a l l y d e n a t u r e d protein were used. vent is vaporized. One of the most i m p o r t a n t is the
The present investigation was u n d e r t a k e n to establish direct contact obtained between solids and superheated
desirable process c~nditions for flash desoDentizing vapors whereby the flakes' extensive surface area is
hexane-extracted flakes without significant protein fully used for heat transfer. T u r b u l e n t v a p o r flow
denaturation. Soybeans f r o m a eurrent harvest were in the desolventizing tube and a high t e m p e r a t u r e
used. differential at the solids inlet also increase the rate.
The flash desolventizer process employs superheated As the solids are simultaneously dried and carried
vapors in direct contact with solvent-wet feed to pro- to the cyclone separator, the t e m p e r a t u r e differential
progressively decreases. Meanwhile solvent and mois-
1 Presented at the meeting of the American Oil Chemists' Society, t a r e evaporating f r o m the solids moderate the lat-
l~ernphis, Tenn., April 2 1 - 2 3 , 1958.
UThis is a l a b o r a t o r y of the Nm'thern Utilization l~esearch a n d De- t e r ' s t e m p e r a t u r e rise. The high heat-transfer rate,
velopment Division, Agricultural R e s e a r c h Service, United States De-
p a r t m e n t of Agriculture. combined with the thin flakes, permits r a p i d solvent