ONE OF THE FUNDAMENTAL PROBLEMS IN THE PHYSICAL CHEMISTRY

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00039R000100030071-0
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 14
• Document Creation Date: December 22, 2016
• Document Release Date: June 1, 2012
• Sequence Number: 71
• Content Type: REPORT

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ayetem with 2 . 3 dropa of water not only atop. the breakdown l.4hs
of thq emul4Iio! but also reestabliahed the emulsion beoauae
point to tnsuffioient kinetic stability of the original emulsion. The
interphase layers here are stable with concentrations of the dispersed
necessary stability o onditione of oonoentrated emul~wiona are s euf-
fioient surface aotivity (soluble emulsifiers) relative to the
1iquid~1iqu1d interphn~e boundary and toughness of the stabilizer in
the d orption layer. These conditions ensure kinetic stability of
emntsione when highly dispersed or when formed from two liquids of
equal specific weights. But if in the ayotem there is found a aigni-
f'ioant number of large drops not having Brownian movement, then the
uniform distribution is disturbed and interphage layers appear, which
or the ~~ _ wa - between the dropa if a greater amount
of water is added to an emulsion of maximu~ concentration or of generally
high o onoentration, the water (or an ,addition of a weak solution of the
stabilizer) the oel ',and separates them from each other. The
free drops which eeeume the unual spherical shape, remain suspended
in the dispersion modium with an early formation of protective layer.
on them; i.e. a t emulsion is obtained whose stability
is baeio~lly determined by the dispersion of the original system.
2. Aoooroing to the generally aodepted views of Rebinder (3), the
metrical spheres because of the polyMdispersion of the system), beoauseo
phase of about 80% (the upper limit of filling the volume by isodiaw
of the presence of strong hardened layers of the stabilizer on the
drops.
Kinetic instability of the original emulsion can be oompenarated
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for even with a small concentration of the dispersed phase; i.e.
with large intervals betwoen the drops. For this purpase, the pro-
tective layers encircling the drops must be fortified so that a spatial
network be formed whose wells are strong enough to maintain the
-.e.......
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euapenaion of the drops. Stating the problem in this way is not soot-
dente,/ einoe in 1934 Talmud and Broiler proposed/k/ that "From cm'
point of view all stabilising adeorption layers and surface filme of
emuleion~ appear to be eepumoid'".
The present etate of oolloidal ohemietry makes it poaeible to
"~? x
oonetruot such atruoturee in tit-eoneet'iird emulsions,
emulsion leads to ooaleoenoe of the drops, whioh are freed when the
leads to the formation of gur&si.emuleione in which the cops are meohani-
oally enoloaed within the epaoee of the Celle. Shaking of the quaei-
uaing, for a sudden inoreaso in stability of con-
centrated emulsions, thixotropic colloidal eolutions of eurfaoe-aotirn
et~bilieere, which are easily reformed after cessation of meohanioril
notion.
The etabilizer should have for this point a) surface activity rela-
tive to the interphaee boundary of water and oil and euffioient
surface strength in a fine layer of the solution and b) the ability
suddenly to form the thixotro io eyntema with a euffioiently rapid reetora-
Lion of ' ep!tti.nl etruoture3Vin emulaifiontion.
The surface activity of the atnbilizor, rya is known, ensurea the
formation of a protective layer on the oil drops. Therefore not all
thixotropio eolutiona oan be uaed for our purpcsea. Colloidal aolutions
of materials which do not have a noticeable surfaoe activity (for example,
thixotropic eolutiona of iron hydroxide or vanaditzn pentoxide) are
uoh
not effeotive stabilizers of emulsions. The use of aubetanoes usually'
oella are disturbed. Only thixotropio solutions of aurface-active
solution between the drops is disrupted shaking the prepared emul-
even in the case where the opatial structure network in the free
aubetancea can ensure the covering of the drops with a protective layer
lion or in forming the emulsion.
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tk
tithe movement of the drope, f ml' ar4 eT eeaeeine "~ LZ4 rar
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Sinoe emulsions are obta#ned as the result of the moohenioal pro-
ooesing off' two fluids, Cfle~,tho prooeas of emul$ifioation ahond
volve a disruption of the epstiul etruaturea in the otabiliair~ aolu-
' W I C1 D. 4 i ''iA.
t,ion~ it is esoential in ~
p-re iMr ,ng the eyetom from ebpiitt4
tang into layers to have A simultaneous aM eu i'ioiontly rapid reatora-
tion of the diarupted apstial atruotures after oosaation of omulaifi-
oati,on, The emulaian will aPp A '
akinetio11y etable for a long period,
if the adsorptian 1ayere on b drops of the dieperaed pbue ae a
pert of the struotur, l alemento oi' thaystem, are rapidly 'eouad A
Vo ertoh
raotur 1 fragm?nte in free aolution, j
ru iL S . Tho etruoturos rhould be disturbed relatively
I
bpr meohanior~l aotion to avoid using large energies in overoomia
g
these resistances during emulsitioation. `e
It ie na.ta, that the
properties of thoeo ayeteme should be studied and oharaoteriaed by
measuring the visooeity of the solutions for variable preseuree
(velooitier~ of flow.
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third minutes of dispersion.
The abability was determined by the omulsion's rate of separation
into layers which was observed in graduated cylinders.
the benzo 1 in various proportions by means of a 400-rpm agitator for
5 minutos and making two 30-seoond interruptions after tho first and
The emulsions were prepared by stirring stabilizer solutions with
That very atablo omulaiona oould be obtained by thia relatively
easy m?thod of uaing thixatropio ?olutiona was proved is a aeriaa at
oaaoo.
In oonnootion with thin, we will now examine the atabiliaing pro.
pertioa of mixtures of sodium oleate with aliphatio aloohola in the
formation of oonoentrated emulaiono.
Experimental Section
the sodium oloate was prepared from oleio acid Ihioh~iad been
fro hly distilled in vaouum and a oaustio soda solution. The aloohola
were ohemioally pure. Carefully purified and dietilled bensel servod as
the diapereud phase. The aloohol was mixed with either the benzol or
a 1 soap solution. The vicoosityr was measured by Oebrald's visooaimetor
in Kroyt'e apparatus. The surfaoe tension was measured by Rebinder'a
maximum-drop and bubble-presoure method.
The influenoe of aloohola on the stabilit of an emulsion.
by the ourves of figures 1 and 2 for emulsions with a 60% (volumetrio)
Investigations ahowed that the introduction of aloohola into benzol
or into the soap solution generally leads to an inoreaso in the stability
of an emulsion of the oilMwater type which may have various volumetric
phase relationships. The stability inoreaeesJ 4hex as 1) fibre
aloohol of any chain longth is introduced into the system and 2) with
the length of the chain for equal oonoentrations of aloohol. This is shown
oonoentration of benzol.
The study of viscosity, carried on earlier in our laboratory
.
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alobhola brim about in sodium-oloato eolutionc tho davalopmont oi' ctruo?
/0/. ahawed that the middle members of a homologous aeries of aliphatio
as is coon from figures 1 and 2, an oxooptionally sharp inoroaeo in etau'
bility ie produced by oetyl aloohol in bwtzol or in a soap solution.
turos ? a ooagulativo nature. Although the spatial etruoturee are euffioiantly
i'ragile, the stability oi' the emulsion is aignifioantly inoroased. Howovar,
It ie very important to nation that the preaonoo of ema11 amounte of
to i'orin an emulsion which is praotioally non?aeparatin fora long period.
cetyl alcohol, about 0.1%, in a 1 solution of sodium oleate in auffioiont
With inorease in aloohol oontent, tho omuision booomoa stable praotioally
1~ighUy"oloeod ooni;ainere,
without limit and nonwaoparatin; for a year and longer if ntore in
T'ho etatomonts of Shulman and Cookbain on tho vory poor stability of emul-
eione preparod with sodium oleate and oontaining ootyl alcohol in the
a
4i1 phase together with their attempt of/ haorotioaal proof of thin seem
strange.
Visoosi of water mixtures of sodium oleate with oet l aloohol.
1~ eodium-oleate solutions were boiled under a reflux for 10 minutes with
various amounts of oetyl aloohol. In 2 hours after preparation, the solu"
tions wore measured with the visoosimeter.
We estimatrid tho solutions' oapaoity of thixotropic restoration in the
following, way. After finishing the measuroment under the hip;hest pressuro,
aould'be considered oomplete.
zero point was peproduoed, then the restoration of the spatial structure
solution under the first pressure at which the test was started. If the
the "zero point" was repeatedly determined; i.e. the time of flow of the
i
i ,
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0.
were conduoted. at 20
G?t"
The obtained data show that tha-d~i~we'i,0eWat oety alcohol in a
In other oneee, the degree of thixotropic restoration of struoturea was
ootabliehed in thie wey.
-nMea-4wwr4 S d t 4 _O_ _P _s
The viocoeimet'io~ so eolutione se a function of oetyl
aloohol oontoat are represented in figure 3. The general preeaure P.
including the average hy4ostatio difference , ie the abeoisee, and
the ordinate is the rotative viscosity `I / ~~G , where h and ~')~ oorre.,
epond reepeotively to the density of the solution and water. The measure-
0
mente
sodium-oleate solution leads to a etruoture-forming eyetem which is
stronger, the higher the alcohol conoentration. 'fie-metts oenaai s
'',1t,1& spatial struoturesdevelopod in solutions, which are partly
menu at zero pressure show in all cases the reeetab iphmont of abnormal
disturbed during increased rates of flow, but which are rapidly re-
established when in a state of rest. Actually)repeated messure~
(otructural) viscosity
t
the lower the alcohol content. This is verified by table 1.
~tV' ty ~
dkethal,ly, for alcohol concentrations up to l%,/the structures
are practically fully restored in a short time after their disruption
as the result of drawing the solution through capillaries, with a gradual
increase in pressure to P ^ 1800 mm of water.
Apparently the struotures are restored as rather loose non-dense
~ r
formatione oa alcohol in the gelatinization process. ' tiV
alcohol concentrations of less than p.l~, structure-formation is not
found in soap solutions. At the same time, these solutions do not mow v+~~,~'
a noticeable increase in stability of the emulsion.
A similar change in viacociity is shown h,.
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lure 4y ,
aorreepondi~ with the 1mo41n r- o'.'
dat ~r the geITt ini ~o~
~ other
colloidal, eysteme there i f
e
Y
S
SA
In conclusion we will
j r~r"
the surf aca actibity of aodium-
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with dacreaae in temperature.
The abnormal, viscosity of tha dia erai~
p ~ medium and itrd d?pondenoe
upon temperature are fully revealed by the y ecntleion viscosity; this is
clear from the cusrves of 8'ige 5, which ra r
k /~ -~~IA.~,,~, p ardent one of many oondubted
Tzotro is v
p iecosity also appears in emu],sione and i eresed
s
xps
,
y a],ooho ae 4( 2 C tcti
(. '-4 c*L.t& 1A
, Bol,utiana waitlcer than 0,06% I~raa 4?'`'%`" 4 "4 cat 4v~
tiaally do not and do ~
not exert any influenoa upon the otabilit
Y of emu/einna prepa,rod with
their aid,
E' aoxution? of ~~r 'uR 1
1 oieate and
set 1
'I b The tomperstore of the mixtur? of ifio 'atwW~ %
ti y inf loons o Q the
progAa (fi
ound in the preoent o(LBe an inoreace in
M t #4& iw oQ~ rte,,
if the abnormal emulsion viscosity in the preaence
of cetyl alcohol in our
The temperature dependenc? of viscosity ie unueuA],
].y ohAraeterist~,c,
preoeuroe. These points on thero~y~a are indicated b ddotte
by d lines
proc1ches the --.----:.t of the initil meneuremont f~
a ler
by the fa.at that the zoo point in. re seta '
V c/ Jd- p d meaouremont-- more e&mi R
i
testa had been chiefly due to the deformation of the
particlea, then tire
could not have explained by third means the
?C AAA4ItW' ..
viscosity at preer~uree depends upon the atructux'k formation of
st)ticture with docreaee in temperature. Thus the abnor
~ w mal emul.ai on
the djpersive medium and atabilizer ablution; but the rreeence of
benzo1 drops apparently increases the capacity of eoa
p..alcohol mix-
tures to gelatinize in the~ water layore between the d.rops.
oheate and cetyl alcohol mjxtures~ 8y the maximum bubble pressure
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i
method we measure th
d the eurfnao tension on the/boundary of aeparntion.
Howover; the maaauremonta on the eurfaoe of baneol..water separation did
net feed to 1vd, uniform reeu1te beoauee of formation of a visooue
f i 1m of alcohol and soap which made tho work ve xy dif f i ou1t ? In eaary
oamn; the ourvea of figure 6 ehow tho inoreaae in eurfncc iaotivity of
the mixture in weak equally,.ooncentrated eolutione. However; the eur-
faoe tension of the ndxturo becomes higher than that of tho original
soap solution. This is due to the formation of heavy mioefoe which
have lower Eidsorption on the eurfnoe.
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Acta phvs. Chim. UBSS 2 , 779, 1935
3, 451, 1935
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In eummeriaing, we come to the omolueion that with suffioient
ootivity of the stabilizer end strength of the adsorption films the
unusually high stability of the studied emulsions is dependent upon
the ability of the et*bili,zer solutions to reatore the etruoturea
thixotropionlly in the emulsifying prooesa, which impeded the ayetem'e
layer] motion.
ono ueione
'rise in suability o? oonoentrated omulaione,
1,
it iii proposed to use thixoropio eolutiona of surfaoe-native eteibi-
'
iSrVtM++R - ~,t
w- VGt
,
the etauotur?e die-
liaera which ~dn reetoxe ,
rupted in the prone:3a of emulnifioation.
2. It was ahown that the use of thixotropic solutions of a
mixture of eodium oleate and oetyl a1ooho1 leads to an unuai* y'
'r
e erf inorease instability of oonoentrated emulsions whioh do not
separate for very long time. ~ 4t4*&
3. The following were studied s the visooeity of mixtures of
sodium o1eate~ end netY1 alcohol"' various oombinationa, the via-
,
CO8ity of the emulsions obtained with their aid, end the influenoo of
temperature variationa upon ~r ~ . '- 4 "~'?4-
4. The influenoe of aliphatio aloohole (homologous anrios )
upon the stability of concentrated emulsions was studied.
Leningrad Submitted for
Teehno1oGioa1 Institute Publioatiof
ice;; Lensovet (Leningrad Adm. Distriot 5 Jan 1947
Bibliography
1 R binder, p. A., Koll. ?,h. g, 157, 1946
2. Kremr ev, L. Ya., Trudy LKhTI1 3, 63, 77 1936
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*FNDw
i1
I i
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3. Rebinder P. A. ZhRKhO, 58, 524, 1926
Zxi. Fie. Kim, l 533, 19,C A
I'ev. Aoad. Soi, ?8R, Chim series X39 196
Rehinder, P. A. and Trapesni{cav, A. A., Zh,Fis, Khim ,
12, 573, 193e
4. Trt1mud, O. L. and A1ea1er, S. C., Surtaoe Jft6et8~
CTTI 1934
,
5. firemnev, L. Ye. e-nc1 Rhasina, Yu. 0., Trudy LKhTI
7, 35, 93, 1939, ,
6. Sohul1narn, I. If. anti Cookbain, L G., Trans, Far. Soa
36, 61, 1940 ,
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figure 1. Influence of alcohols in bensol upon the stability of an
emulsion. I - butyl; II - emyy1= III - octyl; Iv - cctyl alobhole;
v - volume in of the i% eodium-oleato solution separating; N -
z..'?7 figure . (a graph) Relative viecoaity / of 1~ sodium..oleate
a
o;floz' v us iz'esmires d cet a1c h 1 c ncentrations
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L142..Z I 3iguxe 2. The influence of alcohols in a i% sodium-olea,te solution
upon the stability of an emulsion; I. butyl; II .. anr1; III - octyl;
Iv ,- oetyl alcohols; v - volume in % of the eoddium?.oleato solution
 t~lcohol.
figure 5 (p, 24) iacoeity of an emulsion having 60 ,( ~)
r
benzol i
a
di
n
eo um.oleate solution. The y
pf the oetyl
EI1f111~1n1 4M 41%w
i..
nz.l
4~ ~~2 '
Figure 6p. 2Li) Influence of netyl alcohol upon the eurfaoe teneionr'
1.aodivu~a~loleate aolution; 2 equally concentrated eolutione of sodium
o] eete and oetV1 a3_cohol
.
If
I
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lire W a graph
(p. 2k)
py. The influence of temperature upon the vinooeity of a i% aodiumgole~to
fl I q 4 LI wM l iii i' _ __ __ - _. _ __ _ _
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ThixotropZ of the vienaeiby of iiixturee of eo8lum+loloata and oetyl
sioohoit relative vieoooity !/ / y,o of the misEureo.
Relative Vioooeity of squally Concentrated. Solutiono of Soap and Cetyl
Al cAh.
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