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6/01 c:/CIRC/DatoDue.p65-p. 15

 

A T133 3
SUB3ITT33 To T33 FACULTY
03
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33
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1929

CONT. KITS.

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Calculation of interfaciel tension....................{

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IITAfHNflITIOI.

The object of this work was to stu‘v the effect of a
potential on liquid-liquid interfaces. Both the crpillary and
drop wei 11t methods were used to note the cnanée OI inter-
facial tension produced by potentials rwn*ir= fron seven and
.cne half volts to several hundred thousand volts. This worx
is divided in‘p 0 three parts.

The first consists of a study of the e-fect of vary-
seatials on different coiceutrations of sodium 0 cats
solut.cn aJaiist benzene, mutually saturated with each other
and measuring the c11anQe of interfacial tension thus produced.
Ine second art is a study of the behavior of difisr-
eit or“an c liquifs agains water, nutually saturated with
each other, using voltages as hi n as several hundred

q

thousano volts across the interf: the cafi. llArwr

(3
(D
H
C.)

The third part is a re.etition of tne first; the

j '7‘ ‘TP‘ ‘- n, ‘ ‘- A q‘ ‘I. . A N.
crop *6 dub uetnxc 08in.

L
5
[‘3
(D
C“:
H
, J
C:
C’"
(D
{J
{‘1
O
"9
Cr
f‘)
(D

car 1111: y
netnod. It was attenrteo to show that the nollecules Oi an

enulsifyin; agent such as ooiun ole were orient * 13C

frcn tLeir normal direction of orientation or the concen-

_&.

C

trw

}-‘.J

ion 0 the seas noilecules in the interface is Chan/ea

(

under the influence of a certa n direction of fotential.

It we s atten Ifuxxi'to snow tnai.tflre int3rfacial.suL?

:r-
(L
H
L.)
' D
l-J
C
\b
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O
w
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n

0
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w
Cu
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0
p
O
}.

WIS i:.creas ed under
potential and deer-eased when the potential was reversed. A

study is als made of the influence of a jotential on the

p.

epee of saturation of a second liquid such as water in a
water-oenzene systen. This is snoWI bv the difference of

interfacis 1 surface telsion wit11 and without a potential.

THE CAPILLARY HETHOD WITi POTLHTIA S BALE KG FROJ 7 1/2
T0 110 VOLTS.

BJJZJI'L‘ ASA IIS SODIULT OLELLTE S UHIOIIS.

DESCRIPTION OF APPA ulkTUS AID {A 3”ILLS: The apparatus used
in studying the effect of a potential on interfacial tension
by the capillary method consisted of tho lar e 3lass tu
one lon3 with a diamet er of 2.12 cm., and a short one with
a diameter of 2.C3 cn., connected by a capillary of fairly
constant bore. The capillary was in an upri3ht pOu‘ ition.
When two fairly immiscible liquids were put in the systen,
the meniscus was brcu3ht some"here ne ar the center of the
capillary. Thrcu3h stOppers at the spe nin3s of the lar3e
tubes, adjustable platinum electrodes were placed.

Water or aqueous sodium oleate solution was placed
in the long lar3e tube and benzene in the short lar3e tube
with the meniscus in the capillary. Two motor 3enerators,
producin3 direct current, were used, the one producin3 a
potential of 110 and 55 volts, the other producin3 a potential
of 15 and 7 1/2 volts. A millianeter was pl? ced in series

with the capillary apparatus.

METHOD OF PP OCEDW 3:- The 3lass capillary apparatus was
first thorou3hly cleaned, -Hot cleaning solution was first
forced throu3h the capillary. It was then rinsed well and
then steazned with live steam for some tine and then dried.

The two liquids which were mutually saturated were
then placed in the apparatus so that the meniscus between
the two liquids was in the capillary. The electrodes were
then placed in the two liquids. Because of the alnost per-
fect non conductin3 liquid in the short lar3e tube, the
platinum electrode was brou3ht close to the meniscus in
the capillary and adjusted continually to keep a constant
distance between the meniscus and the electrode.

Benzene and sodium oleate solution were used with

a pot ntial raW in3 f won 7 1/2 volts to 110 volts.

CALCULATION OF TITS {FACIAL T3351 N BY THE CAPILLARY ILT TOE.
To calculate the correction of levels in the lar3e

tubes due to unequal surface tensions, the formula was used-

lézsssdsal_2£-§2liali_iiii22§isri - H (1)
(Density)(9d1)( )(r )

which reduces to the fornula-

 

Ldynes/cn. of sol'nLLLEl ,
nsity)(981)(radius)

M
V

H (

The static surfa ace te1sio1 of aqueous solutions of sodium

oleate saturated wit h ben ene is found on 3raph (1), and may

J

be substituted in formula (2), aid the height (H,) due to
surface tension of the sodiun oleate solution is found at

o 1 ‘I I 1 _ 1 ‘ w. . . . ‘...
20 C. Tue nei3nt (H,) of tne benzene in the lar3e tuoe

 

:1

 

 

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QR. H.

 

 

due to surface tension of the benzene saturated with sodium
oleate an‘ water is found by substitutin3 the value of the

surface tension of benzene saturated with sodiun oleate and
water at 2C 0., which is practically constant for all con-

as

centrations of sodiun oleate at 23.00 dynes per on.

To calculate the interfacial tension between the
benzene and sodium oleate solution, let A equal the hei3ht
of the benzene in the capillary apparatus above the meniscus
in centimeters and B the hei3ht of the sodium oleate solution
above the nenisous in centiieters, then;

(A~Hz)(C.879 (B'H,)(1.C) :C

C is the hei3ht of a column of liquid with a specific 3ravity
of 1.C that is supported by the interfaciel tension between

the sodium ate solution and benzene in the capillary, and;

O.CS§ Sodiun Oleate A3ainst Benzene.

I

 

 

Volts Hei3ht of Hei3nt of Hei3ht of Column of Interfacial
Sodium Water Suo- Tension in
Benzene Oleate {eniscus ported by Dynes/Cn.
Solution. Interfacial
In 31. In Cl. In Cl. Tension, Ca.
0 12.C7 11.C3 6.13 C.33C 22.35

b s
I
M

Q
0
U1
0
U1
U]
N
D
D
Q
Li
(J \
O
C J
4‘.

U1
no
0
0
.J
l
.3
P)
x»
O\
O
A
O
u
L)
-J
h:
4 ._
0
IO
.N]

C 11.92 1C.81 5.3C C.)25 22.37
C 12.5C 11.42 5.13 C.317 21.92
11C -12.57 11.52 4.43 C.C16 1.13

O

 

 

 

 

 

 

 

\ 3"
T1“. .'../..J

6.1% Sodium Oleate

3 II.

A3ainst Benzene.

 

 

Volts

C.C
7-5
7.5

U] 0
(7

U!
00

b1
Ul
O O

U]
U1

110.0
110.0

110.0

Benzene

In on.
12.18

~12.17

12.18

11.42

-11041

11.42

11.16

~11.14

11.13

13.75
“13074

13-78

 

Height of

 

Hei3ht of Hei3ht of

Sodiun
Oleate
So 1 uti on
In On.
11.33
11.34

—11.33

10.15

1C.17

~1C.13

no
10
(.7\
b1

[0
O\
10 U1

|
K)
o
O\

Weniscus

 

Column 0

Tension,

0.210

C.CC1

C-335

 

L

5

Water Sup-
ported by
Interfacial
Cm.

 

Interfacial
Tension In
Dynes/C-.

14.40
1C.46

15.51

14.57
am
13.17

 

 

A '3'? 1
T“. .JLJJ

III.

0.5} Sodium Oleate Against Benzene.

 

 

Volts

kn
U1

u]
\fi

11C
110

Height of

 

 

Hei3ht of
Sodiun
Oleate
Solution
In Cn.

11.54

1

1103

i

1105')

12.97

12.93

\O
O\

 

Hei3ht of

Ieniscus

In On.
- )
)0 1"1'
4.67

5.45

7.C3
6.4:}

7.53

 

Colunn of
Water Sup-
ported by
Interfaoial

Tension, Cl.

C.CQ4

C.CC6

 

Interfacial
Tension In
Dynes/Cn.

6.41
0.45
1C.42

6.7
eC.C17

13.63

 

 

DISCULLIJH:- I1 all c: see when the polaritv of the so

U

oleate solution wrs yositive and the pola.itv of the be-1z ens

ne3ative the interfacial tension was decreased and when the
potential was reverse?, the interfacial tens on was increased.
The eXplanation which innediately su33ests itself, is that
the concentration of the sodium oleste at the interface has
chan3ed or some of the mollecules in the interface have re-
oriented thenselves under the influence of the potential.
The fact that t:1e interfacis .l tem1 ion could never be lowered

below zero {within eXperinental error) a1i could not be

benzene

J
<:
{a
c,
(D
*3
in
5

increased above the interfacial tension 0;

fl

r3ues for t1e fao t the t 1.118 oh 5. ".31 e of ne nois us was due
to a chan3e of interfao al tension which was due to a chan3e
of interfacial tension which w.s due to a chan3e of concen—
tration or a reorientation of the mollecules of sodium
oleate in the interface.

If we loos upon the (-COQIa) as the ne 3ative end

of the soap mollecule and the lon3 hydrocarbon chain as the

iun

p.

,ositive end, we would eXpect when the polarity of the so
oleate solution was positive and the Den me e ne 3ative th
the interfacial te.1si01 would be decreased as what was act-
ually observed due to a hig her concentration of sodium oleate
mollecu es in the interface due to the influence of the pot-
ential. It would also be eXpeoted that when the potential
reversed tnat there would be a decrease in the concentration

of the sodium olea te nollecules in tn interffce or a re-

(D

orientation of a oart of the

3,..4

1.:

13C fron their

7‘»
|._J
r

\ U
I!)

J

301).

original direction of orientation thus pro duo oin3 an increase

in interfacial tension as what was actually observed.
However, these results are contrary to the results obtained
by the drOp wei3ht method where the sodiun end of the soap
mollecule acted as the positive e.d instead of the ne3ative
end.

One of the objections to the technique of this method
is that when the platinum electrode in the benzene is very
close to the neniscus but does not touch the thin filn of
sodium oleate solution which crawls up the ca,illary between
the benzene and the glass, no results are obtained with a
potential, or if the meniscus does change it is so snall a
change that it dould not be noticed. However, if the elec-
trode is allowed to touch the thin filn of sodiun oleate
solution that crawls up between the glass and the benzene,
then the results are obta’ned as shown in the tables. Due
to this effect we cannot be certain just what we are measur-
in3 and cannot arrive at definite conclusions as to the
chan3e of interfacial tensionlas can be when usin3 the drop

weight method.

THE CAPILLAAY. YET HOD ‘u'"IT.{ riIG H POTSZITIEJJS, USING PUB. E
LIQUIES AGAIKS WIXTER.

DioCRIPTI N 0.? PPlPJ TUS A”D 13TJ;IAL3.- The apparatus
used in this worK was the same capillary apparatus used in
the previc ous discussion. The source of potential, however,
was obtained from an electrostatic machine run by an electric
motor. In this way a potential of several hundred thousand
volts could be obtained provided the leakin3 of electrons
was minimized out 11 so me cases the leaka3e throu3h the
capillary apparatus wa s considerable thus decree sin3 the
potential to possibly 25,CCO volts.

The lisuids used afiainst water in the sgsten were
be17 ene nitrooenzene, anylacetate, amyl alcohol, ethyl
bromide, carbon disulfid; and carbon tetri cl1loriie

Benzene was also used a3ainst sodiun oleate solution.

JETJOD 0F PROIZDU33z- The nethod was the sane as that in
the previous part. The meniscus of the two liquids was
adjus’r ed to the center of the capillary and the chan3e of
of interfacial tension was
calculated in dynes per centineter.

In this case, however, it was not necessary to
brin3 the platinum electrode in the second liquid near

the interface when a potential was applied.

l0.

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11.

DISCUSSION:- This effect does not seen to be a change of

int rfacit l te_1s on but more of the nature of ttrection

3‘1)

and repulsion between unlike and like chargeu Dooies and
dependin3 partly on the dielectric co.1stam1 and the Specific

cond liquid saturated with water. In all

0.)

nature of the 8
cases the meniscus was cogcave to the water side altwlou h
it sonetines te1ded to flatte1 out Wlen 3 hi h potential
was imposed upo1 it. It was calculated that the CJ&;Jd

of int rfacie l te1sioa using benzene as the second liquid
was about 65 dflr1es c1., less than hcr1al 31d the normal
iw1txrf cial te1 io;1 is only 34.5 dynes/cn. Tie fi Juree
shown in the taoleo show relatively how differe1t liquids
are affec ed by high potemtials. This sane effect will be

obeerre

Q

Dy merely touching the platinum electroles to the

la 5 of the two ends of the rmnillthj apolrutus thou h

U1

5
not so good. IA the cese of begzene and water, water seems
to collect in the benzene on the sides of the lar»e tuoe.

Also violeat agitation t: hes place on t

benzene but Jot so on the water surface.

Th3 Dee; @3133? ijTMOD 331:} 3 c VOLTS.

F)

‘i' 1"“. 91.111- "~- ~ m e r
.- axe-ll. J») Lewis . Li. L 2:41.91“); - L18 '«UTLQJ‘CA. tils
‘

thick welle

E:
(1.
Cr
(1)
'1
O
‘ J
0
U1
.0
4:-
.J
H
H
H
ss
0
C‘"
CD
*3
*3
L)
(D
C?
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F ~<
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07

3lass carill.rJ Wi a ‘roudc flat surface, the outside

hein3 polislle;. The pipette had a volune of 5.22 c.c.,
bot"’%:;1 the rinxkiatagxis o; reitHer*ss«;e of tire eglfiirneqent.
Hear the top of the pipette a. platinum tire was sealed
throu .11 the lass aao brought down. to within an inch aild
a half of the tip. A second electrode is the fora of a
rin3 with a dianeter of 1.05 on., was placed around the

for11n3 drop at the point where the crop broke off.

91.
'.

stopcock at the top of the pipette allowed air to enter

("fi

the pipette slowlv from a lon; drawn out 3lass capilliry.
The resistance of the 081pillary to the pasra3e of air
was so eat tiat it allowed a drop of water to fall in
oLLeei‘ about every fonr'augnrtes. 1A calciua chloride take
was placed in series with the capillar y so the air was
thorou 3hly orieo before fascia; thPONVh the canillarv so
that so moisture coula collect in: 'e the capillarv aad
obstruct the passe e of air. In trier to a1just the level

of the liquid in the hioette, a suction tube was coanected

betwe n the pipette and the capillary. This could be Shut

e flafliiufiw,l

..
.‘.3 3‘ 131

H:

<1 A c. - 4- ‘- I r. ' -, ‘.~ .- A 1 - - a -1 _-- -‘
uuries wiea tqis suction tune to act as a poet 3 Li?

potential consisted of a small notor

q
,-

3e erator which produced aoout one half an anoere at Joe
volts direct current. A switch was arran3eo so the the

L

current could be easily reversed.

'5- -. . . -n . o ‘I . '1, ‘e .
fern/111Q concentrgtiois o; sociun oleate SClJbiC“
was use; a3ainst oenzene. Pure Water was also used a3ainst

f " ’fi ‘\""“ ‘fi "1 fl )"x ’1 "‘ "1“."7" ‘ (T11.

hei.oe on inooeeouuez- .ne water or sodiun olea 3 solution
was C“&Wl up into the pipette and then put in series with
the caji lary for lettin3 in air. The tip if the pipette
was placed about one half a 01., below the surface of a
{er of benzene. It was then nade sure that the sodium
cleate solution covered all of the 3round surface of the

pipette tip but did not ccawl up the polished side of the

tension under the in... lucnce of a potential was due to the
presence of the sodium oleate in the interface runs were

made usin3 pure water and benzene. The followin'

3 runs were

made and the data graphed:-
The two liquids unsaturated with each other.
I. odd drops -zero potential
even droos -wat9” “
‘ 0'1
2. odd drOps ~zero potential

even drops ~

C‘s
02"3

,,)
(D

.4

each other.

with

Gd

segturuit

wo liquidSe

n.
[J

c.

-1163

n;
fiJ

3
Z

5
hi...
n v

d
d

7).

-

re

:zted

tur

4"

0
UL.»

mutually

33

even drops

~23PO

odd drops

(0

n
u’J

droys

-

odd

15.
TABLE ‘.
Water a3ainst benzene «unsaturated.
Volts Polarity of Polarity of Tine of drop
water benzene forqation in sec.
C C C 233.C
3CC - '+ L+).C

3C0 — 4' 245.0

3C0 — + 273.C
C C C 271.0
3C0 - -+ 262.C

O
O
[U
K)
(J
0

CO "' ‘1' 2710:

\A

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I'Ml. tic/V

7/)» e of dm

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T1": 31.2 VI I .

Water a3ainst benzene -ssturuted.
Volts .olrrity Oi Polarity of Time of drop
water benzene fornation in sec.
C C 223.5
c c 227.5
3C0 * - 223.5

0 . C C 235.c

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TA 31.3 IK

C.1fl sodium oleate solution a3ainst benzene -saturated.

Volts Polarity of Polarity of Time of drOp
sodium oleste benzene fornation in
solution

,C C C 114.0
3CC + - 126.0
C C C 11C.3
3C0 + — 12,.5
C C C 113.C
33(— ‘1' - 2.205
C C 0 112-5
3C: * - 121.3
C C C 112.3
3CC + — 126.3
C c c 113.c
)CC + — 123.C
C C C 116.;
399 * — 123.L
C C C 119.C
3L0 + - 133.c
O C C 122.0
SOC + - 129.3
C C C 112.3
3C0 + - 133.5
C P C 115.0
3C0 + - 133.c
O C C 122.C
3CC + ~ 136.5
C C C 123C
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TA;Kl3 X.
0.15 sodium oleate solution against benzone -suturoted.
Volts Polarity of Polarity of Tine of drop
sodium oleate beozoie. fornation in sec.

solution.

C C C 224.C

3CC - + 216.0
C C C 213.C

jCC - + 210.C
C C C 22Co5

3C0 ~ + 221.0
C C 223.0

3CC - + 227.C
C C C 23C.C

3CC - +- 235.C
C C C 237.5

30C - + 257.C
C C C 244.C

300 ~ + 24).C
C O C 253.C

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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21.

TA3L

XI.

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C.C15 sodium oleate solution against benzene ~saturuted.
Volts. Polarity of Polarity of Time of drOp
sodium Cleats benzene. formation in sec.

solution.

C C c 2134.3

3C0 - + No.0
0 c C 193.0

3CC — + 179.C
O C C 2C2.3

3C0 - + 136.5
0 f c 217.c

30c. - + 2c4.5
C c c 216.C

3Cc .. ‘1' 2C3.3
0 C c 211.0.-

3CC ‘ — + 139$
o O c 213.0

BCL - + 209.0

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DISCUSSIONz- According to Ant onow' rule, the interfacial
tension between two liquids is equa to the difference of
the surface tensions of the two liquids mutually saturated
with each other. However, before these unsaturated liquids
in ccnoact with each other becone saturated there must be

a diffe erent interfacinl tension. It is s: own by the first
two rr'xns (315. 516) how the potential no matter which
direction it is directed speeds up tne saturation of the
wa*3r by the benzene,(the benzene was already saturated
with water) and thus lowers the interfacial tension which

decrerses the size of the dronland this in turn dwecre+ses

sane system exceh ct thet the two liquids are nutuully satur‘

steed with each other. These curves oracticallv coincide

A U

with each other which Slows that the iotential has no in-

H

fluence on the interfsci l tensicmi of mutually saturated
liquids.

The next two curves (315. b 1C) are systens of

\C'

0.1% sodium oleate solution a sin

C0

t benzene mutually satur-

C)

etc

Q.
21
Ho
C—r
:3
(D
SD
SJ

other. In the case of the polarity of the
sodium olea te so ution bein5 positive and the benzene ne5a-
tive, there is a decided difference in the len5th of tine
for the drOps to form (avera5in5 about 13 seconds). We

d eroect if we consiler the sodium as the pos tive end
of the soap mollecule that with this direction of potential
there would be a tendency for the soap nollecules to re-

orient themselves at 180 to their nornsl orientation in the

interface or else there would be a tendency to decrease the
concentration of the soap in the interface and thus increase

the interfacial tension and thus i;crense the len5th of

,)

CO

8X8.

0

tine for a drop to form and this 1 t1? what happens.

he ciel tension

m

nterf

Ho

sodiun oleate t

in about 11.2 dynes per cm. Thus if the volune of the drop

is increased about (135/12C) the interfacisl tension is
incrensed about 1 1/2 dynes/on.

Usin5 this same svstem with the potential reversed
the two lines of the 5raph practically coincide, the zero

potential line probably bein5 a trifle hi5her. With the

1

potential in this direction sort soap nollecules should be

ccncentrrted in the interface and thus the interfaoisl ten-

‘ —.

sicn lowered and also the tine 01 drop fornation lowere".
dowever, the concentration of soap in the interfece is
Very hi5h at C.1§ sodium oleate solution and the few nore

that could he crowned into the interface would no hve a

A

very great effect. In order to overcone this a C.C13

I

q. ' I ’ ‘ ' If." w o‘. q ~ ~ \ a h
sociun cleate solition has used and the last 5rnph Was

' . f— 1 x. ‘
obtained, \313 11.). In this 5raph, altnou’n very irre5ular,

\J

there is a deoilel lowerin5 of the interfacisl tension br

3
the potential. As the concentration of tne scan in the inter-

face is very sqall at C.C1 .1

1")

f tire potenti
in ooncentratin5 more soap mollecules in the interface is

quite 5reat. If the ori5inal interfecisl tension of C.C1Z
so‘iun oleate is 32.2 dynes/cn., and the voluae of the drop

., then the

l\)
4;.

f"! ‘Ofl’r Yr 1? \\. '
U ‘Id—‘UULK/L‘KJQ-

1
1 - . - v: L A .. ‘ ., L. ; “- 4 - it. 5
1' T113 :3?ch ‘3f Gna‘d1.lPL-.ti\/-L CL 11:51-81". 2211:.CsU3LL SO-.-].-1'Jl'\/.LL3 1-1

' L ‘- > r ‘ '1 -~ ‘A .- a . ,r- L‘ 1; a“ ‘.
contact witn econ otner is nastcne' oy the use oi L

2. The interfeciel tension between two nutuullv saturated
liquids con not be chanted oy the use of a potential.

The concentration of sodiun oleate in the

\A

be altered or the direction Ci orientation chan5ed with

the influence of a potential. In other W‘PLS, tne inter-

fecisl tension nav oe either increased or d>creased in

C“

+.
0
+3
Lo
1b
CO
C)
C:
H
’1‘
.21
C,
F4
(D
{J
(1'
«D
e
I
1"“
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(L
O
‘,..
".J
(D
la—J.
L.)
U"
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r—h
L)
c—f
\l'
'3
1—1')
0
(L
C)
(L
L3
1‘:
<:
CL
'1)
CO

1- 1+1. A- .-.- u - . .. ,-- “-7 .
tic1i31 .nie Shokiilq e n. were: t:r= 1cmniti./e €}ih Laid tnie

1 -.

lon5 hydrocaroon 0‘

D- J

This work was perforied in the liedzie Clicnica

Laboratorv at iichi5an State Colle5e under the direction

U

0

f Dr. EWi5ht Larbell 3win5.

53 04134
3499030....

“Em

 

4

MICHIGAN STATE LIBRARIES

1293 02244 8058