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UNIVERSITY OF NEBRASKA. UBRARIES
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NAME AID ADDRESS ' EETE
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SFRSAPW HtS880SBS A® SraiADIfG COEFFiaiffiSfS
m ciEmxi sxraoattBoss m fat®
by
James Edwsu?d Sh®i*stoiF
A f « iis
Pr®s#i*%«i. to the Faculty of
fh® Gradna to Gollog# ixi tb® tJnlvorslty of Nebraska
In Partial Fulfillment of Requirements for the
0®p*®@ of Doctor of Philosophy
PogNUrt&MKte of try
Ghher the Smponritl* of Dr* t» 1*
Lincoln, Nebraska
am® 19» 19a
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UMI Number: DP13931
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fhe author wishes to ©xpress hi#
o&Mwr# appreciation. to Dr* 1* S*
\7asliburn who suggested and directed
Ibis InrootlgotloKu
m Is alee indebted to 1* X* da
Pont de XDMttro ond Company and to the
Standard Dll Company of Indiana for
research fellowships.
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*vkmx §f GGlTSifS
t&m
I. . . * • » * * » « • • » • • * * # X
IX* Materials * * * • * • • • « * • • • « • * * • * X©
XIX* Apparatus* * * * , » * * . . . • * » * * • * • IX
X?* g^erlmoiitaX. # , * ♦ . » * * . * ♦ *. • « • • • • St
A. MtturarwMttit of Surfs®# Tension. » * * * * * S©
S« Mooouponont of Xatorfaoisl Tension. * * * * 36
0.* Measurement of Spreading Pressure * * * * *■ 44
B* ®a@ Spreading of SetwtAia* * * * * * * * * 89
I* Comparison of Spreading ©eeffie lent* and
Spreading Pressures * « # * • • « • * * • • 86
V* Dtseueeioft of Results 68
¥1. Additional ©bsermtieits * # * # * . * * . * * ♦ 95
A* The Iffo ut of Water DissoXvfed ia the
Organic Xifuids upon their Spreading
Prosstir®. * * * * * * * . » . . * * • . # * 95
1* Sotemixiatlott of Spreading Pressure from
Snrtae# Tension Measurements by the ling
Method* ♦ * . * * * * * 1©§
¥XX* Summary * * . . * „ * # * * # . * . * . * * # # XXS
libXl«p»«j4iy* • XX4
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1
I. IHTRODTJCTIOH
A* Spi*©adlsig Oaaffialaat*
Although tb® phm m m m of a liquid spoataaaaaaly spread-
tKg upon a horisonf&l n v fw t has bom familiar for a long
1*11,5
tim©. fjawirtae fiyid oo-workors appeal? to have been the
WiFpMfcPa,*^ j* TIB *pF *W' «**^F a** If W « •^! *w:
float to present a attqpeofeiMiaiv* theory treating this behavior,
#T***h_. iBi<4^ wiorailo J1i —r W I y»rf V-t. u-■. nu^.s %—b ■»*e■ ^e -ar-nl ' - , -m» . — JoSi j£d ^3i|t JfP iiMe Jd9 a—-an -Wa ^1® 1*1*1E' Jm t-~-© — ^ n'<3» d.iU,# jSd fcfbcl — ■■y - TOHFi^ifc arkins ajttlfmlA ilj3
■ 4 ■§,.§»? §
0£n#b®rg, Harkins, and Hiller to cover a ll degrees -of
aaraadimm of any liemid or solid moon any uniform surface*
qpwlltatfcr# atatMMMta
lag had been given jrewletisljr, but non© had b««a generally
' f
accepted* Vfe* Vdunam triangle of ft**** led to th» ©oa-
elusion that a liquid B © ill spread upon a liquid A if
SfA > i-tg ♦ wher® ff^ represents the iaterfaoial
tension between the two liquids, m& SfA sad STB the respec
tive surf*** tana Iona* fh# condition for mm-spremdiitg was
St.. < s» # !*»«♦ '$hi* aaaaaad th* surface tension of the
A B AB
sub-phase to b# equivalent t* a for*# la ©a© direction, sad
fee surface tension of the spreading liquid* together with the
i&tarfaalal tension, to be equivalent to far**#
site direction* An «rib*l*a*#4 far** was assumed
tto© edge of Mi© added drop of liquid B* this f@*»iatiok was
*ch on- -ca*. emeA** d**3 «nr* rfca-i*—ff y«*«** wi>*!t*&h•* '* Mm3n . ^i eth■— sr or ^ noStti* s*-■ pimi arn^- eMh| a*b dJs iSa mg* wo<u■ l?%d oaeu* rMfri*
Stadia* by £*rd laylei^h led him to the c@a@lusi«
that all liquids spread on the surface of ©lean water*. 1©
concluded that whenever th*r* was aj^ereaily a ease of
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ft
it was caused by eentasfttoatlea on fee. surface*.
‘ 'feather gonerslisu'tien c oncoming spreading 'and nen-
11*12
to this
vlew''<»Xy those- liquid®. Whose molecule#: are;polar 'or -contain
polar groups* spread m water* m e«* lamgsalr claimed that
IS
par# hydrocarbons would not'-spread upon water. ■ 'Hardy- '.bad
-previously 'reported that pure saturated hydrocarbons did not
spread "upon water iwrfaees*
'1
She -theory' of' SSa^kib# defines - a single -quantity- for'
each liquid Which- is a measure of its tendraey to spread upon
a given surface, This ©ferae terls tie •quantity, dovolopod
entirely fro® fee ttewo^&oai##. of surface-#* is -called the
spreading coefficient of -the .gif-on liquid upon the given
surface* ■ Fortunately*. i t bears- a stasple relationship to ‘fee
surface tensions-of fee spreading ®aferi«l and fee sub-phase
and the- In terfaeial' tension feetm m fees# .■substances*. I t
can* therefore* be eolsulntod for any system for Which fees#
-feree boundary t an*lour are known or can be as soured* Th©
fact'th at no- -satisfactory jweOeduro ha* yet bean devised to
measure - boundary teas-leia* involving solid surfa ces*. limit®,
this .theory only in its. .oxpor&MOtol applleatioss to-fees#
; materials* -dcasiderlng fee great abundance and iaportmee
o*■*. f pwc«r* Bot*. I—c. ess**e. s *Fs Ma'WvwWo*- imvji ^*nHk g *£f*-.*i* lm# aat. na .f£*i*#l' m i.*?.*e rm&at*f .iSo m *u* MpB Io*, ffcnat'tf solijt'd
surfaces* feia expirlaembai limitation is indeed a very
serious one but doe# not affect fee validity of the feeery*.
Harkins1 method of predicting fee-' tendency of a substance
to- spread is based on fee changes in free energy involved -in
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