Louisiana State University LSU Digital Commons LSU Historical Dissertations and eses Graduate School 1966 Aggregation and Solubilization Properties of Decyl, Dodecyl and Tetradecyl Quaternary Ammonium Salts. Joseph William Goerner Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: hps://digitalcommons.lsu.edu/gradschool_disstheses is Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and eses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. Recommended Citation Goerner, Joseph William, "Aggregation and Solubilization Properties of Decyl, Dodecyl and Tetradecyl Quaternary Ammonium Salts." (1966). LSU Historical Dissertations and eses. 1194. hps://digitalcommons.lsu.edu/gradschool_disstheses/1194
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Louisiana State UniversityLSU Digital Commons
LSU Historical Dissertations and Theses Graduate School
1966
Aggregation and Solubilization Properties of Decyl,Dodecyl and Tetradecyl Quaternary AmmoniumSalts.Joseph William GoernerLouisiana State University and Agricultural & Mechanical College
Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses
This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion inLSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please [email protected].
Recommended CitationGoerner, Joseph William, "Aggregation and Solubilization Properties of Decyl, Dodecyl and Tetradecyl Quaternary Ammonium Salts."(1966). LSU Historical Dissertations and Theses. 1194.https://digitalcommons.lsu.edu/gradschool_disstheses/1194
VITA .................................................................................................. 77
L IST OF TABLES
TABLE PAG-E
I . R e su lt s o f S urface T ensionMeasurements on th e D ecy l andDodecyl S e r i e s of D eter g en ts . . . . . 3^
I I . Wavelength o f Maximum A bsorptionPeak o f Benzene in D e c y l , Dodecyland T e tr a d e cy l S e r ie s o f D eterg en ts . 39
I I I . Peak to V a l le y R atio o f Maximum A bsorption Peak o f Benzene in D e c y l , D odecyl and T e tr a d e c y l D e t e r g e n t s .............................................................. lj.0
IV. C r i t i c a l M ic e l le C on cen tration s inthe Presence o f Benzene fo r D ec y l ,Dodecyl and T e tr a d e cy l D eter g en ts . . lj.2
V. S o l u b i l i z a t i o n R e su lts for D e c y l ,D odecyl and T etr a d e cy l D eterg en tsin Water and in 0 .0 5 N NaBr S o lu t io n s . ij.9
V I. E x t in c t io n C o e f f i c i e n t s f o r Benzene in D ecy l , Dodecyl and T etra d ecy l D eter g en ts . . ....................... 56
V II . D is t r ib u t io n o f Quaternary S a l t sBetween Water and Benzene . . . . . . 60
v
L IST OF FIGURES
FIGURE PAGE
1 . Surface Tension Versus Log C fo r theD ecyl S e r ie s in H2O..............................................................33
2 . Surface Tension Versus Log C fo r theDodecyl S e r ie s in H2O......................................................... 36
3- Area per Mblecule Versus the Square of the Number o f Carbon Atoms per Short Chain f o r the D ecyl S a l t s ..................................37
ij.. Absorbancy o f M ice lla r Benzene versu s C oncentration D etergent for D ecyl S e r ie s in H2O and in 0 .0 5 N NaBr S o l u t i o n .....................................................................................lj.3
5- Absorbancy versu s Concentrationfo r Dodecyl S e r ie s in H2 O ........................................... I|lj.
6 . Absorbancy Versus Concentrationf o r Dodecyl S e r ie s in 0 .0 5 N NaBr S o l u t i o n ...............................................................................
7 . Absorbancy versu s C oncentration fo rT etrad ecy l S e r ie s in Water and 0 .0 5 NNaBr S o l u t i o n ..................................... 1 .6
8 . Log cmc in the Presence o f BenzeneVersus the Number o f Carbon Atomsin the Hydrophobic t a i l .................................................. lj.7
9 . M ic e l la r Benzene Versus M ice lla r D etergentfor Dedecyl S e r ie s in H~0 and in 0 .0 5 NNaBr ....................... t .................................................. 50
1 0 . M ic e l la r Benzene Versus M ice lla rD etergent for Dodecyl S e r ie s in HgO...........................51
11. M ic e l la r Benzene Versus M ice lla rD etergen t fo r Dodecyl S e r ie s in0 .0 5 N NaBr....................................................... £3
v i
1 2 . M ic e l la r Benzene Versus M ice l la rD etergent fo r T etrad ecy l S e r ie sin H2O and 0 .0 5 N NaBr............................................... $ k
13 . Benzene sp ec tr a in Various S o lv e n ts ................... 57
I k . Bromobenzene S pectra in D etergen t and inW a t e r ................................................... * ........................... 59
v i i
LIST OP ABBREVIATIONS
DTMAB Decyltrimethylammonium Bromide
DTEAB Decyltriethylammonium Bromide
DTPAB Decyltripropylammonium Bromide
DTBAB D ecyl t r ib u t y l ammonium Bromide
DDTMAB Dodecyltrimethylammonium Bromide
DDTEAB Dodecyl t r i e thylammonium Bromide
DDTPAB Dodecyltripropylammonium Bromide
TTMAB Tetradecyltrimethylammonium Bromide
TTEAB Tetradecyltriethylam m onium Bromide
TTPAB Tetradecyltripropylammonium Bromide
TTMAC Tetradecyltrimethylammonium Chloride
ABSTRACT
The aggregation and s o l u b i l i z a t i o n c h a r a c t e r i s t i c s
o f a s e r i e s o f quaternary ammonium s a l t s were s tu d ie d
in the hope o f determ ining more fa c t o r s which would help
d e v ise a model fo r ex p la in in g the p r o p e r t ie s o f c o l lo id a l
e l e c t r o l y t e a g g re g a te s . Both the len g th o f the hydro-
phobic t a i l and the s i z e of the h y d ro p h ilic head were
v a r ied in the in v e s t ig a t io n . S o l u b i l i z a t i o n , su rface
te n s io n and s p e c tr a l s tu d ie s were performed.
The c r i t i c a l m ic e l le co n ce n tra t io n (cmc) was d e t e r
mined fo r some d e c y l , dodecyl and tetradecylammonium
bromides in pure water by means o f su r fa ce te n s io n
measurements. The cmc was determined fo r the same
substances in the presence o f benzene by means o f a
spectroph otom etrie tech n iq u e.
Head s i z e parameters were c a lc u la te d from the su r
fa c e ten s io n d a ta . The l in e a r r e la t io n s h ip between the
head s i z e parameter and square o f the number of carbon
atoms in the sh ort a lk y l s id e chain was v e r i f i e d .
A l in e a r r e la t io n s h ip between the In cmc determined in
the presence o f benzene and chain le n g th o f hydrophobic
t a i l was reconfirm ed.
S pectra of benzene in a v a r ie ty o f s o lv e n t s ,
in c lu d in g numerous d eterg en t s o lu t io n s , were determ ined.
By su b tr a c t in g the spectrum due to the benzene in the
aqueous phase , the spectrum o f the m ic e l la r benzene was
o b ta in ed . I t was concluded from the character o f the
sp ec tr a th a t the benzene was lo c a te d in the organic
i n t e r io r o f the m ic e l l e .
The fo l lo w in g model was proposed to ex p la in the
r e s u l t s o f th is work and p rev iou s work in t h i s la b
o ra to ry . The aggregate I s s p h e r ic a l ly shaped and has
a l iq u id organic core that i s surrounded by an o rg a n ic -
w ater in t e r f a c e . The water p en e tra te s in to the m ic e l le
and surrounds the f i r s t f i v e to s i x methylene groups
In the hydrophobic t a i l . This p en e tr a t io n reduces the
e f f e c t i v e s o l u b i l i z i n g volume o f the ag g reg a te .
M isce llan eous s tu d ie s were done on the
p a r t i t io n in g o f quaternary s a l t s between water and
benzene and on the a n a ly s is o f d etergent-benzen e
s o lu t io n by means o f a r a d io is o to p e tech n iq u e .
x
CHAPTER I
INTRODUCTION AND SURVEY OP THE LITERATURE
C o llo id a l e l e c t r o l y t e s e x h ib i t p e c u l ia r p r o p e r t ie s
in both the bulk of the s o lu t io n and the su r fa ce phase .
A l l th ese su bstances have approxim ately the same m olecu
la r d e s ig n , a large lyophobic p art on one end and a
l y o p h i l i c part on the other end. In t h i s d is c u s s io n ,
the o n ly so lv e n t to be d iscu sse d w i l l be w ater , th e r e fo re
the more s p e c i f i c terms hydrophobic and h y d r o p h il ic w i l l
be u sed .
These substances form la r g e thermodynamically
s t a b le aggregates c a l le d m ic e l le s which form over a narrow
co n cen tra t io n range known as the c r i t i c a l m ic e l l e con
c e n tr a t io n (cmc) and they e x i s t a t co n cen tra t io n s h igh er
than the cmc. They are a ls o adsorbed in the l i q u i d - a i r
in t e r f a c e w ith a re d u ctio n o f the su r fa ce t e n s io n . Above
the cmc, th ese su bstan ces s o l u b i l i z e water in s o lu b le
2
su b sta n c e s .
The fa c t o r s th a t c o n tr o l th e cmc, aggregate s i z e ,
and s o l u b i l i z i n g power are not w e l l determined and
e v a lu a ted . Many kinds o f experim ents, and t h e o r e t i c a l
in v e s t ig a t io n s have been conducted and many models have
been su g g ested in attem pts to b e t t e r understand t h i s
a ggregation p r o c e s s . The gross s tr u c tu r e o f the aggre
gate c o n s i s t s o f a p r o t e c t iv e h y d r o p h il ic su r fa ce la y e r
around a hydrophobic co re . Further d is c u s s io n o f the
s i z e and shape and th e ir r e la t io n to the le n g th o f the
hydrophobic t a i l and s i z e o f the h y d r o p h ilic head fo l lo w s ;
f i r s t , however, a short d is c u s s io n on water s tru c tu r e
seems to be in order.
A. Water S tructu re and S o l u b i l i t y of Organic M olecules
At one time i t was thought th at water did l i t t l e
more than a c t as a high d i e l e c t r i c medium that reduced
the fo r c e s between io n ic groups in s o lu t io n . Even a f t e r
the s t r u c tu r a l c h a r a c t e r i s t i c s o f water were w e l l known,
many in v e s t ig a t o r s s t i l l con sidered water to have a
secondary e f f e c t on aggregation p r o c e s s e s . Today, however
the e f f e c t s o f water s tr u c tu r e are being introduced in to
the ex p lan ation of most aqueous thermodynamic, k i n e t i c ,
m ech an ist ic and s tr u c tu r a l phenomena.
3
W ater's unusual p ro p e r t ie s maximum d en sity , a t
lp°G, high b o i l in g p o in t , volume change a t fu s io n have
been the f o c a l p o in t o f t h e o r e t i c a l works over the l a s t
h a l f cen tu ry . The f i r s t s t r u c tu r a l model was that o f
lon g hydrogen bonded p o l y m e r s . L a t e r , Bernal and Fowler^
p o s tu la te d the broken down ic e s tr u c tu r e which assumes
th a t most o f the hydrogen bonding in the s o l i d phase
remains in the l iq u id s t a t e . A daptations o f t h i s model
have been p resen ted by numerous in v e s t ig a t o r s in attem pts
to ex p la in th e p r o p e r t ie s o f w ater .
One o f the more re ce n t approaches by Nemethy and
S c h e r a g a ^ u ses a model s im ila r to one proposed by Frank
and Wen.^ȣ Water i s p ic tu r ed as being composed o f an
eq u ilib r iu m d i s t r ib u t io n of sh ort lived, c lu s te r s , which
are h ig h ly hydrogen bonded, and monomer m olecu les that
^For a review o f e a r l i e r t h e o r ie s , see fo r example, H. M. Chadwell, Chem. R evs. , IV (1 9 2 7 ), 375-
2 j . D. Bernal and R. H. F ow ler , J . Chem. Phvs. ,I (1 9 3 3 ), £15- “
3g , Nemethy and H. A. Scheraga, J . Chem. P h y s .,x x x v i ( 1 9 6 2 ) , 3382 . ~ ------- -------
*J-H. S . Frank and W. Y. Wen, D isc u ss io n s Faraday S o o . , XXIV (1 9 5 7 ), 133. -------------------------------
^H. S . Frank, Proc. Royal Soc. (London), ACCXLVII. (1 9 5 8 ), 24-81. ---------- ----------
have a h igh coord in ation number. These c lu s t e r s have
h a l f l i v e s o f the order o f lO- ^ second.
D is s o lu t io n of substances in water and the mech
anism by which water s tr u c tu r e a id s the s o l u b i l i t y o f
p a r a f f in hydrocarbons are the r e a l i n t e r e s t s . A s o lu te
p a r t i c l e can e i t h e r be d is s o lv e d i n t e r s t i t u a l l y or f i t
in to the water s t r u c tu r e . Prank and Evans^ proposed that
organ ic m a te r ia l was lo c a te d in the h o le s in the i c e
l i k e s t r u c t u r e , and in f a c t , proposed th a t the p resen ce
of the organic m olecu les f a c i l i t a t e d the form ation o f an
i c e s tr u c tu r e around th e m olecu le . This s tr u c tu r in g of
the w ater in the presence of the organic m olecule i s
c a l l e d the ''iceberg e f f e c t ." T his reg ion o f water around
the organ ic m olecule has a low enthalpy and a low entropy.7
Nemethy and Scheraga proposed a s im ila r explanation.
The energy l e v e l s of the com p lete ly hydrogen bonded water
m o lecu le s are lowered by the presence o f the hydrocarbon.
A l l the other s p e c ie s o f water have h igher energy, th e r e
f o r e , the i c e - l i k e sheath i s s t a b i l i z e d in the presence
o f the hydrocarbon.
^H. S . Frank and M. J. Evans, J . Chem. Phys. , X III (1911-5), 507. " ------- ------- -------
7G-. Nemethy and H. A. Scheraga, Chem. P h ys ., XXXVI
( 1 9 6 2 ) , 3I4.OI. ------- ------- --------
5
The io n ic and organic p o r t io n s o f the d e terg e n t
m olecu les w i l l be con sid ered to in t e r a c t w ith the water
as two sep ara te p a r t i c l e s . The water surrounding the
i o n ic head is con sid ered to be s im i la r to th a t around
any s in g ly charged c a t io n . The water around the organ ic
p o r t io n i s assumed to have the iceberg s t r u c tu r e . I f
the organic p ortion s are removed from the water and are
p la ced together and i f the io n ic groups form a p r o t e c t iv e
su r fa ce la y e r , the entropy of the water should in c r e a se
and the enthalpy should in c r e a se ; thus the d i s s o lu t io n
i s an e n tr o p ic a l ly driven r e a c t io n .
B. M ic e l l iz a t io n
M ic e l l i z a t io n r e s u l t s from the counterbalancing
of two or more f o r c e s . The f i r s t sim ple ex p la n a tio n was
g iven by D e b y e . g e suggested that the two opposing
fo r c e s were the van der Waals a t t r a c t iv e fo r c e o f the
hydrocarbon t a i l s and the coulombic r e p u ls iv e fo r c e o f
the io n ic heads. An exp ress ion fo r the fr e e energy o f
the m ic e l l e was d er ived and then minimized to ob ta in the
most s ta b le a g g reg a te . The f i n a l exp ress ion conta ined
8P. Debye, J . Phys. Chem. , L I I I , (1949 ), 1 .
9p. Debye, Ann. N. Y. Acad. S c i . , LI (19^ 9), 575 -
6
parameters th a t could be eva luated w ith the use of
experim ental r e s u l t s . These c a lc u la te d parameters were
c o n s is ta n t w ith r e s u l t s from other experim ents; th u s ,
D ebye's model gained co n sid era b le support.
O oshika,-^ H o b b s , a n d S h in o d a ^ m odified t h i s
techn ique by adding su rfa ce e f f e c t s and the entropy con
t r ib u t io n which Debye had n e g le c te d .
R eich l3 po in ted out th a t th ere was a fundamental
error in D ebye's work because Debye had minimized th e f r e e
energy o f the m ic e l le in s te a d of that of the s o lu t io n .
A ls o , Reich extended the theory to in clu d e n o n - io n ic
d e ter g e n ts and p o s tu la te d th a t the su rface o f the m ic e l l e
must be covered w ith the p o lar heads of the s u r fa c ta n t
m o le c u le s . This co n c lu s io n agrees n i c e ly w ith a model
used by Tartar-^- to p r e d ic t the m olecular w eigh ts o f
d e te r g e n ts . This model and m o d if ic a t io n s o f i t have been
10Y. Ooshika, J . C o l l . S c i . , IX (195k), 25k-
i :lM. E. Hobbs, J . P hys.. Chem, LV (1951), 675.
12K. Shinoda and K. K in o sh ita , B u l l , o f Chem.S o c . J a p ., XXVII (19 5k) , 73- ------------
Light s c a t t e r in g s tudies o f d etergent s o lu t io n s
in th e presence o f extraneous s a l t have been conducted
in t h i s la b o ra to ry to determine th e m olecular w eight
o f the m ic e l l e s . Numerous in v e s t ig a t o r s have presen ted
ex p ress io n s w ith which the m olecular w eigh ts of th e se
m ic e l le s are c a lc u la te d . A r e c e n t paper by Overbeek 1
and V r ij p o in ted out th a t one should o b ta in the
d i f f e r e n t i a l r e f r a c t iv e index f o r s o lu t io n s a t Donnan
eq u ilib r iu m rath er than fo r s o lu t io n s a t equal s a l t
c o n cen tra tio n .
D i f f e r e n t i a l re fr a c to m e te r measurements were
attempted under th ese eq u ilib r iu m c o n d it io n s . The
■**J. Th. G-. Overbeek and A. V r i j , J . C o llo id S c ie n c e , XVII (1 9 6 2 ), 570. “
68
69
s o lu t io n co n ta in in g the d etergen t and s a l t was p laced
in a v e s s e l which was in con tact w ith a s o lu t io n co n ta in
ing on ly s a l t . These s o lu t io n s were separated by an
in e r t v is k in g membrane. The s a l t s o lu t io n co n cen tra t io n
could be v a r ie d . The change in emf between the two
Ag-AgBr e le c tr o d e s in s e r te d in th e s o lu t io n s was
measured by means of a p o ten tio m eter . The r e s u l t s th a t
were obtained were not s a t i s f a c t o r y and t h i s p r o je c t
was abandoned.
The e le c tr o d e s were p a r t i c u la r ly s a t i s f y i n g ;
co n seq u en tly , a short d e s c r ip t io n of th e technique used
to prepare the e le c tr o d e s fo l lo w s .
B. P reparation of E lectro d es
This in form ation i s includ ed to a s s i s t persons
who re q u ir e m ech an ica lly and e l e c t r i c a l l y s t a b le Ag-Ag
h a l id e e le c tr o d e s th at have very sm all asymmetric
p o t e n t i a l s . This technique i s not th a t o f the author
but r e s u l t s from the combined e f f o r t s o f many experimenters
and experim ents a t S h e l l Development Company, Houston.
One should use s o f t g la s s because i t has the same
thermal expansion c o e f f i c i e n t as th a t o f p latinum and
th e r e fo r e no m echanical s t r a in w i l l be introduced as the
temperature is v a r ie d . Platinum w ire i s s e a le d in a
70
g la s s tube and th e wire i s wrapped around the end o f the
g la s s tube two or th r ee t im es . The e le c tr o d e i s p laced
in an annealin g oven. The temperature i s ad ju sted so
th a t the g la s s w i l l flow around the w ire and g iv e the
e le c tr o d e m echanical s t a b i l i t y .
The end of the e le c tr o d e i s then covered w ith
pure Ag^O and i s p laced in a furnace at lj.00oC. The
Ag20 w i l l decompose le a v in g a s i l v e r m atrix in in t im a te
co n ta ct w ith the platinum w ire . N ext, the e le c tr o d e i s
anodized in a 0 .0 5 N NaBr s o lu t io n w ith a low current
d e n s i t y o f ip-6 m illiam p eres per square ce n tim eter .
The e le c tr o d e s should then be aged in a d i l u t e
h a l id e s o lu t io n and then r in se d and sto re d in d i s t i l l e d
w ater . These e le c tr o d e s w i l l have an asymmetry
p o t e n t ia l o f the order o f 0 .01 - 0 .0 2 mv. They w i l l
have rapid e q u i l ib r a t io n tim es i f the Ag£0 la y e r was
not too t h ic k . They w i l l be q u ite s ta b le m ech a n ica lly .
C. R a d io iso to p ic S tu d ie s
In t h i s la b o r a to r y , s o l u b i l i z a t i o n l i m i t s have
been measured by e x tr a c t in g the s o l u b i l i z a t e s w ith
cyclohexane and determ ining the amount of m a te r ia l by
u. v . a b so rp tio n , by observing w ith the d i f f e r e n t i a l
re fractom eter the abrupt change in the index o f r e fr a c t io n
n
th a t r e s u l t s from adding increm ents o f s o l u b i l i z a t e and
by d i r e c t determ ination o f the u . v . ab sorption o f the
aqueous d e te r g e n t . The two u . v . ab sorp tion t e c h n i
ques are o b v io u s ly l im ite d to those compounds th a t
absorb in a convenient reg io n . The r e f r a c t iv e index
technique i s reason ab ly accurate and does not have the
p rev iou s l im i t a t i o n , but i t i s t e d io u s . Each d e t e r
m ination re q u ir es s i x or more measurements in order to
i d e n t i f y the s o lu b i l i z a t i o n l i m i t .
In order to stu d y p a r a f f in hydrocarbons the in dex
of r e f r a c t io n technique or some other procedure would
have to be u sed . I t was decided to in v e s t ig a t e the
p o s s i b i l i t y o f u sin g r a d io is o to p e s .
I t was found th a t th is technique would be q u ite
s a t i s f a c t o r y fo r these problems. The u su a l l iq u id
s c i n t i l l a t o r s were u sed , PPO and POPOP. The s o lu t io n
was composed o f 158 m l. x y le n e , 71 ml. e th y l a lc o h o l ,
1.11; grams PPO and 11 mg. POPOP„ *
Two ten th s o f a m i l l i l i t e r of aqueous s o lu t io n
can be d is s o lv e d in 15 m i l l i l i t e r s of t h i s m ixture
w ithout phase se p a r a t io n . This was the s i z e sample used
in the l iq u id s c i n t i l l a t o r . This sm all aqueous sample
p resen ted the problem that a very low r a d i o a c t i v i t y
e x is t e d in the cases o f the d i lu t e s o lu t io n s . For the
72
d i lu t e s o lu t io n s , however, more aqueous s o lu t io n could
be added and the s o lu b i l i z e d m a te r ia l could be e x tr a c te d
in to the x y len e a lc o h o l phase . The sm all amount o f
aqueous phase would not a f f e c t the geometry o f the
em itt in g s o lu t io n .
Aqueous s o lu t io n s o f tagged b en zo ic a c id were
prepared and the above technique was used. The counts
were recorded and the technique proved to be q u ite
s a t i s f a c t o r y fo r our purposes.
S ince in the a u th o r 's s t u d ie s , rep orted h e r e in ,
benzene was used e x c lu s iv e l y , i t was not n e c e ssa r y to
use the r a d io tr a c e r tech n iq u e .
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