PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF...
Transcript of PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF...
PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND NtONAQUEOUS SOLIimON OF AMPfiU^HOiIC
MOLECULES IN PRESENCE OF ADDTTIVES
MssmtAnoH SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS
FOR THE AWARO 6 F THE DEGREE OF
Muitn of t&I|thM(opiip IN
BY
KIR7I
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
ALIGARH (INDIA) 1994
DS2433
PHONE ; (0571) 25515 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY A L I G A R H —202 002
Dated. ]>.9.:S1..
Dr. KABIR-UD-DIN P r o f e s s o r
The d i s s e r t a t i o n e n t i t l e d " P h y s i c o - c h e m i c a l
Behaviour of Aqueous and Non-Aqueous S o l u t i o n s of
Araphiphi l ic M o l e c u l e s i n P r e sence of A d d i t i v e s "
by Miss K i r t i , i s s u i t a b l e f o r s u b m i s s i o n f o r t h e
deg ree of Mas te r of Ph i l o sophy in C h e m i s t r y .
(KABIR-UD-DIN)
Bebttateb ^0 tl)E iHemorp of
(Late) PROF. H. N. SINGH
S-2-5-I-S-S-J-5
@ @ ( § » ^
Page
I n t r o d u c t i o n • . • 1
Expe r imen ta l . « . 18
R e s u l t s and D i s c u s s i o n . . . 20
Rere rences . . . 36
In complating t h i s d i s s e r t a t i o n I have been guided,
encouraged and advised by a numter of t e a c h e r s , s c h o l a r s ,
col leagues and f r i e n d s . I r e a l i s e the debt I owe to each of
them and 1 know tha t i f I were t o be deprived of the coope
r a t i o n of even one s ing le person in t h a t pool of benefac tors ,
fhere would have taeen l e f t a very se r ious def ic iency in the
and product now before my r e a d e r s .
Special and profound thanks are due to Prof.Kaoir-ud-
Din, Deptt . of Chemistry, A.i-i.U., Al igarh . His q u a l i t i e s of
f r iendly guidance and int imate work r e l a t i o n s h i p with his
colleagues and s tuden ts are amply r e f l e c t e d in his supervis ion,
Ha encouraged me t o be f ree , innovative and bold in my inves t i
g a t i o n s . I t is d i f f i c u l t to say i f t h i s work would have oaan
poss iole without his c h a r a c t e r i s t i c overseeing and stewardship.
I aiii p a r t i c u l a r l y g ra te fu l to Prof. A. Aziz Khan,
Chairman, Dept. of Chemistry, for providing the necessary
research f a c i l i t i e s .
I am extremely beholden to my parents and a l l fa/ritly
memLsrs for t h e i r a f fec t iona te encouragement and i h t e r e s t
In my academic p u r s u i t s .
I must express my deep sense of g ra t i tude to my senior
co l league . Dr. sanjeav Kumar, for his pa t i en t and p e r s i s t e n t
sugges t ions , r e l a t e d to my labora tory work.
I would a l s o be f a i l i n g in my d u t y i f I do not
ment ion the c o n t r i b u t i o n of my f r i e n d s . Miss Krishna Kuraari,
Mis s Sara L i s David and a l l o t h e r f r i e n d s whose words o f
endearment and p r a i s e tept a l l f r u s t r a t i o n and d e f e a t i s m
a t a d i s t a n c e .
KIRTI
I N T R O D U C T I O N
1
The domain of surface science i s perhaps one of
the most in terd isc ip l inary areas of modem science and
technology . Although the importance of surface science has
been recognized for more than a century* i t i s only during
the la s t few decades that rapid advances in the understan
ding of surface phenomena have taken place. When one looks
c loser to the earth, one finds that i t i s f u l l of o b j e c t s ,
and that each object i s surrounded by a surface or an inter
face . Fortunately, a l l the i n t e r f a c e can be grouped in f ive
major c l a s s e s , namely, g a s / l i q u i d , l i q u i d / l i q u i d , s o l i d /
l iqu id , so l id /gas and s o l i d / s o l i d (Fig. 1) . All objects
are surrounded by one or more of these basic f ive interfaces .
All of these Interfaces have a common property ca l l ed surface
tension or surface free energy. There i s a c l a s s of compounds 2 3 ca l l ed surface act ive compounds * (or surfactants) that
decreases s t r ik ing ly the surface tension or surface free
energy of these in ter faces .
Surfactants, surface act ive agents, or detergents
are amphiphilic, organic or organometallic compounds having
two d i s t inc t parts , namely, a hydxrophilic (watet soluble)
or polar part, And « l i p o p h l l i c ( o i l soluble) or non-polar
part . The l ipoph i l i c part Is general ly a long hydrocarbon
chain. Depending on the chemical structure of the hydrophilic
moiety bound to the hydroi*iobic por t ion , the surfactant may
be c lassed as cat i o n i c , anionic, non i o n i c , or ampho ly t i c
(zwitterionic) . An exhaustive l i s t of both synthetic
o o
UNIVERSE
SUN EARTH
OBJECTS
MOON STARS GALAXIES
GAS
LlOmD LIQUID UQUID
GAS SOLID
LIQUID SOLID
SOLID SOLID
Fig. No. 1 The five inferfaces
3
and natural ly occurring surfactants Is available* Their
preparation and propezrties in general have been given in
the exce l lant monograph of Feildler and Pendler . Ttie
charac ter i s t i c propert ies of surfactants in so lut ion which
render poss ible t h e i r pract ica l appl icat ions such as washing
c l ean ing , wett ing, emulsifying, dispersing and foaming
depend in a l l cases on the tendency of these compounds to
accianulate at in ter faces between the solution and the adja-14 cent gaseous, l i q u i d , or so l id phases •
Surfactant molecules form assoc iat ion c o l l o i d s or
m i c e l l e s in so lut ion with in a f a i r l y narrow concentration
range. Micelle do not e x i s t at a l l concentrations and
temperatures. Tliere i s a very small concentration range
below which aggregation to mice l le i s absent and above
which assoc iat ion leads to mice l le formation* It i is concen
t ra t ion i s c a l l e d c r i t i c a l mice l le concentration (CMC), The
number of molecules that aggregates to form mice l l e s i s
c a l l e d the aggregation number. Micel iar aggregation can be
demonstrated by measxirements of physical properties against
surfactant concentration. The most s ign i f i cant property i s
surface (or i n t e r f a c i a l ) tension (Fig* 2 ) .
The reason 'why do mice l l e s form' may be explained
by taking into account the changes occurlng i hen a monomer
i s transferred from i t s aqueous environment in to the
m i c e l l e . On transferring the monomer in to mice l l e , the
CMC
log (concentrotion)
F I 9 • N o . 2 * Surface (a i r -wa fe r ) tension os a function of surfactant
concentration for on aqueous miceHar solution. Schematic
structure of the solution is shown below and above the
crirical mic9liar concentration ( C M C )
:»
h i g h e n e r g y o f t h e h y d r o c a r b o n / w a t e r I n t e r f a c e I s l o s t ,
a s t h e c h a i n i s now i n c o n t a c t w i th o t h e r s of a l i k e
n a t u r e . T r a n s f e r of monomer i n t o m i c e l l e a l s o means t h a t
t h e s t r u c t u r i n g o f water around the hydrocarbon part of
the monomer i s l o s t , t h e r e f o r e an o r d e r e d s t a t e has become
a d i s o r d e r e d one w i t h regard t o t h e w a t e r , i m p l y i n g a
p o s i t i v e e n t r o p y change and a d e c r e a s e i n f r e e e n e r g y .
The f a c t o r o p p o s i n g t h e m i c e l l e f o r m a t i o n i n i o n i z e d s u r
f a c t a n t s i s r i s e i n f r e e e n e r g y due t o e l e c t r i c a l work and
t r a n s l a t i c n a l freedom l o s s e s due t o i n c o r p o r a t i o n o f monomer
in t o a m i c e l l e . T h i s d i s o r d e r t o o r d e r t r a n s i t i o n g i v e s
a n e g a t i v e e n t r o p y change %#hich w i l l oppose t h e p o s i t i v e
e n t r o p y c h a n g e s o c c u r i n g from l o s s o f water s t r u c t u r e , the
o v e r a l l d e c r e a s e i n f r e e e n e r g y due t o l o s s o f h y d r o c a r b o n /
water i n t e r f a c i a l e n e r g y and water s t r u c t u r e o u t w e i g h s
t h e f r e e e n e r g y r i s e due t o e l e c t r i c a l work and t r a n s l a
t i c n a l freedom l o s s e s , g i v i n g a remarkable t e n d e n c y t o
m i c e l l i s e . Mukerjee and M y s e l s have c o m p i l e d CMC data
of v a r i o u s c l a s s o f s u r f a c t a n t s u s i n g d i f f e r e n t t e c h n i q u e s .
Normal M i c e l l e s
Aggregate formed i n aqueous s o l u t i o n s o f s u r f a c
t a n t m o l e c u l e s a t CMC are known a s normal m i c e l l e s . They e q u i l i b r i u m ,
dre a lways in dynamic / Such m i c e l l e s are thought t o be 16 —18 r o u g h l y s p h e r i c a l ^°. A s c h e m a t i c two d i m e n s i o n a l
r e p r e s e n t a t i o n o f an i o n i c s p h e r i c a l - m i c e l l e i s shown
r,
In Fig. 3. In the case of ionic surfactants , part of the
counterions are "bound" to the surface of the mice l l e ,
forming vrtiat i s ca l l ed the "Stem layer", whereas the
remaining counterions are local ized at greater distances
from the surface of the mice l l e , inwhat i s ca l led the
"Gouy-Chapmann e l e c t r i c double layer".
Results of l ight scatter ing, v i s c o s i t y , diffusion
and ultracentrifugation studies on nonionic cetomacrogol
mice l les indicated the ir shape to be e l l i p s o i d a l with an 20 axial ratio of 2:1 . Some water molecules may be entraped
2 1 22 by the micelle and under certain circumtances part
of the hydrocarbon chain may extend into the aqueous 2"? I ^ a s e . The amount o f water i n t h e mice l i a r i n t e r i o r
v a r i e s from s u r f a c t a n t t o s u r f a c t a n t , but water i s c o n s i
d e r e d , at p r e s e n t , t o p e n e t r a t e t h e m i c e l l a r s u r f a c e o n l y
up t o d i s t a n c e s o f a p p r o x i m a t e l y t h r e e t o s i x carbon
21 23-25 atoms ' . The i n t e r i o r , or c o r e , of the m i c e l l e has
g e n e r a l l y been i n f e r r e d t o be h y d r o c a r b o n - l i k e from
2 6 2 1 2 7 e s r and nmr * s p e c t r o s c o p y and from t h e u t i l i z a t i o n
28 o f f l u o r e s c e n t p r o b e s
R e v e r s e M i c e l l e s
S u r f a c t a n t s in n o n - p o l a r s o l v e n t s , in t h e p r e s e n c e
of t r a c e s o f w a t e r , a s s o c i a t e t o form t h e ao c a l l e d
" r e v e r s e " or " i n v e r t e d " m i c e l l e s . The s l tructure of t h e
m i c e l l e i s r e v e r s e d , t h e p o l a r head groups of t h e monomer
—Stern layer
Gooy Chapman double loyer
P i g ' . 1 ^ 3 ' ^ two-dimensional schematic representation of the regions of a
spherical ionic micelle. The counteriops ( X ) , the heod group5(rj)) ,
and the hydrocorbon chains (^v^—) ore indicoted .
being present in the centre of the mice l l e , and the
hydrocarbon chains extending outwards into the solvent.
Such micel les could be formed in pf^sence of traces of
water v*iich forms a water pool in the interior of the
mice l iar aggregate. The s ize and properties of' reverse 2 9-32 mice l les vary with the amount of water present . A
possible structure of reverse micel le in a nonpolar
medium in equilibrium with monomer i s shown in Fig. 4.
The discontinuity in some physical property ( v i s
c o s i t y , s o l u b i l i t y , surface t e n s i o n , e t c . ) of the solution
can be used to identify the CMC, and techniques such as
scatter ing, ultracentrifugation and v i s c o s i t y are used to
determine the s ize and shape of the micel le . Some other
techniques which have been developed to determine the CMC
include dye solubilization"'-^ ••^*, water solubil ization^^,
nmr ' . The different experimental methods available
for determining the CMC are given in the compilations 17 18
of shinoda et a l , . Elworthy et a l . and Mukerjee and Mysels
Mixed Micelles
The formation of micel les from more than one
chemical species gives r ise to v4iat are known as mixed
mice l l e s . In the simplest case , binary or ternary mixtures
of surfactants of s imilar, but not ident ical chain lengths
may be studied and the thermodynamics of t h i s type of
^
M o n o m e r so lu t i on ( Ideal s o l u t i o n )
M ice l l e ( H y d r o c a r b o n po r t )
( N o n i d e a l s o l u t i o n )
FIG.fSlo REVERSE MICELLE
10
38 39 40
m i c e l l e formation has been descr ibed * . Cl int deve
loped an a n a l y t i c a l descr ip t ion which Included both m i c e l l e
composit ion and oonotner concentrat ion above the mixed CMC
for mixtures of nonlonlc s u r f a c t a n t s . C l i n t ' s treatment
assumed Ideal mixing In the m i c e l l e . Furthermore, the
express ion of Lange and Cl in t * for the CMC va lues of
mixtures of nonlonlc sur fac tant s has been experimently 40,4
v e r i f i e d for c a s e s inhere idea l mixing might be expected The propeirtles of the mixtures of an anionic surfactant
A ^ A ^
and a nonlonlc surfactant ' , and c a t l o n l c and nonlonlc 44 s u r f a c t a n t s have been in terpreted with the aid of mixed
41 m i c e l l e formation between the s u r f a c t a n t s . Lange and Beck
and Cl in t pointed out that the CMC of the mixed m i c e l l e s
i s lowered more than that of the s i n g l e sur fac tant .
Another cl<iss of mixed m i c e l l e s r e s u l t s when low_
molecular weight molecules are s o l u b l l i z e d by m i c e l l e s
formed from s u r f a c t a n t s conta in ing a r e l a t i v e l y larger
non-polar cha in . The s o l u b l l l z e d subs tances , a l s o c a l l e d 45 a penetrat ing a d d i t i v e . may be located in the hydrocarbon
core or the hydrophi l lc mantle " .
Structural a spec t s of surfactant m l c e l l a r systemg :
Inf luence of a d d i t i v e s
Surfactant molecules can be considered as bui lding
b locks . Surfactant s e l f - a s s o c i a t i o n in aqueous media i s
s t rong ly cooperat ive and s t a r t s g e n e r a l l y with the
11
formation of roughly sf^ierlcal m i c e l l e s arovind the c r i t i c a l
m i c e l l e concentra t ion . When the surfactant concentrat ion
markedly exceeds the CMC, the shape of the spher ica l or
e l l i p s o i d a l m i c e l l e undergoes gradual changes *
Figure 5 schemat ica l ly shows var ious s t ruc tures that are
formed upon increas ing the concentrat ion of sur fac tant .
In the beginning of s t ruc tura l changes sF*ierical m i c e l l e s
become c y l i n d r i c a l , upon further increas ing the concen
t r a t i o n , there i s a hexagonal packing of water c y l i n d e r s ,
Vpon addit ion of an o i l and a shor t -cha in a l c o h o l , one
can convert such water c y l i n d e r s in to w a t e r - i n - o i l
(w/o) rnicroemulsions*
I t i s p o s s i b l e t o induce a t r a n s i t i o n from one
s tructure t o another by changing the physico-chemical
c o n d i t i o n s such as temperature, pH, addi t ion of ion ic and 18 52—58 nonionic s o l u t e s , in the surfactant s o l u t i o n ' . The
rod shape s tructure f i t s the r e s u l t s f o r dlmethyldodecyl 54 amineoxide m i c e l l e s in s a l t s o l u t i o n s at low pH va lues
For ion ic surfactant sys tems, m i c e l l a r growth increases
very s trong ly with decreasing temperature, with increas ing
counter ion s i z e ( c l " , Br ' , I~) and with the addi t ion of 5 5-57 s a l t s . For nonionic m i c e l l e s , r a i s i n g the tempera-
58 ture favours m i c e l l a r growth .
Since m i c e l l e s are dynamic s t r u c t u r e s comprising
a l i q u i d c o r e , i t i s probably u n r e a l i s t i c to regard them 59
as r i g i d s t ruc tures with a p r e c i s e shape . The shape
^h
li.
o to w z ° i^ O O 2 < — Q- d
>-_. ^ < ^ z °^
>< UJ I
z o — to
1
c r - C o
CO •>-'
( u L O D ^
^ L. U D D l/ L-
•^ t ; (/) O
w c 3 O o Z i_ O o •-C *-" > c
CJ
° ^ ^ o C o o
• ^ 0 )
O JZ
6 - l_
o en >*- c
l_ O
o c « • - • " "
§ 1 _ d *- D O »- C
:;; 2 r ) "*-• d D —' —.
o u '
•*^ •*->
o c E o
01 L. D
< 01
2 LU o a to
o"
LL
13
and s ize of these mice l iar aggiregates can^ln principle^ be
determined by various methods, such as l ight scat ter
ing , di f fusion, sedimentation v e l o c i t y , sedimentation
equilibrium * , ultrasonic absorption^^, time resolved 66 67
fluorescence * , e t c . Viscometric technique has been used In a number of experimental Investigatlons^^'^^'^^*^'^ of micellar solutions both because of i t s siroplicity and
i t s s e n s i t i v i t y to detect changes in the s ize of the
anisotropic micellar aggregates. The sphere-to-rod tran
s i t i o n s of ionic and nonionic mice l les have been studied
by a number of workers^°'^^'^^"^"^ •^^"''^. For sodium
dodecyl sulphate and for a ser ies of catlonic surfactants
in Nacl so lut ions , a sharp break in apparent micelle
molecular weight i s observed when the Vacl concentration
reaches a value of 0,45 M and the break point would 72 73 correspond to the sphere-to-rod trans i t ion * . The
micellar sphere-to-rod transi t ion i s highly dependent
upon the nature of the counter ions and was concluded
that strong counterion binding promotes the trans i t ion
from small si*ierical to cyl indrical mice l les ' .
Temperature a f fec ts the sphere-to-rod trans i t ion .
The v i s c o s i t y of the cyl indrical micellar solution dec
reases with the increase in temperature due to the break-57 Ing up of the cyl inders to smaller aggregates . Decrease
in micellar s ize with temperature at high concentrations
of e l ec t ro ly te s has been reported by various authors * *
14
Importance of Mice l i ar Solutions
Hicellar solut ions are known to increase the solu
b i l i t y of s l i g h t l y soluble or insoluble organic compounds 13 18 in water ' . Mice l iar solutions are used extens ive ly in
synthet ic , analyt ica l , i*iarmaceutical and industrial che
mistry* The change in the micellar structure have pronoun-77 ced e f f ec t s on micellar ca ta ly s i s . Several reports on
the structures of micel les of cetyltrlraethylammonlum
bromide (CTAB) have recently appeared * , and t h i s
micel le has been used to catalyse a variety of react-. 77-79 ions
The engineering applications of surface science
range from agricultural sprays to o i l recovery Including
areas such as c a t a l y s i s , coating, dispersions, e l ec tron ics ,
f loatat ion of minerals, lubrication, and retardation of
evaporation from lakes and reservoirs .
Among biomedical areas, the applications of surface
science extend from anesthesiology to zoology Including
f i e l d s such as a r t i f i c i a l implants, biomembranea, b io -
lubrication, l ipoprote ins , lung surfactant, opthalmology,
pharmaceutical and pharmacology. The surface active agents
may influence the biological e f f icacy of the drug or pes
t i c i d e . Many poorly soluble drugs and pest ic ides are
administered in a solubll lz«d form using micellar solutions
in order to increase the b ioava i lab i l i ty and targett ing to
the s i t e of action, certain surfactants have the a b i l i t y
If)
to Increase the permeability of some bacterial c e l l wal ls ,
and hence are synergist ic with some antibacterial agents.
Micellar solut ions in reverse mice l les play a
v i t a l role in removing polar dirt from c lo thes , in motor
o i l s to so lubi l i ze corrosive oxidation products and to
prevent them firora reacting with engine parts. Solubilized
systems are used in removing odour causing molecules from
food packaging plants , photographic processes and in
surfactant type corrosion inhibi tors . A very important
application of micel lar solution i s in separation 80 science . Aqueous micellar systems have the a b i l i t y to
s o l u b i l i z e , compartmentalize and concentrate (or separate)
so lu te s , a l ter the local environment about associated
so lu te s , a l ter the posit ion of equilibrium systems and
alter the photophysical and chemical pathways and rates
among others. Although a l l of these micellar features can
be exploited to aid the separation s c i e n t i s t in spec i f ic
instances, the main basis for the successful u t i l i z a t i o n
of aqueous micel lar media in separation stems from the
fact that they can d i f f e r e n t i a l l y so lubi l i ze and incor
porate a variety of so lu tes . Some of these are micel lar
f a c i l i t a t e d sampltlag considerations, extractions based
on the d i f ferent ia l so lubi l iz ing a b i l i t y of mice l l e s ,
micellar Electrokinetic capi l lary chromatography, micellar
liquid chromatograi*iy, micellar enhanced detect ion.
In
micellar enhance u l t r a f i l t r a t i o n , and micel le mediated
extract ions or preconcentrations of polyaromatic hydro
carbon.
I t i s c lear from the above mentioned l i terature
that micellar media have attracted wider attention than
any other media in recent years, with speci f ic and judicio
us choice of media, chemical transformations can be
carried out more swi f t ly , under milder conditions with
higher yie lds and fewer by-products and, if necessary,
with good stereo and regio-chemical control .
Importance of ftesearch Problem
Increasing attention i s being devoted to the study
of the "incorporation" or so lubi l izat ion of neutral organic
molecules into micel les in aqueous solut ions . Some of the
most studied so lub i l i za tes are a lcohols , because of the 81 important role they have in preparation of microemulsion
I t i s generally accepted that the medium chain length
alcohols intercalate between the surfactant ionic head 82 groups to decrease the micellar surface charge density .
This e f fec t i s correlated with modification of the growth 83 and shape of the mice l les . Recently some linear medium
chain al iphatic amines have been gett ing more recognisation
as cosurfactants in microemulsion preparations . Des
p i te the significance of amines in microemulsions proper
attention has not been paid so far to the contribution of
17
medium chain normal amines In mlcellar systems.
Visualizing the significance of mlcel lar structure
trans i t ions and the ir dependence upon the nature of e l e c -87 88 t r o l y t e s ' , temperature and, in some c a s e s , the Influence
8 9 of org'inlc additives , i t was thought worthwhile to
persue a study of the e f fec t of a l iphat ic amines on concen
trated mlcellar solutions in aqueous potassium bromide
(KBr). Compared with other techniques, the capi l lary v isco-
metry method i s simple and re l iab le and can provide a
large body of Important information with respect to the 90 invest igat ion of the Increase in micel le s ize . The results
of studies on the ef fect of the addition of various a l i
phatic amines on the v i s c o s i t y of 0,1 m CTAB + 0.1 m KBr
solutions are presented herein. Prom the temperature depen
dence of the v i s c o s i t y , the act ivat ion free energies (A-G*) >
enthalpies ( A H ) and entropies (AS*) for the viscous
flow have also been calculated.
E X P E R I M E N T A L
1 ?
(a) Mate r ia l s :
Cetyltrimethylaramoniifln bromide (CTAB) from E. Merck
(98.5%) was r e c r y s t a l l i z e d twice from acetone,
CH2(CH2)j 5 N'''(CH3)3Er"
Ttie surfac tant was dr ied a f t e r f i l t r a t i o n in a hot a i r oven
at 50 c. The pu r i ty of the surfac tant was ascer ta ined from
the absence of minimum in the surf^^ce tens ion versus loga
rithm of concent ra t ion p l o t s . KBr from E. Merck was heated
for one hour (rJeO c) and was kept in a des icca tor (^2^5^
t i l l use.
The amines, v i z . n-hexylamine (CgNH2)» n-heptylamine
(C7NH2) and n-octylamine (CgNH2) ( a l l "Purum grade") were
obtained from Fluka, vrtiilst n-butylamine (C.NH2) was a
R iede l -de^aen product . All chemicals were used as supplied.
Demineralized water, r e d i s t i l l e d from a lka l ine potassium
permanganate, was used. The speci f ic conduc t iv i ty of water
was in the range IxlO" to 2xlO~ ohm" cm" . Water, equ i
l i b r a t ed with atmospheric carbondioxide, was used throughout
the work.
(b) Prepara t ion of so lu t ions ;
0 .1m CTAB in 0,1 m KBr so lu t ion was prepaired by
dissolving required amounts of CTAB and KBr in a s ingle
volumetric f l a sk in d i s t i l l e d water. The concent ra t ion of
mixed solvent was f ixed throughout the work. Different
ID
so lu t ions of amines were prepared in the mixed solvent
(0.1 m CTAB + 0.1 m KBr) and the concen t ra t ions of amines
were ca l cu l a t ed as mol per kg mixed so lven t .
(c) v i s c o s i t y measurements :
v i s c o s i t i e s of the so lu t ions were measured in an
Ubbelohde viscometer immersed in a thermostated bath. The
r e l a t i v e v i s c o s i t y of a solut ion was ca l cu l a t ed using the
r e l a t i o n :
-t „ _t_ . . . . (1) % ^o
where n and "n are the v i s c o s i t i e s of the so lu t ion and
water, r e spec t ive ly , at the experimental temperature an<3
t and t are the respec t ive flow times for the same volume
of so lu t ion and water. Density co r r ec t i ons were not made
since i t was found t h a t these were neg l ig ib le . The solvent
flow time was always longer than 200 seconds. At leas t four
flow-time measurements were made at each concent ra t ion and
a mean deviat ion from the mean of a l l measurements not
exceeding 0.1 second was required. The temperature of the
bath was con t ro l l ed to an accuracy of + O.l^c. The measu
rements were made at 30° . 35^, 40° , 45°C.
RESULTS AND PISCUSSION
: n
The effect of add i t ion of KBr on the r e l a t i v e v i sco-
c i t y (i\/%^ °^ 0.1 m CTAB solut ion at 3O3.I6 K i s i l l u s t
ra ted in Fig. 6. vJhen a s a l t i s added to a sur fac tan t
so lu t ion and i t s concent ra t ion reaches a threshold v a l u e ,
non spher ica l mice lies.form because the presence of s a l t ions
near the polar heads of the surfac tant molecules decrease
the repuls ion force between the head groups. A reduction in
the repuls ion makes i t j jossible for the sur fac tant molecules
to approach each o the r more c lose ly and form larger aggre
gates which requires much more space for the hydrophobic
cha ins . This leads to a sharp r i se in T^A^p; in the present
system (of 0.1 m CTAB) i t occurs around 0.1 m KBr indica t ing e g Q 1
the formation of l a rger aggregates ' (rod-shaped micel les) :
t h i s being the reason of choosing 0,1 m CTAB + 0.1 m KBr
system for the de t a i l ed study of the e f f ec t of n-alkylamines
and temperature.
Figures 7(a) to (d) show the v a r i a t i o n of 't^Au with
concent ra t ion of added amines at 3O3.I6 K, 308.16 K, 313.16
K and 318.16 K. v i s c o s i t y data for d i f fe ren t amines at
d i f fe ren t temperatures are given in Table I . Data in Table
I and Figures 7(a) to (d) indica te t ha t the addi t ion of an
amine may e i t h e r decrease or increase the v i s cos i t y of
s t a r t i n g so lu t ion (O.i m CTAB + 0.1 m KBr). I t i s fu r the r
seen t h a t the increase or decrease of v i s c o s i t y depends upon
the chain length and the nature of added amines. With Cg,
C7 and Cs-amines, the v i s c o s i t y f i r s t r i s e s abruptly followed
21
30.0 -
24.0 -
18.0 -
12.0 -
6 0 -
0 .0 0.0 O.OA 0.08 0.12
[KBr ] (m)
0.16 0.20
F ig . N o . g : Effect of K B T concentrafion on fhe relative viscosity
of 0.1m C T A B micellor solution at 303.16 K.
' ) 0
T a b l e - I
R e l a t i v e v i s c o s i t i e s of 0 . 1 m CTAB + 0 , 1 m KBr i n p r e s e n c e of n - a m i n e s a t d i f f e r e n t t e m p e r a t u r e s .
Amine Amine c o n c e n t r a t i o n
( m o l . k g )
R e l a t i v e v i s c o s i t i e s
l°cT 30 35
InS^L
40 45
n-But y l i m i n e 0 . 1 0 0 0 .150 0 . 2 0 0 0 . 6 0 0
77 79 56 31 39
2 , 1, 1, 1, 1.
82 43 38 23 36
1. 1. 1, 1. 1.
94 31 28 22 35
1, 1. 1. 1. 1,
48 22 20 19 34
0.700 1.40 1.38 1.37 1.35
n - H e x y l a m i n e 0 . 0 2 0 0 .050 0 .100 0 .175 0 .250 0 . 3 5 0
6 . 6 9 8 . 0 7 5 . 2 9 3 .65 3 .18 2 . 9 7
,76 ,29 .75 ,73 .79 .89
1, 2. 2, 2, 2
81 67 67 50 54
1. 1. 2, 2, 2,
64 91 04 09 34
2.72 2 . 5 7
n - H e p t y l a m i n e 0 . 0 2 5 0 . 0 6 0 0 . 0 7 5 0 . 1 0 0 0 .125
3 1 . 6 0 115 .02 117 .20
9 7 . 1 4 4 5 . 1 0
12 46 48 47
,80 ,09 ,85 ,91
5 16 22 23
91 49 13
,84 1 7 . 3 6 11 .96
3 . 3 3 7 . 6 4
1 0 . 6 9 10 .99
7 . 9 0
n - O c t y l a m i n e 0 .010 0 .020 O.O3O 0 , 0 4 0 0 . 0 6 0 0 . 0 7 5
11 .85 73 .52
2 5 9 . 9 9 5 3 2 . 8 4 6 7 8 . 5 8 1 9 0 . 6 9
5 20 30
131 251
10 ,70 86 78 47
2, 8.
10. 35. 89 .
77 74 33 90 90
1 4 4
13 37
91 26
,18 05 82
1 7 5 . 8 6 135 .83 8 4 . 9 4
23
7 0\-
6 0
5 0
4 . 0
3 0
2 0
1 O
0 OL
Q ~
m ~ <g) -
o -
C4NH2
C6NH2
C7NH2
C8NH2
0.2 0.3 0.4
[ n - amines] (m)
0,5 0 .6 0.7
Fig. No.7(oX'--090''ifhms of relotive viscosities of 0 . 1 m CTAB -l-0.1mKBr
solutions OS a func t ion of added n-amines at 303 .16 K .
2 ;
7.0
6 .0
0.0 0
e #
<s o
C4NH2
C6NH2
C7NH2
C Q N H 2
0.1
Rg.Na7(b)
0.2 0 3 0.4 0.5 0.6 0.7
[ n - amines J ( m)
Logarithms of relative viscosities of 0.1 m CTAB + d m KBr
solutions OS o function of added n - a m i n e s at 308 .16 K
o
C4 NH2
Cg NH2
C7 NH2
C 8 N H 2
0 2 0,3 0.4
( n - amines ] ( m)
0.5 h.6 0.7
Fig.NCxT (c) • Logonthms of relotive viscosities of 0.1m C T A B - h 0 . 1 m KBr
soluf/on OS a function oi added n - omines ot 313.16 K
5.0 Q C4NH2
# C6NH2
C7 NH2
O CQ NH2
0 2 0 3 0 4 0 5 [ n - omines] (m )
0 6 O 7
Fig .rsio.7(d) . Logarithms of relafive viscosiries of 0 1m C T A B + O l m KBr
solutions OS a function of added n -am ines at 318 16 K
Z l
by decrease in v i s c o s i t y . The e f fec t was p rog re s s ive ly more
pronounced f o r C , and Cg amines. In case of C^NH2/Viscosity
decreases r igh t from the beginning. The v i s c o s i t y increments
a t low concen t r a t i ons of h igher amines (Cg-Cg) can be i n t e r
p re t ed in terms of the formation of large mice l l e s owing
to t h e i r s o l u b i l i z a t i o n / i n c o r p o r a t i o n in to the m i c e l l e s .
The decrease in the v i s c o s i t y on a f u r t h e r add i t ion of these
amines i s a r e s u l t of the breaking of l a r g e r mice l l e s in to
small aggrega tes . Addition of C^NHj r e s u l t s in breaking of
i n i t i a l l y presen t rod-shaped mice l l e s t o sphe r i ca l with a
concomitant decrease in the v i s c o s i t y value comparable t o
g lobu la r mice l l a r s o l u t i o n . The preceding d i scuss ion r e f l e c t s
t h a t l a r g e r amines s o l u b i l i z e p r e f e r e n t i a l l y in m i c e l l a r
so lu t ion and lower the surface charge d e n s i t y which i s r e s
pons ib le fo r m i c e l l a r sphere - to - rod t r a n s i t i o n . Fur ther
add i t ion of the amine beyond the optlmun concen t r a t ion
a f f e c t s the water s t r u c t u r e predominant ly , r e s u l t i n g in the
breaking of g iant aggrega tes to r e l a t i v e l y smal ler ones and
hence a gradual decrease in v i s c o s i t y i s observed. The
behaviour of C^NH2 d i f f e r e n t than o t h e r s i s due to the
hydroph i l i c nature of t h i s amine, i t i s p a r t i t i o n e d more
in the aqueous phase; hence t h i s a f f e c t s the water s t r u c t u r e
and causes the breaking of i n i t i a l l y p r e s e n t large m i c e l l e s 92
in the so lu t i on . Such t r a n s i t i o n s from rod- to - sphere by
the a d d i t i o n of lower a lcoho ls t o dodecyl t r imethyl ammonium
bromide-sodium s a l i c y l a t e mice l l e s have been repor ted from
28
93 l i g h t s c a t t e r i n g m e a s u r e m e n t s
F i g . 8 shows t h e I n ( ' ' lA^) v s . 1 / T p l o t s f o r d i f f e r e n t
c o n c e n t r a t i o n s of h e p t y l a m i n e ( s i m i l a r t y p e of p l o t s were
o b t a i n e d f o r o t h e r a m i n e s ) . The o b s e r v e d l i n e a r i t y o f t h e
p l o t s shown i n F i g u r e 8 i s i n t e r p r e t e d i n t e r m s of t h e
r e l a t i o n
In T^/TJJ^ = I n A + A G * / R T . . « . (2 )
where A i s a c o n s t a n t and ^G* i s t h e a c t i v a t i o n f r e e e n e r g y
f o r v i s c o u s f l o w . As d e n s i t i e s o f t h e s o l u t i o n s were c l o s e
t o d e n s i t y o f w a t e r , k i n e m a t i c c o r r e c t i o n s were n e g l e c t e d ,
and v a l u e s o f /s^G* were c a l c u l a t e d f rom t h e s l o p e s of t h e s e
s t r a i g h t l i n e s shown i n F i g u r e 8 . As s t a t e d e a r l i e r , ^^.A^
were o b t a i n e d o n l y a t f o u r t e m p e r a t u r e s i n t h e r a n g e of
30 t o 45*^C. The l a c k of more e x p e r i m e n t a l d a t a p o i n t s d o e s
n o t p r e c l u d e i n o b t a i n i n g good c o r r e l a t i o n c o e f f i c i e n t s ( r ) .
E s t i m a t i o n of a c t i v a t i o n p a r a m e t e r s a r e , t h e r e f o r e , s u f f i
c i e n t l y a d e q u a t e . The r a n d c a l c u l a t e d / \ G * v a l u e s a r e
shown i n T a b l e I I .
U s i n g t h e G i b b s - H e l m h o l t z e q u a t i o n
3 ( ^ i G * / T ) / a ( l / T ) - A n * . . . (3)
alongwith the dependence of A<2* on T (Figure 9), the a c t i
va t ion en tha lpy (AH*) for the v iscous flow was c a l c u l a t e d .
The /^H* values r e f l e c t the energy used in the r o d - t o -
sphere t r a n s i t ion-When the temperature i s increased by a
2'I
6.00 F
4.00h
c
2,00U
0.0(>
0.060m) (0.075 m)
(0 lOOm)
(0 .125m)
( 0 . 0 2 5 m )
(0 .00m)
X X 3.10 3.20
1/T(10'^K~S 3.30 3.40
F ig . No . 8 ; Voriofion of Ln(n./n.o) with 1/T for 0.1 m CTA8-»-
0.1 m KBr solutions in the presence of various
concentration of n - heptyl amine maintioned in ( )
30
small value dT the t o t a l energy added to the system i s
Cpdt, where C i s the heat capacity at constant pressure.
This amount of energy w i l l p a r t i a l l y be spent on "evaporating"
some of the amphii*iiles previously attached to the mice l l e s .
At high temperatuire these evaporated surfactant molecules are
unable to remain in s o l u t i o n , so i t i s a necessary consequence
that they form new m i c e l l e s cons i s t ing of a smaller number
of monomers. This mechanism i s involved in t rans i t i on of
rod-shaped mice l l e s to spherical ones at e levated temperatures.
The obtained AH* values (from Figure 9) are also
given in Table I I . The values of /^G* and A.H* show that
^ H* covers the t o t a l contribution to zi G* and, therefore,
the entropic contribution i s n e g l i g i b l e . I t may be noticed
that the observed l i n e a r i t y in the In ifjA o v^* /" p lo t s
(Figure 8) indicates that enthalpic contribution to AG*
i s independent of temperature.
Figure 10 shows the variat ion of ^H* with concen
trat ion of added amines. From Table II and Figure 10, i t
may be seen that Z G* and AH* values are highly dependent
on the nature and concentration of added amines. The higher
values of ^H correspond to the formation of larger aggre
gates (elongated rods) , and low values towards the smaller
aggregates (spherical m i c e l l e s ) . The magnitude of ^O*
and AH* for different amines indicates tha^ higher chain
length amines are capable to induce the growth process of
I
XI
C
o •H .
^ ^
^ ^
PQ
o
^ c - ' O
» -H O 4J
nj + -H CQ (0 < >
m E d)
C
o
o o
(0 l-i
O
m 4J
H C > 0)
^
^ ^
U 0) o o
0) C
•H (0
c u V O
0) 0) •H 4)
o» c
C § O I
O V 4) M-i
c o
o c •
4J « '
> u •H a x : o c -H
c o o
o 1 - 4
0)
o * -
c
«
«o l-(
* CO rH CO
:><
VO r-l • ro •-» ro
i>C
VO 1-t
• 00 0 m
i<i
VO 1-1 • n 0 m II
1
u:. ro ^ i-H
• ro
rH 1 >< ^ ro c t-«
• ro
r-«
1 u; tn V 0» ro
rH 1 u: Ov Ov CM • ro
n ro 0
c o
4J ^ 10 (0 I
*J -H ^
O 5 c o *« u o
o E
f-i ro r- ro <N CTv 00 'a* 00 r^ f^ <H Ov ON 0> CD CT> (TV <7> <7\ Ov OV CT' Ov
• • • * • • o 0 0 0 0 0
t-H
CO 00 •
If)
r-r-
t ro 0
Tf Ov 00
r CM in
CM rH Tj-
Tf 00 00
^ r-r-
00 ro 0
ro ov 00
r-CM in
r-o (TV
VO VO
•* ro o o o
ro
Tf ro o O O
i n r- VO «-H VO CM CO ^ i n r-O CM -^ VO O " ^ i n • * CM CN» CM >-• o o o
• • • t • 0 0 0 0 0
0 CM OV
ro
0 r-Ov •H
0 CM 0 CM
0 CM ( rH
0 r-ev CM
0 • *
0 ro
o o o o
0 0 0 0 0 C7V VO Tp "«r 00 VO ^ O O t-H CM CM CM ro ro
* • * • • 0 0 0 0 0
0 r-ro 0
0 r in ro
0 00 tH
ro
0 CO 0 CM
0 0 in ro
0 ^ CM ro
0 0 0 0 0
0 CM VO in
CM CM 00 in
0 CM V TT
0 00 VO CM
0 00 CM ro
0 00 ro ro
0 0 0
in 00 CM (M 00 VO Cv CM Ov ov in r-Ov Ov Ov CO ov ov 0\ o\ &i o^ &> (y\ 31 0
Ov CO rn
0
CM r-ro
0
ro (N CM
0
i-H
in t
0
in r 00
0
ro r-'j'
• •
T5 V C 0 u
CD 00 CM VO ro
in t-H <-H CM ro ro 00 c CM in r» r-' c^ n cvi r* 00 ^
CO 00 CM VO r o <-•
5 in
m ov
in in • CM <^
in 0 in t-H
VO
CM 00 c ro ro
ro ov ^ C7V rH
CM f-H
"T
r-0 0 0 0 0 0 0
o o o o o o ^ r*' ro r« o ^ ov ^ t-i ro i n •* ^ VO r - r^ CO crv 0 0 0 0 0 0
o o o o o o ^ CM CM m CM O ov CO CO »-• ro O i n Ov Ov Ov ov o
• • • « • • O O O O O -H
0 0 0 0 0 0 ^ VO CM ^ VO tH CM m CM O CM VO ro •* ro o O O
0 0 0 0 0 0 •H CO in in VO ro o 00 VO c^ in in
<T> O VO CM fH O
i-H CM t-H ^H t-H r H
0) c •H i rH >t iJ 3 m c
0 0 rH •
0
0 in t-H
• 0
0 0 CM •
0
0 0 VO «
0
0 0 r-•
0
V
^
i r-l >. X 0) X f c
0 CM 0 •
0
0 m 0 •
0
0 0 •H •
0
in
r» rH •
0
0 tn Ci •
0
0 in ro •
0
o> • o\ ON • o
o a\ (T> o • o
o r-a\ a> • o
»H ON
o Ot • o
r~-'* 00 a> • o
o m M" u^ r~ \o 00 •* •-< 00 c> o^ O^ <7 CO C^ <T* CO cr (7N o^ o^ ci o^ o o o o o o
22
m vo in •
00 CM
t-H
CO ON •
• *
m
•*»•
^ «t • o m
CO o f-• r-OJ
0^ <«)• •«3"
• t->
fN)
O ^ m
ro CM
n n ON
if) m
in ON
vo ^ in
vc CN in
r-
^ • *
o r-ro
in r-t CN
o t-H
r-( VO in
CO <N
in r~ c ««f ro
1 •xr t
o fO
in .-« 1
r-<N
00 ^ ^
»-« (N
c n ro
en <NI
I O) CTi
in ro
vo Ov vo 1-<
in
vo (N in
r ij-
o •««'
o r-ro
r tH
CM
O >H
00 ^ r-ro •*
(N O vo r-
ro fN
m in
on Tf a m
Tf C r-o
vo Tf
r .-1
.H CO o CO
t 1-1
o vo
r-i-i
Ov oo
r-t '* VO CO
f-t
• ^
»H in
<N CM
o o o o o n ro cjv o t^ O f^ vo (TV vo CM o ro n o
•H CM (N (N <N
o o o o o o vo o o o rn o ^ in ro r ro • vo 'V ^ in vo ^
•-• <*M C N ro
o o r-r-
o CN
o CO
o r-Ov o
o o r-»H
o o 00 Tt
o o CN o •
o r vo •
o in ro ro •
o o CO in •
o ^
•
o o r-4
• CN ro ro CN OJ CN ro
o o c • *
o o ro CO
O CO 00 00
o OV vo CO
o o in 00
CN ro ro ro (N
O O o O O O o o <y> o r- o\ ro ro CN CO CN vo vo o ^ CD in «-«
r-i ro ro ^ in in
o o o o o O O O vo CO in ^ vo r* o ^ r^ t^ in CO ro ro
o ro r-
o o (TV CN
O o vo in
O CO r CN
o o (N in
o o in CN
CN ^ in VO VO in
M
•-t
T3 C
o
•H
e >i in o in o 4J CN vo r^ O 0 . 0 0 0 - ^ 4) • • • •
as o o o, o
in CN
0) c
r-* o o o o o in >« rH CN ro '<f in ( *j o o o o o o u • • • • • • o o o o o o o
33
12.00-
10.00-
\: 8 0 0 -
>a>
o u
O
•^
o ^
( 0 . 060 m)
(0 .075m)
( 0 . 0 2 5 m )
(0.100m)
6 00
(0 .125m)
(0 0 0 m )
ooL _L 3.10 3.20 3 30
l /TdO^K S 3 4 0
Fig. No . 9 : Gibbs- Helmholfz plots for 0 1m CTAB-»- 0 1 m KBr m fhe presence of various concentrafion of n-heptyl amine mentioned in ( )
34
I o o
<]
56.0
42 0
14.0
0 0
n -• -
® -O -
C4NH2
C6NH2
C7NH2
C8NH2
0.2 0 4
[ n - amine J (m)
:SL 0.6 0.8
F i g . N o , 1 0 ; Voriofion of activation enthalpy ( A H * ) for the viscous flow
of 0.1 m CTAB H- 0,1 m KBr solutiorvs as a function of odded n-amines
3r)
mice l l e s upto a optimum concentration, beyond which a solvent
structure comes In p ic ture . While the low values for A H*
for C-NHo show that the water structure factor plays an
Important role with hydrophlllc addit ive with a concomitant
breaking of larger aggregates. The behaviour of these amines
Is due to the combined e f f e c t of two opposite e f f e c t s , namely^
part i t ion ing in mice l lar phase and part i t ioning in bulk
solvent . At higher concentrations the l a t t e r e f f ec t plays
an Important role in breaking the larger aggregates.
R E F E R E N C E S
3r,
1. V. Ramamurthy, Tstrahadron Report No, 211, T&trahedron,
£3 , 5753 (1986) .
2. J.W. Mcaain, • 'colloid 3019009", D.C. Heeth and Co.,
Boston, 1950.
3. W.C. Pres ton , j . Phys. and c o l l o i d Chem., 52, 84 (1948),
4 . G.S. Har t l ey , "Aqueous s o l u t i o n s of Pa ra f f in chain s a l t s " ,
Hermann, P a r i s , 1936.
5. J .K. Thomas, "The Chemistry of Exc i t a t i on a t I n t e r f a c e s " ,
American Chemical Soc ie ty , Washington D . C , 1984.
6 . W.L. Hinze, in "Colloids and Sur fac t an t s i Fundamentals
and App l i ca t ions" , -Sditad oy E. Burni and S. P e l i z z a t t i ,
soc i e ty Chemica I t a l i a n a , Rome, pp. 167-207, 1987.
7. P.H, Elworthy, A.T. Florence and C.iJ. Macfarl^ne, in
" S u l u o i l i z a t i o n by Surface Active Agents and i t s Appli
ca t ions in chemistry and Bio log ica l s c i e n c e s " . Chapman
and H a l l , London, 1968.
8. M.J. Shick, J . c o l l . SCi . , r 7 , 801 (1963) .
9. M.J, schwuger, j . Am, Oi l Chem. S o c , 59., 258 (1982).
10. J . Leja , "Surface Chemistry of Froth F l o t a t i o n " , Plenum,
New York, 1982.
1 1 . R.H. O t t a w i l l , in "^^onionic S u r f a c t a n t s " , Edited by M . j .
Shick, Dekksr, New York, 1967,
12. P. ^*ukh^rJaa, in "Solut ion Chamistry of S u r f a c t a n t s " ,
Edited by K.L. M i t t a l , Plenum Pre s s , Naw York, 1979.
3
1 3 . J . H , Pand l a r and 3 . J . F e n d l a r , • ' C a t a l y s i s i n M i c e l l a r
and M a c r o n o l a c u l a r Systems'*, Acadamic P r a s s , I n c . ,
New York, 1975 .
14. M a r t i n j . S c h i c k , ( a d , ) , • •^^nionic S u r f a c t a n t s P h y s i c a l
Crjemistry'*, Marce l Dakkar, I n c . , New York, 1987,
1 5 . P . Mukerjae and K . J , M y s e l s , " C r i t i c a l M i c e l l a concen
t r a t i o n s of Aqueous S u r f a c t a n t S y s t e m s " , NSRDS-NB3 36,
s u p e r i n t e n d e n t of Documents, Washington , B . C . , 19 7 1 ,
16 . K . J , M y s e l s , " I n t r o d u c t i o n t o c o l l o i d c h e m i s t r y " . I n t e r , ,
P u b . , Naw York, 1959.
17 . K, Sh inoda , T. Nakagawa, B. Tamaroushi, and T. Isemura
" C o l l o i d a l S u r f a c t a n t s % some P h y s i c o - c h e m i c a l P r o p e r t i e s
Academic P r e s s , New York, 1963 ,
1 8 . a, Llndmann and H. Wannarstrom, " M i c e l l e s " , Topics in
C u r r a n t Chemis t ry , Vol 87, P . 5 . S p r i n g e r - V a r l a g , Bar l l ry '
Haideloarg/New York, 1980; Y. C h a v a l i a r and T, aaroo,
r e p . P rog , P h y s , , 5_3# 279 ( 1 9 9 0 ) .
1 9 . S, C a p o n e t t i , D. C h i l l u r a ^ ^ a r t i n o , M.A. F l o r i a n o , and
R. T r i o l o , J . Am. Cham. s o c . , 9., 1193 ( 1 9 9 3 ) .
20 . CIS. M a c f a r l a n a , K o l l o i d - z , Z. Polym. , 2 39 , 682 ( 1 9 7 0 ) .
2 1 . J . C l i f f o r d , and a .A. f ^ t h i c a . T r a n s . Faraday S o c ,
6 1 , 182 ( 1 9 6 5 ) .
22 . N. ^ i u l l e r and R.H. a i r k h a h n , j . Phys , Cham,, Jl* 957 ,
( 1 9 6 7 ) ; J . Phys . Cham., 12^, 583 ( 1 9 6 8 ) .
2 3 . J . C l i f f o r d , T r a n s . Faraday S o c , £ 1 , 1276 ( 1 9 6 5 ) .
24 . C . J . C l eme t t , j , Chem. S o c , A, 2251 (197^1^*"" '^ " ^ \
3.S
2 5 . N. M u l l a r , In "Reac t ion K i n e t i c s in M i c a l l e s " , Amar.
Chain, S o c . Syinp.# Sdi^ad oy S . Cordes , Planum, Naw York,
p . 1, 1953.
26 . T, Nakagawa and H, J i z o m o t o , K o l l o i d - z . 2 . Polyni . , 250
594, ( 1 9 7 2 ) ,
27 . F. Tokiwa and K, T s u j i , J , C o l l o i d I n t e r f a c e S c i , , £ 1 ,
343 , ( 1 9 7 2 ) ,
2 8 . S . J . R e h f e l d , j . C o l l o i d I n t e r f a c e S c i . , 34, 518, (1970) ;
J . Phys . Cham., 2±* 117 ( 1 9 7 0 ) .
2 9 . G.W, tJrady and M. Kaplan , j . Chera, P h y s . , 5 J , 3535 ( 1 9 7 3 ) .
30. G.W, Brady, J . Chem. P h y s . , 58 , 3542 ( 1 9 7 3 ) .
3 1 . M, Yves T r i c o t , D, P u r l o n g , N a i l , S a r s e , H .F . Wolfgang,
Aus t . J , Chem,, 3 7 ( 6 ) , 1147 ( 1 9 8 4 ) .
32 . J . H . f ^ n d l e r . Ace, Chem, R e s . , J ^ , 7 ( 1 9 8 0 ) .
33 . C.W. Brown, D. Cooper, and J . C . S . Moore, j . C o l l o i d
i n t e r f a c e S c i . , ^ l * 584 ( 1 9 7 0 ) .
34. M, wantz , W.H. Smith and A.R. M a r t i n , J . C o l l o i d I n t e r
face s c i . , ^ , 36 ( 1 9 6 9 ) .
35 . H. S a i t o and K. s h i n o d a , J . C o l l o i d I n t e r f a c e s c i . , ^ ,
359 ( 1 9 7 1 ) .
36. J . F . Yan and M.d. Pa lmer , J . C o l l o i d I n t e r f a c e S c i , , 3£'
177 ( 1 9 6 9 ) .
37 . J . H . F e n d l e r , 3 . J . P a n d l e r , R .T . Medary and O.A. 21 saoud,
J . Chem. s o c , Faraday T r a n s . I . , 69 , 280 ( 1 9 7 3 ) ; J . Phys .
Cham., J 7 , 14 32 ( 1 9 7 3 ) ,
3n
3 8. K. shincxia and T, Nakagawa, i n " C o l l o i d a l S u r f a c t a n t s * /
i l d i t ad by B , I , Tamamushi and T, I semura .* Academic P r e s s ,
New York, 1963 .
39 . P . a a c h e r , i n " C a t i o n i c S u r f a c t a n t s* E d i t e d by E. J u n g a r -
mann. Marce l Dakkar, New York, 1970,
4 0 . J . C l i n t , J . Cham, s o c . Faraday T r a n s , I . , 2 i ' 1327 (1975^ ,
4 1 . H. Lange and K . H . Beck. K o l l , z . Z. Po lym, , 2 5 1 , 424 (1973)
4 2 . T. Nakagawa and H. Inoua , j . Cham, s o c , J a p a n . , 7^ , 104
(1956 ) ,
4 3 . J . K . C o r k i l l , J . F . Goodman, and J . R , T a t e , T r a n s . Faraday
s o c , 60 , 986 t l 9 6 4 ) .
44 . D.N.Rubingh and T, J o n e s , I n d . Sng. Chara, P r o d . R e s .
Dav. , ^ , 176 ( 1 9 8 2 ) .
4 5 . M.F. Smerson and A. H o l t z e r , J . P h y s . Chem,, 2i,» 3320(1967)
46 . P . Muker jee , j . Pharm. s c i . , 6£ , 1528 ( 1 9 7 1 ) .
4 7 . P . Muker jee , j . Pharm. s c i . , 6£ , 1531 ( I 9 7 l ) .
4 8 . Ch. Durga P r a s a d , H.N. S i n g h , P . s . Goyal and K.
S r i n i v a s a n Rao, j . C o l l o i d I n t e r f a c e S c i , , 155 , 415
( 1 9 9 3 ) ,
4 9 . P,M, Lindarouth and G, L , a a r t r a n d J , P h y s . Chem.,
9 7 , 7769 (199 3 ) .
50 . K.S. B i r d i , i n " M i c e l l i z a t i o n , s o l u b i l i z a t i o n and Micro-
e m u l s i o n s " , E d i t e d by K.L, M i t t a l , V o l . 1, p p , 151-169 ,1977 .
5 1 . P . Ekwal l , L . Mandel l and P . so lyom, j . C o l l o i d I n t e r f a c e
S c i . , _35, 519 ( 1 9 7 1 ) .
52 . R. zana , S . Yiv , C. S t r a z i e l l a , and P . L l a n o s , j .
C o l l o i d I n t e r f a c e S c i . , 80, 208 ( 1 9 8 l ) .
'tn
53 . S. Y l v . , R. Zana , W. u l b r l c h t , and H. Hoffmann, J . C o l l o i d
I n t e r f a c e S c i . . 8 0 . 224 (1981) .
54 . Hercmann, J . P h y s . Chem. , ^ , 1540 ( 1 9 6 4 ) .
55 . M.A. Mazer and G. O l o f s s o n , J . P h y s . Chem., £<6, 4584
( 1 9 8 2 ) .
56. C. Gamboa and L. Sepu lveda , J . C o l l o i d I n t e r f a c e S c i . ,
113 . 566 (1986 ) .
57. L. Sepulveda and C. Gamboa, J . C o l l o i d I n t e r f a c e S c i . ,
118. 87 (1987) .
5 8 . P .H . E l w o r t h y . K o l l o i d - Z . , 20_3_, 67 ( 1 9 6 5 ) .
59. D. Attwood and A.T. F l o r e n c e . " S u r f a c t a n t Sys tems , T h e i r
C h e m i s t r y , Pharmacy and Biology",Chapman and H a l l ,
L o n d o n , ( 1 9 8 3 ) .
60. P .H. E lwor thy and C. McDonald, K o l l o i d - Z , 195, 16 ( 1 9 6 5 ) .
6 1 . D. Attvrood. J . Phys , Chem., 72_. 339 ( 1 9 6 8 ) .
62. H. Hoffmann, H .S . Kie lman. D. P a v l o v i c . G. P l a t z . W.
U l b r i c h t . J . C o l l o i d I n t e r f a c e S c i . , ' 8 0 , 237 (1981 ) .
63 . P . 3. N i l s o n . H. Vfennerstorm, and B. Lindman, J . P h y s .
Chem.. 8 7 , 1377 ( 1 9 8 3 ) .
64. R.H. o t t e w i l l , c,C. s t o r e r , and T. w a l k e r . T r a n s . Faraday
S o c . , ^ . 2796 ( 1 9 6 7 ) .
65 . J . Lang, A. D javankh t , and R. Zana , J . Phys . Chem., 8 4 ,
1541 (1980 ) .
66. M. Almgren and S h a n t i Swarup, j . P h y s . Chem.^£2 ' ^"^^
( 1 9 8 3 ) .
67. P . L i a n o s and R. Zana , J . P h y s . Chem., 8_4, 3339 ( 1 9 8 0 ) .
41
6 8, S. Ozeki and S. I k e d a , J . C o l l o i d I n t e r f a c e s c i , , 77,
219 ( 1 9 8 0 ) .
6 9 . H. Hoffman, G. P l a t z and W. U l b r i c h t , J , P h y s . Cham,,
_85, 1418 ( 1 9 8 1 ) .
70 . T. Imaa, A. Aba and S . I k a d a , J . P h y s , Cham,, 92# 154 8
(19 8 8 ) .
7 1 . K.G. Gotz and K. Hackroann, j . C o l l o i d I n t e r f a c e S c i . ,
1 2 , 206 ( 1 9 5 8 ) .
72 . S . Hayashi and S . I k a d a , J . P h y s . Chetii.i 84, 744 (1980 ) .
7 3 . S. I k e d a , S . Ozaki and i'*. Tsunoda, J . C o l l o i d I n t e r face
s c i . , 22, 27 (19 80) .
74. G. Lindolom, B. Lindxnan and L , M a n d e l l , J . C o l l o i d
I n t e r f a c e 3 c i . ; , 4 2 ' ^00 (19 7 3 ) .
75 . R. Dorshow, J . B r i g g s , C.A. Bunton and D, ^ i c o l i , j .
Chem. P h y s . , 86, 2388 (19 8 2 ) .
76 . C.Y. Young, P . J . M i s s e l and G. tenedeck, J . Phys . Chem.,
^ , 1375 ( 1 9 7 8 ) .
77 . C.A. Bunton i n ••Reaction K i n e t i c s i n M i c e l l e s " , Ed i t ed
by E.H. Cordes , Plenum, New York, 1973 ,
78 . E.H. Cordes and R .B . Dunlap , Accounts Chem, R e s , , 2
329 ( 1 9 6 9 ) .
79 . G.J . U i s t , C.A. J u n t o n , L. Rob inson , L. S e p u l v e d a , and
M. Statn, J , Amer. Cheni. S o c . , 92# 4072 ( 1 9 7 0 ) .
80. w.L, Hinze and D.W. Armst rong , iSds, "Ordered Media i n
Chemical S e p a r a t i o n s " , APiarican Chemical S o c i e t y ,
Washington, 1987.
o
8 1 . P«G. DeGennes^nd C. T o u p i n , J . P h y s . Chem.^ 86 , 2294
( 1 9 8 2 ) .
8 2 . M, Almgren and J . E . L o f r o t h , J . C o l l o i d I n t e r f a c e S c l . j
81 J 486 ( 1 9 8 1 ) ; M. Almgren and S. swarup , J . C o l l o i d
I n t e r f a c e S c i . . ^ ! » 256 ( 1 9 8 3 ) .
8 3 . D . J . M i t c h e l l and B.W. Ninham, J . Chem. Soc . , Faraday
T r a n s . ; 2 , 2Z • ^^^ ( 1 9 8 1 ) .
8 4 . K.R. vtormuth and E.w. Kale^ J . P h y s . Chem. ,91 6 1 1 ( 1 9 8 7 ) .
8 5 . J . Fang and R.L. V e n a b l e , J . C o l l o i d I n t e r f a c e S c i . » 1 1 6
269 ( 1 9 8 7 ) .
8 6 . H. N. S i n g h , C D . Prasad and S. vumar, J . Am. O i l
C h e m i s t s S o c 2 2 * ^^ ( 1 9 9 3 ) . 8 7 . A. K h a t o r y , F. K e r n , F. Lequeux* J . A p p e l l , G. P o r t e ,
N. M o r i e , A. O t t and W. Urbach , L a n g m u i r . r ^ , 933 ( 1 9 9 3 ) .
8 8 . A. K h a t o r y , F. Lequeux , F. Kern and S . J . Candau,
Langmuir . , 2 • ^^56 ( 1 9 9 3 ) .
8 9 . P.M. L in temuth and G.L. B e r t r a n d , J . P h y s . Chem. , 22.
7769 ( 1 9 9 3 ) .
9 0 . Z.K. Zhou, P . Q . Wu and C. X i a o , Acta P h y s . Chim. S i n . ,
_4 . 340 ( 1 9 8 5 ) .
9 1 . V. R a j a g o p a l a n , P . S . G o y a l , B. S. v a l a u l i k a r and B. A.
Darannacharya , P h y s i c a B*, 180 , 525 ( 1 9 9 2 ) .
9 2 . H.N. S ingh and S. Sv/arup, B u l l . Chem. s o c . J p n . , ^ ,
1534 ( 1 9 7 8 ) .
9 3 . 0 . B a y e r , H. Hoffmann and W. U l b r i c h t , "Proc . I n t .
Symp. S u r f a c t a n t i n s o l u t i o n " . E d i t e d by K.L. M i t t a l
and P. B o t h o r e l , v o l . 4 , Plenum P r e s s , New York, 1 9 8 6 .