physico-chemical behaviour of aqueous and … · 2018. 1. 4. · phone; (0571) 25515 department of...
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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
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DS2433
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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)
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Bebttateb ^0 tl)E iHemorp of
(Late) PROF. H. N. SINGH
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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
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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.
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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
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I N T R O D U C T I O N
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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
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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
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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
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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 )
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:»
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
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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
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—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 .
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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
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^
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
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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
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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
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^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
![Page 21: PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY A L I G A R H —202 002 Dated. ]>.9.:S1.. Dr](https://reader035.vdocument.in/reader035/viewer/2022081615/5fe5067b12f77d62950f4810/html5/thumbnails/21.jpg)
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 * *
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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
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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.
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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
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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.
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E X P E R I M E N T A L
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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
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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.
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RESULTS AND PISCUSSION
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: 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
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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.
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' ) 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
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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 .
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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
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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
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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
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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
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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
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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 ( )
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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
![Page 41: PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY A L I G A R H —202 002 Dated. ]>.9.:S1.. Dr](https://reader035.vdocument.in/reader035/viewer/2022081615/5fe5067b12f77d62950f4810/html5/thumbnails/41.jpg)
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)
^
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U 0) o o
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ro
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0
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ro (N CM
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in t
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ro r-'j'
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CO 00 CM VO r o <-•
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m ov
in in • CM <^
in 0 in t-H
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CM 00 c ro ro
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CM f-H
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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
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0) c •H i rH >t iJ 3 m c
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0
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• 0
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0
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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 ^ ^
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c n ro
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in ro
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r ij-
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CM
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m in
on Tf a m
Tf C r-o
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t 1-1
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r-i-i
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r-t '* VO CO
f-t
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•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
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o o c • *
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O CO 00 00
o OV vo CO
o o in 00
CN ro ro ro (N
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r-i ro ro ^ in in
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o ro r-
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O o vo in
O CO r CN
o o (N in
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CN ^ in VO VO in
M
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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
![Page 43: PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY A L I G A R H —202 002 Dated. ]>.9.:S1.. Dr](https://reader035.vdocument.in/reader035/viewer/2022081615/5fe5067b12f77d62950f4810/html5/thumbnails/43.jpg)
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 ( )
![Page 44: PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY A L I G A R H —202 002 Dated. ]>.9.:S1.. Dr](https://reader035.vdocument.in/reader035/viewer/2022081615/5fe5067b12f77d62950f4810/html5/thumbnails/44.jpg)
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
![Page 45: PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY A L I G A R H —202 002 Dated. ]>.9.:S1.. Dr](https://reader035.vdocument.in/reader035/viewer/2022081615/5fe5067b12f77d62950f4810/html5/thumbnails/45.jpg)
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.
![Page 46: PHYSICO-CHEMICAL BEHAVIOUR OF AQUEOUS AND … · 2018. 1. 4. · PHONE; (0571) 25515 DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY A L I G A R H —202 002 Dated. ]>.9.:S1.. Dr](https://reader035.vdocument.in/reader035/viewer/2022081615/5fe5067b12f77d62950f4810/html5/thumbnails/46.jpg)
R E F E R E N C E S
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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
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and H a l l , London, 1968.
8. M.J. Shick, J . c o l l . SCi . , r 7 , 801 (1963) .
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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.
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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 . ,
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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 , ,
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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,
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26 . T, Nakagawa and H, J i z o m o t o , K o l l o i d - z . 2 . Polyni . , 250
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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 ,
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