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=
|
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.
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( 3 )
w h e r e I - t h e a d s o r p t i o n c o e f f i c i e n t a t t h e e q u i l i b r i u m c o n c e n t r a t i o n o f t h e s u r f a c t a n t i n s o l u t i o n
c ; I
m
- t h e m a x i m u m a d s o r p t i o n c o e f f i c i e n t ; K - t h e c h a r a c t e r i s t i c c o n s t a n t o f t h e i n t e r a c t i o n
b e t w e e n t h e a d s o r b e d m o l e c u l e s a n d t h e s o l i d s u r f a c e s i t e s , e - a p a r a m e t e r d u e t o i n t e r a c t i o n
b e t w e e n a d s o r b e d m o l e c u l e s .
T h e e q u a t i o n ( 3 ) i s a l i n e a r e q u a t i o n ; t h e s l o p e i s d e n o t e d w i t h a l p h a ( ) w h i c h i s e q u a l t o
2 / 2 . 3 0 3 .
F r o m t h e F o w l e r - G u g g e n h e i m e q u a t i o n w e c a n o b t a i n t h e f r e e e n e r g y o f a d s o r p t i o n
A G
a d s
a n d t h e f r e e e n e r g y o f i n t e r a c t i o n A G
i n t
( T a b l e 3 ) .
Tabl e 3. A d s o r p t i o n a n d i n t e r a c t i o n e n e r g y v a l u e s b e t w e e n a d s o r b e d m o l e c u l e s a t
c o t t o n / w a t e r i n t e r f a c e a t 2 5
0
C ( F o w l e r - G u g g e n h e i m M o d e l ) .
Surfactant Ln K Kx1 0
3
al pha
ads
G A
kj /mol
int
G A
kj /mol
R
2
C
1 6
P
y
C l - 5 . 2 0 5 . 5 - 2 . 0 1 - 2 . 3 1 - 1 2 . 9 9 - 5 . 8 1 0 . 9 8 4
A M -
C
1 6
P
y
C l
- 8 . 3 3 0 . 2 3 - 1 . 3 2 - 1 . 5 2 - 2 0 . 9 - 3 . 8 0 0 . 9 8 7
R T - C
1 6
P
y
C l - 3 . 3 0 3 6 . 7 - 3 . 4 0 - 3 . 9 1 - 8 . 2 7 - 9 . 8 2 0 . 9 6 5
[ R T ] - 6 . 6 5 1 . 2 8 - 1 . 1 9 - 1 . 3 7 - 1 6 . 6 7 - 3 . 4 7 0 . 9 3 1
K ln RT G
ads
= ( k j / m o l ) , RT G
int
= ( k j / m o l ) , = 2 / 2 . 3 0 3 .
120 Tyut yunni k, Chkhet i j a, Get si na, Badul i na, Gal uzi nskaya, L evi t an, K ubrakova
T h e m o d e l r e v e a l s t h e e x i s t e n c e o f e l e c t r o s t a t i c i n t e r a c t i o n s i n r e g i o n I . F o r t h e s y s t e m
A M - C
1 6
P
y
C l , a h i g h e r v a l u e o f G
a d s
w a s r e g i s t e r e d t h a n i n t h e c a s e o f a s i n g l e s u r f a c t a n t ,
w h i c h s h o w s t h e h i g h e r a d s o r p t i o n p o w e r o f t h e d y e . I n t h e c a s e o f t h e m i x e d s y s t e m s R T -
C
1 6
P
y
C l , a d e c r e a s e i n t h e a d s o r p t i o n e n e r g y a n d a n i n c r e a s e i n t h e i n t e r a c t i o n e n e r g y i n
c o m p a r i s o n w i t h a q u e o u s c a t i o n i c s u r f a c t a n t s o l u t i o n s i s o b s e r v e d .
M O D E L Langmuir: a m o d e l w h i c h e x p l a i n s t h e e l e c t r o s t a t i c i n t e r a c t i o n s b e t w e e n
s u r f a c t a n t , d y e m o l e c u l e s a n d c o t t o n s u r f a c e .
F o r d e t e r m i n a t i o n o f t h e m a x i m u m s u p e r f i c i a l e x c e s s I
m a x
, d e f i n e d a s t h e m a x i m u m m o l
n u m b e r o f t h e s u b s t a n c e t h a t c a n b e a d s o r b e d o n t h e i n t e r f a c e a n d t h e m i n i m u m s u r f a c e
o c c u p i e d b y a n a d s o r b e d m o l e c u l e o n l i q u i d - g a s a n d l i q u i d - l i q u i d i n t e r f a c e , t h e L a n g m u i r
i s o t h e r m i s u s e d :
2
2 ) 1 (
2
1 Kc
Kc
RT
B
+
= I ( 4 )
w h e r e K i s t h e a d s o r p t i o n c o n s t a n t .
T h i s e q u a t i o n c a n b e d e d u c e d f r o m t h e i n t e g r a l e q u a t i o n o f s u r f a c e t e n s i o n i s o t h e r m
c o m b i n e d w i t h G i b b s e q u a t i o n . T h e l i n e a r f o r m o f t h e a d s o r p t i o n e q u a t i o n p e r m i t s g r a p h i c
d e t e r m i n a t i o n ( F i g . 5 ) o f t h e m a x i m u m a d s o r p t i o n c o e f f i c i e n t a n d t h e c o n s t a n t k :
K
c c
I
+
I
=
I
max max
2
2
2
1
Fig. 5. L a n g m u i r a d s o r p t i o n i s o t h e r m
H a v i n g i n v i e w t h e d e f i n i t i o n o f s u p e r f i c i a l e x c e s s , t h e i n v e r s e o f t h i s v a l u e i s e q u a l t o t h e
s u r f a c e o c c u p i e d b y a m o l e c u l e i n t h e s u p e r f i c i a l l a y e r . I
m a x
b e i n g k n o w n , w e h a v e c a l c u l a t e d
2
2
I
c
c
2
( m o l / L )
max
1
I K
max
1
I
Eurasi an J. Anal . Chem. / Vol :3, N o:1, 2008 1 21
the minimum surface occupied by a molecule at the interface,
*
A by equation (2).
Tabl e 4. Evaluated values by Langmuir equation
Studi ed
system
a
max
1 0
5
mol/g
max
1 0
6
mol /m
2
kx1 0
5
nm
2
/
molec
Ln K F
ads
=-
RTl nK
kj /mol
R
2
C
16
P
y
Cl 3.35 1.056 2.58 1.57 -10.56 -26.45 0.998
AM 0.684 0.215 1.580 0.775 -11.05 -27.71 0.923
AM-
C
16
P
y
Cl
0.203 0.640 4.63 2.59 -9.97 -24.99 0.995
RT 5.708 1.800 37.40 0.926 -7.88 19.78 0.920
RT -
C
16
P
y
Cl
3.340 1.053 3.32 1.57 -10.31 -25.86 0.996
In the case of mixed aqueous solutions of AM - C
16
P
y
Cl, the specific molecular surface
was 2.5 nm
2
/molecule at the cotton/water interface, while for the aqueous surfactant solutions
the occupied surface is 1.57 nm
2
/ molecule.
For the cationic dye system RT - C
16
P
y
Cl, the minimum surface occupied by a molecule
at the interface is equal to the surface occupied by surfactant molecules, which confirms the
preferential adsorption of surfactant molecules at the cotton/water interface (Fig. 4).
4. Concl usi ons
The adsorption isotherms of cationic surfactants of alkylpyridinium chloride type at the
cotton/water interface belong to the L class, 4 under-classes of preferential adsorption
isotherms. In the first stage of adsorption, the cationic surfactant is adsorbed on the cotton
surface by electrostatic interaction. At surfactant concentrations close to CMC an increase in
the adsorbed quantity on the substrate is observed due to hydrophobic interactions between the
hydrocarbon chains of molecules adsorbed at the interface and those in solution; close to CMC
a maximum is observed which points to the fact that the formation of micelles in solution
prevails over the formation of a bi-layer at the interface.
It was found that the cationic change capacity of cotton fibres can be measured using
the cationic dyes AM and RT. The adsorption isotherms of aqueous mixed solutions of
alkylpyridinium chloride - methylene blue (C
16
P
y
Cl-AM) were obtained. These isotherms pointed
to a competitive adsorption between surfactant and dye. The studies revealed that the dye is
dissolved in the micelles of the cationic surfactant, which hampers its adsorption on the fibres;
the depth of dyeing is proportional to the cationic change capacity or to the increase in ion pair
adsorption.
122 Tyut yunni k, Chkhet i j a, Get si na, Badul i na, Gal uzi nskaya, L evi t an, K ubrakova
T h e t y p e o f i n t e r a c t i o n s a n d t h e o r i e n t a t i o n m o d e o f c a t i o n i c s u r f a c t a n t m o l e c u l e s i n
e a c h s t a g e o f a d s o r p t i o n a t t h e c o t t o n / w a t e r i n t e r f a c e a r e s t u d i e d b y v e r i f i c a t i o n o f o r i g i n a l d a t a
o n c l a s s i c m o d e l s ( F o w l e r - G u g g e n h e i m , L a n g m u i r ) c o n c e r n i n g t h e a d s o r p t i o n o f i o n i c
s u r f a c t a n t s o n s o l i d s . F o r d y e s u r f a c t a n t a q u e o u s s o l u t i o n s A M - C
1 6
P
y
C l , h i g h v a l u e s o f t h e
a d s o r p t i o n e n e r g y w e r e o b t a i n e d i n c o m p a r i s o n w i t h t h e v a l u e s o b t a i n e d f o r s u r f a c t a n t a q u e o u s
s o l u t i o n s . T h i s p o i n t s t o a h i g h e x t e n t o f d y e a d s o r p t i o n o n t h e c o t t o n / w a t e r i n t e r f a c e . F o r t h e
d y e s u r f a c t a n t R T - C
1 6
P
y
C l s y s t e m , t h e a d s o r p t i o n e n e r g y i s l o w e r , b u t t h e i n t e r a c t i o n e n e r g y
i s h i g h e r , w h i c h c o n f i r m s t h e p r e f e r e n t i a l a d s o r p t i o n o f s u r f a c t a n t m o l e c u l e s a t t h e c o t t o n / w a t e r
i n t e r f a c e .
References
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8 . E l e n a I r i n a M o a t e r , M i h a e l a O l t e a n u , Bulletin of University Petrol-Gaze Ploiesti, v o l .
L V I I , 2 / 2 0 0 5 p . 1 7 6 - 1 7 9 , I S S N 1 2 2 1 - 9 3 7 1 .
9 . G i l e s G . H . , D . S m i t h a n d A . H u i t s o n , J. Colloid and Interface Sci. , 4 7 , n o . 3 , 1 9 7 4 , p . 7 5 5 .
1 0 . G i l e s , C . H . , T . H . M a c E w a n , S . N . N a k h v a , a n d D . S m i t h , J. Chem. Soc. 5 6 , 3 9 7 3 .
1 1 . E l e n a I r i n a M o a t e r , M i h a e l a O l t e a n u , C r i s t i a n a R d u l e s c u , I o n i c a I o n i , Review of
Chemistry, 5 6 ( 1 1 ) , 2 0 0 5 , p . 1 1 6 0 - 1 1 6 3
1 2 . F o w l e r R . , G u g g e n h e i m E . A , Statistical Thermodynamics, C a m b r i d g e U n i v e r s i t y P r e s s ,
1 9 5 6 , L o n d o n , 4 2 9 .
Corresponding author: E l e n a I r i n a M o a t e r
Address: U n i v e r s i t y V a l a h i a f r o m T r g o v i t e , F a c u l t y o f S c i e n c e s a n d A r t s , D e p a r t m e n t o f C h e m i s t r y ,
B l v d . U n i r i i , 1 8 - 2 0 , T r g o v i t e , R o m a n i a
Phone: ( + 4 0 ) - 2 4 5 2 2 2 1 7 5 ; 7 2 4 2 6 0 1 0 5
Fax: ( + 4 0 ) - 2 4 5 2 2 2 1 7 5
E-mail: i r i n a m o a t e r @ g m a i l . c o m