Electronic Supplementary Material (ESI) for RSC Advances

This journal is © The Royal Society of Chemistry 2013

Supporting information for:

Interactional Behaviour of Surface Active Ionic Liquids with Gelling Biopolymer

Agarose in Aqueous Medium

Pankaj Bharmoria and Arvind Kumar*

†
Salt & Marine Chemicals Division, CSIR-Central Salt and Marine Chemicals Research
Institute, Council of Scientific & Industrial Research (CSIR), G. B. Marg, Bhavnagar-
364002, Gujarat, India
Electronic Supplementary Material (ESI) for RSC Advances
This journal is © The Royal Society of Chemistry 2013

Annexure S1.

1. Adsorption efficiency pC20 was calculated from surface tension vs. concentration graphs
using equation 1.
pC20 = −log C20 (1)
Where C20 is the concentration required to reduce the surface tension of pure solvent or
solution by 20 mN·m−1. A higher pC20 value is indicative of a higher adsorption efficiency of
the surfactant at the interface and more efficiency in reducing surface tension.
2. Surface pressure at cmc, Пcmc was calculated from the difference of surface tension of
native solution and surface tension at cmc using equation 2.
Пcmc = γo–γcmc (2)
where γ0 is the surface tension of pure solvent or solution and γcmc is the surface tension of
the solution at cmc. The parameter indicates the maximum reduction of surface tension
caused by the dissolution of surfactant molecules and hence becomes a measure for the
effectiveness of the surfactant to lower the surface tension of either pure solvent or native
solution.
3. Γmax is calculated following the Gibbs adsorption equation 3.
1    (3)
 max   ltC 0  
nRT   ln C T
where n, R, T and [C] are the number of species formed per IL molecule in solution upon
ionization (it is 2 for both [C4mim][C8OSO3]) and [C8mim][Cl], the universal gas constant,
absolute temperature and the molar concentration of IL in solution respectively. The
parameter indicates, relative amount of surfactant adsorbed at the interface. Higher surface
excess value signifies higher adsorption. Here concentration was used in place of activity, as
the solutions used were fairly dilute.1-3
4. Amin was obtained from the equation 4.

1
Amin    (4)
N Amax
                                                                                                        

Where NA is the Avogadro number.1‐3  Parameter signifies the minimum area occupied by
surfactant monomer at the interface. Lower value of Amin indicates higher adsorption of
monomer at the interface. 
Electronic Supplementary Material (ESI) for RSC Advances
This journal is © The Royal Society of Chemistry 2013

5. The degree of counter-ion dissociation, α was calculated from the ratio of slope
(S2/S1) of linear fragments of conductivity profiles of post-micellization(S2) to pre-
micellization (S1) region. Parameter indicates the feasibility of micellization. Lower value of
α indicates better binding of counter ion with surfactant head group thus increases the
feasibility of micellization.

6. The standard Gibbs free energy of micellization Gmo was calculated using equation 5.

∆ 2 ⍺ ln 5  

7. The standard Gibbs free energy of interfacial adsorption (ΔGad°) was calculated using the
equation 6.

∆ ∆ /Γ   (6)

The parameters of equation (5) and (6) indicate feasibility of micellization in the bulk and
adsorption at the interface. Higher negative value of these parameters indicates better
feasibility of the process.

4 10
10
(A) C3(cmc) 2 (B) C3(cmc )
3 8
8
/ (mS.cm )

/ (mS.cm )

/ (mS.cm )
-1
/(mS.cm )

2 6
-1

1 6
C2 cmc
1 (cmc ) 4 4

0
-1

-1

2
0 2
Without Agarose Without Agarose
0.02% Agarose 0.02% Agarose 0
-1 -1 0
-10 0 10 20 30 40 50 60 70 80 0 20 40 60 80 100 120 140 160
-1 -1
C / mmol.kg ) C / (mmol.kg )

Fig. S1 Specific conductance (κ) as a function of IL concentration: (A) [C4mim][C8OSO3] and

(B)[C8mim][Cl] .Various transitions are marked with vertical line.( hollow and solid symbols
correspond to left and right y-axis respectively)
Electronic Supplementary Material (ESI) for RSC Advances
This journal is © The Royal Society of Chemistry 2013

10
50

0 25

-10 0

-25
Watts

Watts
-20
-50
-30
-75
-40 -100

-50
(A) -125
(B)

0 20 40 60 80 100 120 140 160 0 50 100 150 200 250 300 350
Time / (minute) Time / (minute)

Fig. S2 Differential power plots of interaction of Ag with (A) C4mim][C8OSO3] (B)

[C8mim][Cl] 

6
[
C
8
m
i
m
]
[
C
l
]
i
n
w
a
t
e
r
d
d
H
/
d
c
o
f
[
C
8
m
i
m
]
[
C
l
]
i
n
w
a
t
e
r

-1500 ︵ ︶

-1550 5
dH / (J.mol )
-1

d (dH)/dc

-1600
4

-1650

3
c
m
c

-1700

-1750 2
40 60 80 100 120 140
-1
C / (mmol.kg )

Fig. S3 ITC thermogram of [C8mim][Cl] dilution in water.

Derivative of thermogram showing transition at cmc.
Electronic Supplementary Material (ESI) for RSC Advances
This journal is © The Royal Society of Chemistry 2013

1.0
-1
0.9 Pure Ag 4.5 mmol.kg 6.44 mmol.kg
-1

0.8 158nm 158 nm 158 nm

0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
-0.1
1.0
-1 -1 -1
0.9 10.43 mmol.kg 15.13 mmol.kg 19.73 mmol.kg
0.8
207 nm 207 nm 212 nm
0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
-0.1
1.0
-1
-1 -1 37.02 mmol.kg
0.9 25.15 mmol.kg 33.4 mmol.kg
0.8
187 nm
212 nm 187 nm
0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
-0.1
1.0
-1 -1 -1
0.9 41.727mmol.kg 47.04 mmol.kg 51.24 mmol.kg
0.8 146nm 187 nm 207 nm
0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
1.0
-0.1
0.9 -1 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4
57.37 mmol.kg Rh / (m) Rh / (m)
0.8
262 nm
0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
-0.1
1E-9 1E-8 1E-7 1E-6 1E-5 1E-4
Rh / (m)

Fig. S4   Hydrodynamic Radii (Rh) distributions plotted against normalized intensity of

Ag−[C4mim][C8SO3] complexes at various concentrations of [C4mim][C8SO3] in 0.02%
agarose solution. 
Electronic Supplementary Material (ESI) for RSC Advances
This journal is © The Royal Society of Chemistry 2013

1.0
0.9 Pure Ag 3 mmol.kg
-1
9.27 mmol.kg
-1

0.8 158nm 158 nm 705 nm

0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
-0.1
1.0
-1 -1
0.9
19.27 mmol.kg
-1 31.5 mmol.kg 40.16 mmol.kg
0.8
723 nm 833 nm 238 nm
0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
1.0
-0.1
-1 -1
0.9 -1 69.41 mmol.kg 85.57 mmol.kg
51.82 mmol.kg
0.8 221 nm 200 nm
221 nm
0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
1.0
-0.1
-1 -1 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4
0.9 96.41 mmol.kg 111 mmol.kg
Rh / (m)
0.8 198 nm 160 nm
0.7
0.6
Intensity

0.5
0.4
0.3
0.2
0.1
0.0
-0.1
1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4
Rh / (m) Rh / (m)

Fig. S5 Hydrodynamic Radii (Rh) distributions plotted against normalized intensity of

Ag-[C8mim][Cl] complexes at various concentrations of [C8mim][Cl] in 0.02% agarose
solution. 
Electronic Supplementary Material (ESI) for RSC Advances
This journal is © The Royal Society of Chemistry 2013

(A) (B)

2µm

Fig. S6 SEM micrographs of (A) Native Ag (B) Ag-[C4mim][C8OSO3] complex, and (C)
Ag-[C8mim][Cl] complex (bar in images correspond to 2 μm). 

References:
1. Chakraborty, T.; Chakraborty, I.; Ghosh, S. Langmuir 2006, 22, 9905.
2. Chakraborty, T.; Chakraborty, I.; Moulik, S. P.; Ghosh, S. J. Phys. Chem. B 2007, 111,
2736.
3. Mitra, D.; Bhattacharya, S. C.; Moulik, S. P. J. Phys. Chem. B 2008, 112, 6609.