Journal of Molecular Liquids 142 (2008) 150–154

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Journal of Molecular Liquids

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / m o l l i q

Viscosity and activation parameters of viscous flow of sodium cholate

aqueous solution
Ting Wang a, Tong-Chun Bai a,⁎, Wei Wang a, Jian-Jun Zhu b, Cheng-Wen Zhu c
a
Department of Chemistry and Chemical Engineering, Suzhou University, Suzhou, 215123, China
b
Department of Chemistry, State University of New York, Stony Brook, New York 11796, USA
c
Research and Development Center, China Tobacco Industrial Corporation of Jiangsu, Nanjing, 210019, China

A R T I C L E I N F O A B S T R A C T

Article history: Viscosity, density and electrical conductance of sodium cholate aqueous solution in dilute concentrations are
Received 16 April 2008 reported. Concentration and temperature effects on the viscosity are discussed. Molar conductance of the salt
Received in revised form 11 June 2008 at infinite dilution is obtained by fitting experimental conductivity in Quint–Viallard equation. Viscosity data
Accepted 13 June 2008
is analyzed by Jones–Dole equation, and viscous B-coefficient and activation parameters are evaluated, which
Available online 20 June 2008
shows a strong effect of sodium cholate aggregation on viscosity flow. Our result shows that salt diffusion is
Keywords:
characterized by molecular aggregation, and is enhanced progressively as the concentration of bile salt
Electrical conductance monomer increases.
Viscosity © 2008 Elsevier B.V. All rights reserved.
Sodium cholate
Activation parameters of viscous flow

1. Introduction by their considerably smaller aggregation -number and higher poly-

Drugs are mainly hydrophobic organic compounds, and many of
them show a rather low solubility and dissolution rate in water.
Therefore, study of the dissolution enhancement of these compounds
is an important task in pharmaceutical technology because it can lead
to a better bioavailability. A broad variety of solubilization methods
have been developed in recent years, which include introducing a
drug carrier, for example a bile salt, into water [1,2]. A drug carrier can
increase the drug solubility, but often causes increase of the viscosity
of the medium, and therefore limits drug diffusion rate. This
contradicting role played by the drug carrier has been our interest
in recent years. [3,4]
Drug diffusion rate in aqueous solution is basically governed by the
restrictive effect of the carrier on drug mobility, whether due to a
reduction in free volume or an increase in medium viscosity. Systems
of this type generally show an inverse relationship between diffusion
rate and viscosity, which is predicted by the Stokes–Einstein equation.
This has led viscosity being used as a predictor of resistance against
diffusion.[4]
One bile salt is called sodium cholate, whose molecule structure is
shown in Fig. 1. It is an amphiphilic molecule that aggregates in solution.
Aggregates of bile salt are of fundamental physical-chemical interest [5–9],
as their behavior is different from ordinary aliphatic surfactance. The
critical micelle concentration (cmc) appears not as a definite concentration
but over a certain concentration range. Bile salt micelles are characterized
⁎ Corresponding author. Tel.: +86 512 65880363; fax: +86 512 65880089.
E-mail address: tcbai@suda.edu.cn (T.-C. Bai).
dispersity than that of the conventional amphiphiles. The mean
aggregation number of cholate ion is about 2–5 in solutions of 10–
50 mM, but becomes about 20 when the concentration is increased above
100 mM. In the primary–secondary micelle model [5], the primary
oligomers are formed by hydrophobic backs of the steroid nucleus
associate. The larger secondary aggregates are built up by the association
of these primary oligomers via intermolecular hydrogen bonds among
their hydrophilic outer surfaces. This model invokes a progressively
aggregation mechanism.
In this paper, we will continue our study on the effect of solution
viscosity on drug carrier diffusion. The diffusion kinetics of sodium
cholate will be studied by measuring the density, viscosity and the
electrical conductivity of the solution. We focus our attention on the
dilute concentration range, which include the pre-cmc dilute region
and the aggregation transition region. In the pre-cmc range, sodium
cholate is treated as a monomer. In the cmc transition region, the
effect of progressive aggregation is shown through some relevant
parameters. From the activation parameters of viscous flow, informa-
tion about the effect of the aggregation on the bile ion diffusion will be
obtained.
2. Experimental section
2.1. Materials
Sodium cholate (C24H39O5Na) was purchased from the National
Chemical Company of China. Its purity is 99.0%. It was dried at 60 °C
under vacuum for 24 h before use.

0167-7322/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.molliq.2008.06.010
 T. Wang et al. / Journal of Molecular Liquids 142 (2008) 150-154 151

Table 2
The values of α/(103g2 cm− 3 mol− 1) and the V02/cm3 mol− 1 of sodium cholate in aqueous
solution

T/K α/(103g2 cm− 3 mol− 1) V02/cm3 mol− 1

293.15 0.1067 324.2
298.15 0.1048 326.3
303.15 0.1035 327.9
308.15 0.1023 329.5
313.15 0.1013 330.9

Fig. 1. Molecular structure of sodium cholate (3α,7α,12α-Trihydroxy-5β-cholan-24-oic
acid, monosodium salt).
2.2. Density and viscosity measurement
Sodium cholate aqueous solutions with given concentrations were
prepared. Its concentration is controlled in dilute range to interrupt the
formation of larger micelle. Densities were measured with an Anton Paar
DMA 602 vibrating tube densimeter with an uncertainty of ±0.00002 ×g
cm− 3. The temperature of the cell was controlled by circulation of water
from a water bath with the temperature within ±0.01 K. The densimeter
was calibrated by using degassed water as calibration substances.
Viscosities were measured by a suspended level Ubbelohde
viscometer. The efflux time of the fluid was measured with a digital
stopwatch to ± 0.01 s. The viscometer was kept in a water
thermostat controlled to ± 0.01 K. Viscometers were calibrated by
water as described in our previous work.[4] Two viscometers were
used in the experiments. Detection was performed at least in six
replicates for each composition at each temperature. The estimated
relative standard deviation for η was ± 0.1%. The reference data for
density and viscosity calibration are from literature.[10] Other
experimental details and procedures are the same as those
described in previous work.[4]
2.3. Electrical conductivity measurement
value for 10 min, conductivity data was recorded for three times. Then
a gastight syringe with 0.5 ml capacity was used to inject 0.1 ml sodium
cholate solution (with known concentration) into the container. The
concentration of the new solution was calculated from the amount of
mixing. After 10 min, a new conductivity data was recorded. Then
another injection and recording is followed. In this way, the
conductivity with the concentration change was recorded. The relative
error of the measurement was b0.1% during the experiments.
3. Results and discussion
3.1. Density and partial molar volume at infinite dilution
The partial molar volume of solute at infinite dilution, V02, is an
essential parameter for analyzing the solute–solvent interaction and a
necessary data in evaluating activation parameters of viscous flow.
Densities of sodium cholate aqueous solution are given in Table 1. At
present concentration range, they are linear functions of concentration.
ρ ¼ ρ0 þ αm ð1Þ
where m is the molality of sodium cholate in solution (mol kg− 1), ρ and
ρ0 represent the densities of the solution and pure water, respectively.
The value of α is obtained by a least-squares regression method. The V02
can be calculated by Eq. (2).
M2 1000α
V20 ¼ − ð2Þ
ρ0 ρ20

Electrical conductivity was measured using a digital conductivity where, M2 is the molecular weight of sodium cholate. The values of α
meter, CON 1500 model, EUTECH Company, USA, with a cell having and V02 are listed in Table 2.
platinum electrodes. The electrode was calibrated by a standard sample
of KCl aqueous solution at different temperatures.[11] The cell constant 3.2. Conductivity and molar conductance at infinite dilution
is 1.218 cm− 1. According to the instruction of the instrument manual the
optimal conductivity range of this electrode is from 10 to 2000 µS cm− 1. Fig. 2 shows the specific conductivity (κ) of sodium cholate
The conductivity was measured in a glass container, where sample aqueous solution derived from experiment at several temperatures.
solution was stirred by an electromagnetic stirrer. The temperature of
the container was controlled by a water bath with a precision of
±0.01 K. The container was sealed with a rubber cap, through which
the conductivity cell had been inserted. Conductivity was determined
by the following procedure. Weighted amount of water was trans-
ferred to the container. After the temperature was hold at the setting

Table 1
Density (ρ/g cm− 3) of aqueous sodium cholate solution at several temperatures

m/mol.kg− 1 ρ/g.cm− 3
293.15 K 298.15 K 303.15 K 308.15 K 313.15 K
0 0.99820 0.99705 0.99565 0.99403 0.99224
0.002344 0.99841 0.99725 0.99590 0.99431 0.99253
0.004655 0.99860 0.99748 0.99607 0.99449 0.99268
0.009337 0.99911 0.99793 0.99654 0.99495 0.99318
0.014017 0.99972 0.99851 0.99709 0.99546 0.99371
0.018747 1.00021 0.99901 0.99750 0.99599 0.99417
0.023465 1.00070 0.99948 0.99810 0.99643 0.99456
0.028222 1.00118 0.99996 0.99855 0.99691 0.99512
Fig. 2. Plot of experimental electrical conductivities κ versus bile salt concentration c at
0.037776 1.00221 1.00100 0.99954 0.99793 0.99608
temperatures: ■, 293.15 K; ●, 298.15 K; ▲, 303.15 K; ▼, 308.15 K; ♦, 313.15 K; and lines,
0.047417 1.00319 1.00196 1.00052 0.99887 0.99706
the prediction by Quint–Viallard equation.
152 T. Wang et al. / Journal of Molecular Liquids 142 (2008) 150–154

Table 3
The parameters of Quint–Viallard equation for sodium and cholate ions in aqueous
solution at different temperature

Q–V 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

parameters
λ0j 44.81 50.15 55.72 61.53 67.34
(9.699) (11.58) (14.02) (16.05) (18.07)
Sj 37.03 41.79 46.83 52.12 57.63
(29.03) (32.94) (37.16) (41.48) (45.98)
Ej −0.1891 − 0.1233 0.01479 0.1222 0.1964
(−3.103) (− 3.452) (−3.763) (− 4.147) (−4.568)
J1 101.1 114.5 128.6 143.9 159.8
(51.78) (60.23) (70.24) (79.81) (89.61)
J2 142.3 162.0 183.4 206.0 229.4
(92.86) (108.9) (128.4) (146.9) (165.7)

Note: For a given pair of data a(b), a is for to Na+ and b is for Cholate−.

Unlike the micelle solution with a definite cmc, at present concentra-

tion range, no break point was found in the conductivity curve. Our
experiment does not seem to support the step-wise aggregation
mechanism, but does support a progressive mechanism where sodium
cholate aggregation is a continuous process. In the concentration
region lower than 10 mM, conductivity is related to the monomer
motion. In the higher concentration region, a continuous trend was
prolonged. The effect of progressive aggregation is presented here.
Along the curve to infinite dilution, we can obtain the parameters at
infinite dilution, which represents the properties of un-associate
solute. From the data at infinite dilution and by using a non-associate
Fig. 4. The values of ln[λ0j ρ3/2
0 ] against 1/T for anions: ■, nicotinate; ●, hydrogen
tartrate; ▲, H2PO−4; ▼, Cl− ; ♦, cholate; and lines, linear relations.
electrolyte model, the property we can predict is suit for monomer.
Furthermore, by comparing the theoretical prediction with the
experimental data, the deviation generated from ion association will
be shown. Then we have a procedure to analyze the effect of
aggregation: firstly, to get the infinite molar conductance of ions;
then to predict the behavior of un-associated electrolyte at higher
concentration; and finally, to observe the deviation between predic-
tion and experiment.
The molar conductance Λ can be calculated from electric con-
ductivity (κ) by its definition. However, the more dilute the electrolyte
concentration, the bigger the error of molar conductance. To avoid this
error, Eq. (3) was used to regression the parameters involved.


κ ¼ λ þ þ λ− c ð3Þ

where, λj is of the form of Quint–Viallard equation [12].

pffiffiffi
λj ¼ λ0j −Sj c þ Ej clnc þ J1j c−J2j c3=2 : ð4Þ

The definition of Sj, Ej, J1j and J2j can be found from literature [12]
and calculated theoretically. Based on the principle of independent
motion of ions at infinite dilution, literature data of λ0j of Na+ ion was
used in this solution. Then the only adjustable parameter is the λ0j of
cholate ion, which can be obtained by non-linear least-square
regression method by using Eqs. (3) and (4). Once λ0j is obtained,
the conductivity curve can be predicted by Quint–Viallard equation.
Some parameters obtained in this way are listed in Table 3, in which,
λ0j of Na+ is got from literature[13]. The predictive curve is shown in
Fig. 2. Our result shows that, there is no clear change between
theoretical and experimental in the plots over a wide concentration
range. This phenomenon is because the molar conductance of sodium

Table 4
Viscosity (η/mPa s) of aqueous sodium cholate solution at different concentration m/
mol kg− 1 and temperature

m/mol kg− 1 293.15 K 298.15 K 303.15 K 308.15 K 313.15 K

0 1.002 0.8904 0.7975 0.7194 0.6529
0.002344 1.007 0.8943 0.8010 0.7231 0.6566
0.004655 1.012 0.8984 0.8044 0.7264 0.6600
0.009337 1.021 0.9061 0.8115 0.7329 0.6649
0.014017 1.031 0.9170 0.8213 0.7416 0.6720
0.018747 1.041 0.9231 0.8262 0.7454 0.6763
0.023465 1.050 0.9319 0.8337 0.7527 0.6826
0.028222 1.061 0.9405 0.8413 0.7593 0.6889
0.037776 1.082 0.9598 0.8579 0.7740 0.7016
Fig. 3. Molar conductance of (a) Na+ and (b) cholate ion, at temperatures: ■, 293.15 K; ●, 0.047417 1.105 0.9782 0.8750 0.7887 0.7154
298.15 K; ▲, 303.15 K; ▼, 308.15 K; ♦, 313.15 K.
 T. Wang et al. / Journal of Molecular Liquids 142 (2008) 150-154 153

Table 5 Table 6
The A- and B-coefficient of viscous flow, and the standard deviation, s, of the fitting by Activation parameters of viscous flow for sodium cholate aqueous solution
Eq. (5)
T/K Δµ≠1/kJ mol− 1 Δµ≠2/kJ mol− 1 ΔS≠m,2/kJ K− 1mol− 1 ΔH≠m2/kJ mol− 1
T/K A/(dm3 mol− 1)1/2 B/dm3 mol− 1 s 293.15 9.30 263 5.01 1731
293.15 0.1504 1.52 0.003 298.15 9.16 227 5.04
298.15 0.1473 1.23 0.003 303.15 9.04 202 5.04
303.15 0.1428 1.02 0.003 308.15 8.93 181 5.03
308.15 0.1415 0.85 0.003 313.15 8.83 162 5.01
313.15 0.1412 0.70 0.003

ion is much larger than the value of cholate ion, and because the
counter ion binding to the micelle is quit small. The relevant molar
conductance is shown in Fig. 3. When the progressive aggregation
runs in the primary stage, only small oligomer is formed between
cholate ions with the form of back to back hydrophobic interaction.
Their electrical charge is toward the outside of oligomer. But the
motion of sodium ion is independent of the aggregation. In spite of the
aggregation effect is not clear, we can obtain the parameters at infinite
dilution, which, characterize the motion of monomer. The λ0j will be
used in viscosity analysis.
To compare the effect of ion size on motion at infinite dilution, the
curves of ln[λj0ρ3/2
0 ] against temperature for some ions are shown in Fig. 4.
The data of nicotinate [13], hydrogen tartrate [14], H2PO−4 [15], and Cl− ion
[16] are presented. Fig. 4 shows that these ions have similar curve feature,
but cholate ion is at the lower side. It means that cholate anion is of the
character of isolated ion with bigger size at infinite dilution.
3.3. Viscosity and viscous B-coefficient
The data of viscosity of sodium cholate aqueous solutions are given
in Table 4. For electrolyte solution, Jones–Dole's equation was usually
used to express the relation between the viscosity and electrolyte's
concentration, c.
ηr ¼ 1 þ Ac1=2 þ Bc:
only for the data at c is much small. Applying Eq. (6) to sodium cholate,
A-coefficient will responsible to the motion of monomer.
The B term depends on solute-solvent interaction and is related to
the volumes of the solute, but so far in a theoretically inaccessible
manner. Practicably, B-coefficient is obtained by fitting experimental
data. If Eq. (5) is applied to sodium cholate aqueous solution, where its
concentration is over the pre-cmc range, it will deviate from the un-
associating approximation. This means that the effect of cholate
aggregation on viscosity can be reflected by the B-coefficient. The
theoretical values of A-coefficient and the experimental fitting values
of B-coefficient are presented in Table 5, where the fitting deviation by
Eq. (5) is given. Fig. 5 shows the dependence of B-coefficient on
temperature. It shows the value of B-coefficient decreases with the
increase in temperature.
3.4. Activation parameters of viscous flow
For binary solution, a solute 2 dissolves in solvent 1, the kinetics of
viscous flow obeys Eyring's transition state theory, which is expressed
as:


η12 ¼ ðhNA =Vm12 Þexp Δμ ≠12 =RT ð7Þ
where, Vm12 is the mean molar volume of solution, and the Δµ≠12 is the
Gibbs free energy of activation for viscous flow of 1 + 2. For dilute
solution, we can split Δµ≠12 into two parts.
ð5Þ

where, ηr is the relative viscosity. Δμ ≠12 ¼ x1 Δμ ≠0 ≠

1 þ x2 Δμ 2 ð8Þ
The A-coefficient depends on the interionic force and can be
where, the Δµ≠2
is the contribution from per mole of solute 2 in
evaluated theoretically by Falkenhagen equation as expressed in the
solution. For an electrolyte solution where Eq. (5) is obeyed, Eq. (9) can
paper of Jenkins and Marcus [17]
be derived with the combination of Eqs. (7) and (5). [18]
2 !2 3


0:2577Λ 0 41−0:6863 λ0þ −λ0− 5 B ¼ mVm1 −V20 þ ðVm1 =RT Þ Δμ ≠2 −mΔμ ≠0 ð9Þ
A¼ ð6Þ 1
η0 ðeT Þ1=2 λ0þ λ−
0
Λ0
In Eq. (9), Vm1 is the molar volume of pure solvent. The V02 is the
3 − 1 1/2
where, A is in (dm mol ) , η0 in Pa s and λ0j
in (S cm mol ) . The 2 −1 −1 partial molar volume of solute at infinite dilution, ν is one for an un-
parameters in Eq. (6) correspond to the state of ions at infinite dissolved species, and 2 for a dissociated uni-univalent electrolyte.
dilution. For most salts, the A term affects appreciably the viscosities The Δµ≠2 can be calculated from B-coefficient by Eq. (9).

Fig. 5. The dependence of viscosity B-coefficients on temperature T/K. Fig. 6. The dependence of (Δµ≠2/T) on temperature (1/T).
154 T. Wang et al. / Journal of Molecular Liquids 142 (2008) 150–154

Table 7 point was observed in the curve of viscosity vs. concentration and no
Comparing the activation parameters of viscous flow for some solutes in aqueous and definite cmc exist in sodium cholate aqueous solution, it is difficult to
non-aqueous solution
observe the effect of aggregation on viscosity. However, from the
System Δµ≠2/ System Δµ≠2/ bigger viscous activation parameters, the effect of aggregation is
kJ mol− 1 kJ mol− 1 shown. The physical meaning of bigger Δµ≠2 also indicate that, the ion
NaCl in water [18] 26.4 Dimethylformamide in 13.2 diffusion is characterized by molecular aggregation, which is
methanol [19]
enhanced progressively as the concentration of bile salt monomer
Dimethylformamide in water [19] 41.3 Formamide in methanol 14.6
[19] increases.
Tert-Butyl Alcohol in water [18] 75.4 Formamide in 12.3
acetonitrile [19] 4. Conclusion
Hexanedioic acid in water [4] 74.5 Et4NBr in acetonitrile 45.67
[20]
Sodium dodecylsulfate in 299.6– Bu4NBr in acetonitrile 64.03
Our result of electric conductivity shows that there is no
diethylsulfoxide aqueous solution [21] 307.4 [20] discrepancy between theory and experiment in conductance over a
wide concentration rang. This is because the molar conductance of
System ΔHm2≠/ sodium ion is much larger than that of cholate ion, and the counter ion
kJ mol− 1
binding to the micelle is quite small. The molar conductance of the salt
Tert-Butyl Alcohol in water [18] 245 at infinite dilution is obtained by fitting experimental conductivity.
Hexanedioic acid in water [4] 223
Sodium dodecylsulfate in 1673–
These data is characterized by the un-associated ions.
diethylsulfoxide aqueous solution [21] 1781 The B-coefficient and the activation parameters of viscous flow
have been obtained from viscosity measurement. These parameters
show that anion diffusion is characterized by molecular aggregation,
which is enhanced progressively as the concentration of bile salt
If Δµ≠2 is known at several temperatures, the molar activation
monomer increases.
enthalpy can be calculated from Eq. (10).

≠   ≠ Acknowledgement
d Δμ 2 =T =dð1=T Þ p ¼ ΔHm2 ð10Þ

And the molar-activation-entropy of solute can be calculated from Tong-Chun Bai acknowledges the support of the Key Academic
Eq. (11) Discipline of Organic Chemistry of Jiangsu Province of China.

≠ 
ΔS≠m2 ¼ ΔHm2 −Δμ ≠2 =T: ð11Þ References

Activation parameters of viscous flow obtained in this way are [1] K. Mastsuoka, Y. Kuranaga, Y. Moroi, Biochim. Biophys. Acta 1580 (2002) 200.
listed in Table 6 and plotted in Fig. 6. It is seen that the curve of (Δµ≠2/T) [2] J.R. Cardinal, Y. Chang, D.D. Ivanson, Inter. J. Pharm. Sci. 67 (1978) 854.
[3] T.C. Bai, G.B. Yan, J. Hu, H.L. Zhang, C.G. Huang, Inter. J. Pharm. 308 (2006) 100.
vs. (1/T) is approximately linear. Then ΔH≠m2 is obtained from the curve [4] Y. Zhang, T.C. Bai, J.Q. Xie, J. Chem. Eng. Data 52 (2007) 676.
slope. Because Δµ≠2, ΔH≠m2 and ΔS≠m2 are derived from the B-coefficient, [5] D.M. Small, in: P.P. Nair, D. Kritchevsky (Eds.), The Bile Acids: Chemistry,
their values will reflect the effect of aggregation on viscosity, and so on Physiology, and Metabolism, vol. 1, Plenum Press, New York, 1971, Ch.8.
[6] H. Sugioka, Y. Moroi, Biochim. Biophys. Acta 1394 (1998) 99.
the ion diffusion. [7] K. Matsuoka, Y. Moroi, Biochim. Biophys. Acta 1580 (2002) 189.
Comparing the activation parameters of some solutes in aqueous [8] H. Sugioka, K. Matsuoka, Y. Moroi, J. Colloid Interface Sci. 259 (2003) 156.
and non-aqueous solution [4,18–21], which are listed in Table 7, we [9] L.B. Partay, P. Jedlovszky, M. Sega, J. Phys. Chem. B 111 (2007) 9886.
[10] R.C. Weast, CRC Handbook of Chemistry and Physics, 70th ed.CRC Press Inc., Boca
can confirm that the activation parameters of sodium cholate is Raton, Florida, 1990.
responsible for aggregation. For those un-aggregated solutes, their [11] J. Barthel, F. Feuerlein, R. Neueder, R. Wachter, J. Solution Chem. 9 (1980) 209.
Δµ≠2 and ΔH≠m,2 are much lower than the value of sodium cholate. For [12] J. Quint, A. Viallard, J. Solution Chem. 7 (1978) 533.
[13] Z. Orekhova, M. Ben-Hamo, E. Manzurola, A. Apelblat, J. Solution Chem. 34 (2005)
sodium dodecylsulfate (SDS) in diethlsulfoxide aqueous solution [21],
687.
their activation parameter is of the order of sodium cholate. In the case [14] M. Bester-Rogac, R. Neueder, J. Barthel, A. Apelblat, J. Solution Chem. 27 (1998) 299.
of SDS, the viscous flow is a micelle system, the B-coefficient and the [15] E.N. Tsurko, R. Neueder, J. Barthel, A. Apelblat, J. Solution Chem. 28 (1999) 973.
activation parameters of viscous flow were calculated within the [16] M. Bester-Rogac, R. Neueder, J. Barthel, J. Solution Chem. 28 (1999) 1071.
[17] H.D.B. Jenkins, Y. Marcus, Chem. Rev. 95 (1995) 2695.
micelle region. Its activation parameter is of the character of micelle [18] D. Feakins, F.M. Canning, W.E. Waghorne, K.G. Lawrence, J. Chem. Soc., Faraday
solution. Based on this observation, we predict that, for a solute with Trans. 89 (1993) 3381.
micelle size, when it moves in a solvent whose molecular size is [19] K. Hickey, W.E. Waghorne, J. Chem. Eng. Data 46 (2001) 851.
[20] N. Saha, B. Das, J. Chem. Eng. Data 45 (2000) 1125.
smaller, an unusual bigger value of Δµ≠2 and ΔH≠m,2 will be produced. [21] S.A. Markarian, L.R. Harutyunyan, R.S. Harutyunyan, J. Solution Chem. 34 (2005)
Therefore, in the case of sodium cholate, the unusual bigger activation 361.
parameter is generated from the anion aggregation. Because no break