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The Multiple Equilibrium Model of Micelle Formation Author(s): J. M. Corkill, J. F. Goodman, T.

The Multiple Equilibrium Model of Micelle Formation Author(s): J. M. Corkill, J. F. Goodman, T. Walker and J. Wyer Reviewed work(s):

Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical

Sciences, Vol. 312, No. 1509 (Sep. 2, 1969), pp. 243-255 Published by: The Royal Society

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Proc. Roy. Soc. A. 312, 243-255 (1969)

Printed in Great Britain

The multiple equilibriummodel of micelle formation

BY J. M. CORKILL, J. F. GOODMAN,

T. WALKER

and J. WYER

Proctor and Gamble Limited, Basic Research Department, Newcastle upon Tyne

(Communicated by D. Tabor, F.R.S.-Received

Revised 14 January

1969)

28 November 1968-

In dilute aqueous solution surface-active molecules aggregate to form micelles. This process has been described by a multiple equilibrium model which considers changes in the distribu- tion of micelle aggregation numbers with concentration. Analysis of the colligative properties of dilute aqueous solutions of non-ionic surface-active agents has enabled the concentration of monomer to be determined as a function of the total solute concentration. The validity of the treatment has been confirmed by showing that these monomer concentrations are in good agreement with those deduced from nuclear magnetic resonance experiments, which do not depend on the assumptions employed in the thermodynamic method. Only one colligative property need be determined as a function of concentration in order to describe adequately the average aggregation numbers and free energies of micelle formation.

INTRODUCTION

The abrupt change in the colligative and other solution properties of surface-active molecules in dilute aqueous solution at a critical concentration, known as the critical micelle concentration (c.m.c.), is attributed to the formation of molecular aggregates known as micelles (see McBain I950). The description of this process has been approached from two viewpoints, as a single kinetic equilibrium (Jones & Bury I927; Hartley I936) and as a phase separation (Stainsby & Alexander I950). Both models are limited by an oversimplification in the specification of the micellar species. Hall & Pethica (i 967) have applied Hill's (i 963, I964) small system thermo- dynamics to overcome this objection and have obtained exact thermodynamic relations for micellar systems. The multiple equilibrium model provides an equally rigorous approach for the thermodynamic treatment of micellization. This model is developed here in a manner analogous to treatments of association in liquid mixtures (Prigogine & Defay I954) to obtain relationships between the average thermodynamic properties of a micellar system; some of which are similar to those derived for protein aggregation (Steiner I952; Adams & Williams I964). The theory is used to obtain the concentration of monomeric solute as a function of the total solute concentration from thermodynamic measurements, and the validity of the treatment confirmed by determining this quantity using a spectroscopic method which is independent of thermodynamic assumptions. The variation of the surface tension of a micellar solution with solute concentration calculated on the basis of this treatment agrees with values determined experimentally. Finally, the change in the standard free energy of micelle formation with aggregation number has been calculated.

[

243

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244 J. M. Corkill, J. F. Goodman,

THEORY

T. Walker and J. Wyer

1. Colligativepropertiesof micellarsolutions

It is well known that the colligative properties of ideal solutions are determined

by the mole fraction of the solvent,

in

both the monomeric and associated states, we may define a solute colligative mole fraction xc, by

xl. In a system in which the solute

=

I

xi,

exists

=

(1.1)

where x2 and xr are the mole fractions of the monomeric and rth associated species respectively and the summation extends over all aggregated species. The total solute concentration, C (g/ml), is related to these mole fractions by

C = (M2/Vm)(X2+ E nrXr),

(monomer) molecular weight, Vmis the molar volume of the

solution and nr is the aggregation number of the rth micellar species. For dilute

solutions, Vmwill be indistinguishable from

subsequent analysis, we shall find it useful to employ a 'stoichiometric' solute mole

the solvent molar volume, Vl. In the

where M2 is the solute

(1.2)

fraction, xt, rather than C, where

(1.3)

in which the solute species are in chemical

equilibrium it is possible to determine x2 from the dependence of xc upon xt (or C).

If ar and

respectively, we have for the equilibrium between the monomeric and any associated

species

Xt

=

We can now show that for systems

X2+

EfnrXr.

t2 are the chemical potentials of the rth micellar species and the monomer

nr/2

=

1br

(1.4)

We choose the hypothetical standard states in which the solvated species have the partial enthalpies and heat capacities corresponding to dilute real solutions and free energies and entropies corresponding to unit activity (Lewis & Randall I96I). For solutions sufficiently dilute to behave ideally, we have, from (1.4),

(1.5)

where ,ar and 4a?are the standard chemical potentials

meric species respectively,

By differentiation

ln xr =-(#0-nr?)/RT

+nrln x2

of the associated

and mono-

R is the gas constant

and T the absolute temperature.

and pressure we have

of (1.5) at constant temperature

(1.6)

We multiply each side of this equation by nrk where k is a positive integer and sum with respect to xr to obtain

dlnx2

nrxr

now

xrn

d

E, nrk x

di

dlnX

2

-

k +1(1

(1.7)

If we now differentiate

x, (equation (1.1)) with respect to In X2, substitute

for the

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Micelle formation

245

derivative

of the sum from (1.7) (k = 0) and introduce the definition

of xt from

(1.3) we have

dxc/xt = dlnx2.

(1.8)

Integration of (1.8), using an experimentally determined relation between xc and

xt, enables the change in lnx2 to be calculated. By choosing for the lower limits of

integration

x2 may be determined as a function of xc and hence xt (or C). The colligative mole

fraction may be determined from any suitable colligative property; thus in ideal

dilute solution from (1.1) pi/P1 = xi = 1 -Xe,

(1.9)

solutions sufficiently dilute for association to be negligible (xc -- xt),

where pi and p? are the equilibrium vapour pressures (strictly fugacities) of the solvent in the solution and pure liquid states respectively.

2. Light scattering

system, the condition of

chemical equilibrium between the solute species means that there is only one

compositional variable. The solute specific refractive increment is independent of the concentration above the c.m.c. in these systems and so we may assume that the

specific refractive increments

ditions, it is permissible to employ the two component

(Debye I947)

Although

we

are dealing

with

a multi-component

of all solute species are the same. For these con-

- HCRTV

light scattering

equation

(2.1)

where T1 is the excess turbidity of the solution due to the solute, H is an optical constant containing the specific solute refractive increment and ir the solution osmotic pressure. For ideal dilute solutions

x

of this expression with respect to C and substitution

7V1/RT = -ln

e.

x,

By differentiation

we have from (1.2), after rearrangement

(2.2)

into (2.1)

HC

1dxc

1 dxc

(2.3)

This equation enables either xc or x2 to be determined from the experimental

upon xt (or C). By choosing the lower limits of integration to

correspond to solutions with negligible association (IICM2/1l --

1) integration with

respect to xt enables xc to be calculated. By multiplying each side of (2.3) by

dlnxt and M2we obtain from (1.8)

dependence of HC/I1

T1

VdC

V,

14d0 M2dx~~~~~~~~~

M2

.

&t

HCM2dlnxt = dxc = dInX2.

T

d

Xt

(2.4)

Integration of this expression enables x2 to be determined.

Since the same information may be obtained from light scattering or colliga-

by the relative

tive property measurements,

the choice of method is determined

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246 J. M. Corkill, J. F. Goodman,

experimentalaccuracy.It has been foundthat vapourpressuredepressionmeasure- ments are the more sensitive when the degreeof associationis low, light scattering when it is high.

3. Aggregationnumbers The average association numbers are a set of parameters characterizing the distribution of the solute between the monomeric and associated species. With respect to all solute species we may define number (N.) and weight (Nw)average association numbersby

(3.1)

T. Walker and J. Wyer

N

-

X2

-rXr=--T

(from (1.1), (1.3))

X2+

>Xr

Xc

and

N

=

x2+nr(nrxr)

X2

+

E nrXr

(3.2)

By differentiating

obtain

xt with respect to lnx2 and substituting

dxt/dlnx2

=

x2+En2xr.

from (1.7) (k =

1) we

(3.3)

(3.4)

(3.5)

From (1.8) we have

dx,/d lnx2 = x2+ EnrXr,

and hence, by division, N, = dxt/dx,.

We note than Nw may be obtained from either the dependence of xt upon xc or directly from light scattering data (equation (2.3)). Average association numbers may also be defined with respect to the associated solute species. Thus we have for the number (<n>) and weight (<n>w)averages

<n> =

rxr

EXr

XtX2

Xc-X2

(3.6)

<n>w=

>2nr(nrxr) N-Xtx2 =

(3.7)

If we differentiate (3.6) with respect to lnx2 we obtain, with the aid of (1.7) for the

derivative

(3.8)

Since for a system in which there is more than one associated species <n>w> <n>, it follows that <n> must increase with concentration since d lnx2 has the same sign as dxt.

of the sums, after rearrangement,

d<n>/d lnX2 =

(<n>w-<n>)

<n>.

4. Nuclear magnetic resonance chemical shifts

If the resonance corresponding to a particular chemical group within a molecule

has a chemical shift Vjfor a particular environment of the molecule, and if there are several possible environments with rapid exchange between them, then the observed

chemical shift, P, is given by _ E <g01E0,

(4.1)

where Cj is the concentration

of the molecules

in the jth

environment

and the

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Micelle formation

247

summation

molecules have a shift of v2and all associated species have the same shift vm, then

extends

over all sites. If we assume that in solution the unassociated

Rearrangement

v

X2 v2 +(EnrXr)vm Xt

of this equation leads to

(4.2)

x2= v2 -v

Xt.

(4.3)

Thus, if Pm) P2 can be determined, the dependence of v upon xt leads to x2 as a function of xt.

5. Surface tensions

For a plane interface at constant temperature and pressure the Gibbs adsorption isotherm may be written in the form

-dy

=

Fj d,j,

(5.1)

where y is the interfacial tension, F- and ,aj the surface excess and chemical potential of the jth solute species and the summation extends over all solute species. For an associating solution, we have from (1.4)

-dy

= (F2 + E Frfnr)d/a2.

(5.2)

As the surface excess Fr involves nr Fr moles of solute, the term in brackets in (5.2) is the total surface exceess (Ft) in terms of monomeric solute. We can express d,a2

in terms of dlnxt

since

dlnxt

1

dlnxt

and hence by substitution

we have

dln2 =R1Tdlnx2'

from (3.3) and the introduction dy

-

RTFt

 

(5.3)

of Nw (equation

(3.2))

dlnxt

Nw(54

If Ft can be determined,

Nw and

xt.

then y can be calculated from the relationship between

6. Standardfree energiesof association

of the thermodynamic theory it has proved useful to ignore

the individual micelles and consider only their average properties. If the average

chemical potential <,a> of the micellar species is defined as the mean Gibbs free energy <G> per mole of the associated species then since

(6.1)

In the development

<G> =

,arXr/

EXr,

it follows

that

<a> = <MO> + RT<lnxr>.

(6.2)

micellar species in their respective

standard states in proportions corresponding to the distributions in a real solution,

If we consider a mixture

of the individual

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248 J. M. Corkill, J. F. Goodman,

the free energy change of this mixing process will be

T. Walker and J. Wyer

The standard

(<00>) is given by

chemical

DmG =RT

E

>Xr

Xr-n( Exr)

\X2r/

= RT[<ln xr>-ln

(E xr)].

(6.3)

potential

of the

associated

species

in the

mixed

state

Kv0>-Kito> = iMG,

 

(6.4)

and thus from equations (6.2) to (6.4) the free energy change for association per mole of monomer referred to the mixed standard state is given by

<0

>2

<n>

R>-T

(lnx2n

<n>x))

(6.5)

Thus <K vO> is related to

The converse problem, that of calculating the standard free energies for particular micelles entirely on the basis of experimental results may in principle be solved by

the method given below. From (1.5), by summation with respect to the associated species, we have

quantities

which may be determined experimentally.

EXr

a)

= E>f(nr)exp(-nrs),

0

(6.6)

wheref(O),f(l)

are zero and for n > 2 (integer)

 

f(nr)

= exp

(-[?

- nr/,tO]/RT)

(6.7)

and

s=-lnx2.

(6.8)

The sum Exr is (XI - x2) and hence, from the experimental data, this may be obtained as a function of s, say g(s). Equation (6.6) then becomes

g (s)

=

co

>f(nr)

0

expHnr

8).

(6.9)

The right hand side of this equation is related to the Laplace transform and from

the Fourier integral theorem (Sneddon I95I),

f(nr) =

1

2ni)j

Ifd+ir1

g(s)exp(nrs)ds

it can be shown that

(nr >

0, integral),

(6.10)

where a is a constant such that all singularities of g(s) in the complex plane lie to the left of the path of integration.

(6.10) provides a formal solution to the problem of obtaining the free

energies of formation of the individual micelles from experimental data. In principle

Equation

f(nr) may be obtained by fitting a suitable function of s to the relationship between

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Micelle formation

249

s and g(s) obtained from experimental

results and applying (6.10). The approxima-

tion of replacingthe seriessummation (6.9) by an integrationand using the normal Laplace inversion to obtain a continuous approximation to f(nr) leads to large errors (- 20 %)when <n> is small (- 5) for the simple trial function we investi- gated (f(nr) cx I/n +,8In- + Awhere a, /3,Z and Aare constants).

EXPERIMENTAL

Materials

The

zwitterionic surface-active agent

3(dimethyloctylammonio)-propane-1-

sulphonate

(C8H17N Me2(CH2)3SO ) was chosen for this study. The change in the

nuclear magnetic resonance chemical shift between the monomeric and micellar states is much largerfor a fluorinenucleus than for a proton (Muller& Birkhahn I967), and to enable 19Fnuclearmagnetic resonance experiments to be conducted the seven terminalprotons were replacedby fluorineatoms to give the heptafluoro compound C3F7(CH2)5N+Me2(CH2)3SO. Both compoundswere preparedfrom the correspondingbromides by the following synthetic route.

HNMe2

RBr- 2RNMe2

CH2CH2CH2

I

I

0~~S02

-RN+Me2(CH2)3SOj

The products were recrystallized from acetone and ethanol and gave the correct elemental analyses. The bromide used to prepare the heptafluorocompoundwas synthesized from 4-pentene-1-ol and heptafluoropropyliodide as follows:

CH2=CH(CH2)30H

C3F71

C3F7CH2-CHI(CH2)30H

-

 

PBr3

C3F7(CH2)5Br

PBr3

C3F7(CH2)50H

Zn/HCI

Thermodynamicmeasurements

(i) Lightscattering Aqueous solutions of the fluorinatedsurface-activeagent were clarifiedby filtra- tion through 'Millipore' filters (100nm pore size) and the intensity of scattered light at 25 ?Cmeasuredat angles of 45, 90 and 1350 to the incident beam by means of a Sofica model 4200 P.G.D. instrument. The disymmetry (Z45) of the scattered light was less than 1.05 in all cases and the turbidities, T, weretherefore calculated from the scattering at 900 on the basis of a benzene calibration (Coumou I960). Correctionsfor depolarization of the scattered light were found to be negligible. Refractive index incrementswere determinedwith a Rayleigh interferometer.

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250

J. M. Corkill, J. F. Goodman,

T. Walker and J. Wyer

(ii)

Vapourpressureosmometry

The differencein temperature between a drop of solution and a drop of solvent contained in a constant temperature enclosure saturated with solvent vapour is proportionalto the vapour pressure depression of the solution (Huff, McBain & Brady I95I). Thermistor beads are used to measure the temperature difference and the apparatus calibrated with aqueous sucrose solution of known activity (Robinson& Stokes 1959). The Mechrolab301 and Hitachi-Perkin-Elmer instru-

ments were used for

requiredto detect the small activity change in micellarsolutions of the fluorinated

compound.

these measurements. The latter is more sensitive and was

(iii) Surfacetension

Surface tensions of aqueous solutions of the fluorinated solute were measured using a drop volume apparatus which was immersed in a water thermostat (25.00+ 0.05?C). The drops were formed in a Teflon tip because difficulty was experiencedin wetting correctlythe glass tips normallyused. The tip was attached to a micrometersyringe held in an atmospheresaturated with solvent vapour and the surfacetension was calculatedby the proceduredescribedby Harkins &Brown

(I 9I9).

(iv) Nuclearmagneticresonance(n.m.r.)measuremnents

N.m.r. measurementsfor the 19Fnucleus were carriedout using a Varian DA 60 system at a frequency of 56.4MHz at 25 ?C.The external referencesolution (40 % trifluoroaceticacid in water) was contained in a 1mm capillary and centred in the sample tube with Teflon bushes. The chemical shift of the terminal CF3group of C3F7(CH2)5N+Me2(CH2)3SOwith reference to trifluoroaceticacid was measured by using a side band calibration with a Hewlett Packard 200CD audiofrequency oscillatormonitoredon a Vennerfrequencycounter. Chemicalshifts were corrected for bulk susceptibility effects, which were found to be small.

RESULTS

The turbidities, T,of aqueous solutions of C3F7(CH2)5N+Me2(CH2)3SO3and the colligativemolefraction(xc)fromosmometrymeasurementsareshownas a function of the total solute concentrationin figures1and 2respectively.Valuesof xcobtained by integrating the light scattering data using equation (3.5) are in good agreement with the values obtained directly by osmometry (figure 2), thus verifying the equivalence of the two methods. The chemical shift of the terminal CF3 group is plotted as a function of the reciprocalconcentration (x-y1)in figure 3, and the variation of the surface tension with the logarithm of the solute concentration (lgxt) in figure 4. The surface tension decreases with increasing concentration

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Micelle formation

6-

!;4 -

2-

251

0

5

10

0

2

4

6

 

102

C/gml-1

103Xt

 

FIGURE1

 

FIGURE2

 

FIGURE 1.

Light

scattering,

C3F7(CH2)5N+(CH3)2(CH2)3SO-solutions,

turbidity

against

concentration.

FIGURE 2. Colligative

0,

Osmometry;

properties,

C3F7(CH2)5N+(CH3)2(CH2)3SO-solutions,

xc against

xt,

, integration of light scattering results (calculated by using (3.5)).

300 -

250-

0

0.5

1.0

1.5

FIGURE

3. Chemical

10-3x-1

shifts

C3F7(CH2)5N+(CH3)2(CH2)3SO-

of the

CF3 group

for

solutions

against

x-1.

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252 J. M. Corkill, J. F. Goodman, T. Walker and J. Wyer

at all concentrations, but the decline is relatively small in micellar solutions

(Xt

>

1.5 x 10-3).

Precise turbidity data could not be obtained for aqueous solutions

of C8H17N+Me2(CH2)3S0- because

variation

numbers, but the

of xc with xt from osmometry measurements is shown in figure 5. The

of the

small

aggregation

36

-

34

-

0

-0_Q

-0

cn

32 -3.0

-2.5

FIGURE

FIGURE

lgxt

4. Surface

tension

of C3F7(CH2)5N+(CH3)2(CH2)3SO-

8-

lg

xt.

0,

Experimental;

4 -~~~~~~~~~~~~~

0

-

-,

calculated

(by using

10

103 Xt

solutions

(5.4)).

20

against

5. Vapour pressure osmometry, C8Hl7N+-(CH3)2(CH2)3SO solutions.

0,

x. against

xt;

, x2 against

xt (calculated

by using

(1.8)).

absence of any clearly defined discontinuity illustrates the difficulty in defining a c.m.c. precisely for surface-active agents with low aggregation numbers. The

from ideal behaviour at concentrations well

below the c.m.c. region. A verification of the interpretation of the deviations from

ideal behaviour in terms of solute aggregation was obtained by examining the homologous compound C6Hl3N+Me2(CH2)3SO , which was found to behave almost ideally over the same concentration range.

plot of xc against xt shows deviations

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Micelle formation

DISCUSSION

253

Multiple equilibriummodel The large change in the chemicalshift for the 19Fnucleus in the monomericand micellarstates enables x2to be determined as a function of xt by a method that is independent of thermodynamic assumptions. By extrapolation of the linear portions in figure 3, V2 and vmwere found to be 241.0 and 315.0Hz respectively relative to trifluoroaceticacid. The effect of micelle size on vmis assumed to be negligible.Valuesof x2as a functionof xt calculatedfrom(4.3)arein good agreement with those obtained by light scattering measurementsby means of (2.4), as shown in figure 6. We concludethat the multiple equilibriummodel adequately describes the aggregationof surface-activemoleculesin dilute aqueous solution.

2-

 

0

0

2

4

6

10wxt

FIGURE 6. The concentration of monomeric detergent, C3F7(CH2)5N+(CH3)2(CH2)3SO3, X2 against x,. 0, From n.m.r. results (calculated by using (4.3)); , from light scatter-

ing results (calculated

by using

(2.4)).

Surfacetension It has been shown for a number of surface-active agents that a plot of surface tension against the logarithm of the concentration is linear well below the c.m.c. (van Voorst Vader I960) which is consistent with the experimental observation madeby directradiotracermeasurementsthat the adsorbedmonolayeris essentially complete at concentrations well below the c.m.c. (Corkill, Goodman, Ogden & Tate I963). Assuming that Ft is defined by the linear region of the relation of y against lg xt below the c.m.c. (figure4), the variation of y with xt over the whole concentration range may be calculated by using (5.4) and values of NRobtained from light scattering experiments. The agreement with the experimentally deter- *minedvalues of y against lg xt is good, showingthat the abrupt changein y against xt observed at the c.m.c. is simply a consequence of the abrupt change in NR (Elworthy &Mysels I966).

I7

Vol. 312.

A.

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254 J. M. Corkill, J. F. Goodman, T. Walker and J. Wyer

Aggregation numbers and free energies of micellization

at any well defined

concentration (figure 5) and values of <n> and <n>w calculated from (3.6) and (3.7)

are small and increase markedly with increasing concentration (figure 7). The large differencle between <n> and <n>w at any particular concentration shows that the micelles are polydisperse with respect to size.

For C8Hl7N+Me2(CH2)3SO-, x2 does not change abruptly

10

3>5

0 5 -

/

<n>w

<n>

0

10

1O3xt

20

FIGURE7. Aggregation numbers for C8H17N+(CH3)2(CH2)3SO3, (calculated by using (3.6) and (3.7)).

(n>,

and (n> against xt

As <n> is small in the concentration range in which it can be accurately determined the integral approximation to the series inversion formula cannot be applied to obtain the dependence of the individual standard free energies of micelle formation (,u? - nr/O) upon n,. However, the average free energy of micelle formation, with respect to the mixed standard states can be obtained. The value of <(ziqO> for

at

C8H17N+Me2(CH2)3SO-decreases

4.5RT and is

dependent upon <n>. Thus as the micelle size increases the free energy for

the addition of a further monomer molecule tends to become constant. For these small micelles a considerable alkyl chain-water interaction in the core of the micelle is to be expected. As the association number increases the extent of alkyl chain- water interaction in the core region will decrease. The limiting value, approached

at high association numbers, represents the difference between the transfer of the hydrophobic chain from an aqueous to a non-polar environment and the free energy term associated with the packing of the head groups. The variation of x2with xt for C3F7(CH2)5N+Me2(CH2)3SOTis small at the higher concentration (figure 6) and the concept of a critical micelle concentration (x* = 1.50 x 10-3) is reasonable. <n>w calculated from equation (3.7) increases from 20 to 25 over the concentration range studied above the c.m.c. Values calculated using the Debye approximation (Debye I949), where the micelles are considered to

<n> = 2.5 much less

sharply

with

increasing

<n> from

-2RT

at small values of <n>. For <n> = 8, <zJ00> has the value -

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Micelle formation

255

be in a solvent defined by the solution composition at the c.m.c., are the same as those calculated from (3.7) within the experimental error.For this compound,the standard free energy of micellization with respect to the mixed standard state is

is

well approximated by AGO= RT lnx (Corkill, Goodman & Tate I968), and

- 6.50RT at 25 ?C.

Conclusions

The use of the multiple equilibrium model in the treatment of the properties of micellar solutions has shown how the various colligative properties may be related to the distribution of the solute between the monomeric and associated states. The connexion between the colligative and other (spectroscopic, surface) properties of the system has been demonstrated. Although a formally exact relationship enabling the free energy of formation of a particular species to be calculated from the colligative properties has been deduced, mathematical difficulties have pre-

the average free

vented

energy of association as a function of the average association number. The behaviour

of this quantity state.

us from applying

it. It is, however,

possible to obtain

is consistent with the currently accepted model of the micellar

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