Journal o f Solution Chemistry, Vol. 13, No.

2, 1984

Critical Micelle Concentrations for

Alkyltrimethylammonium Bromides in
Water from 25 to 160 ~
D. Fennell Evans, t Martin Allen, 1'2
B. W. Ninham, 3 and Abdel Fouda 4
Received October 17, 1983
Critical micelle concentrations were determined by conductance measurements .for
decyl-, dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromide in water
at 25, 60, 95, 130, and 160~
The results are discussed in terms of the equilibrium model and the nonlinear Poisson-Boltzmann model for micelle formation.
The free energies o f transferring a methylene group from water to the oil-like interior of the micelle are found to be -781 at 25~ -796 at 60~ -819 at 95~
-815 at 130~ and -787 at 160~ cal-mol "l.

KEY WORDS: Critical micelle concentrations;

bromides; hydrophobic interactions.

alkyltrimethylammonium

1. I N T R O D U C T I O N

There is surprisingly little information on micellar properties in

water at elevated temperatures. With the exception of critical micelle
concentrations (CMC) for tetradecyltrimethylammonium bromide (l~
which have been determined up to 166 ~ there is little information on
micelles above 90 ~
An analysis of the change of the CMC with
temperature provides information on hydrocarbon-water interactions
across an extensive temperature range. With increasing temperature,

1Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis,

MN 55455.
2Department of Chemistry, College of St. Thomas, St. Paul, MN 55105.
3Department of Applied Mathematics, Research School of Physical Sciences, Australian National
University, Canberra ACT 2600, Australia.
4Department of Chemistry, Mansoura University, Mansoura, Egypt.
87
0095-9782/84/0200-08753.50/0 9 1984 Plenum PublishingCorporation

88

Evans, Allen, Ninham, and Fouda

the unique structural properties of water diminish and water becomes a

more normal polar fluid. The analysis by Shinoda (3~ suggests that this
occurs at 160 ~
In this paper we report CMC's for a homologous series of
alkyltrimethylammonium bromides from 25 to 160 ~C.
2. EXPERIMENTAL

The alkyltrimethylammonium bromides (Eastman Kodak) were

recrystallized from acetone and dried in a vacuum oven at 6 0 ~ .
Surface tension measurements o n solutions of purified samples gave no
indication of a minimum near the CMC.
Doubly distilled
CO2-saturated water was used in the preparation of all solutions.
The resistance measurements were made on a Jones-Dole conductance bridge. The conductance bath was an insulated 16 liter stainless steel vessel filled with silicone oil (Dow-Corning 200). The bath
temperature was set with a platinum resistance thermometer and controlled with a Tronac Precision Temperature Controller (Model
PTC-40). Above 25 ~ some cooling to the bath was provided by
passing compressed air through a 0.25 in. copper tube immersed in the
bath; at 25 ~ water was passed through the cooling coil. The top of
the bath was covered with a polycarbonate (Lexan 1 / 4 in.) shield to
protect lab personnel from being sprayed with hot silicone oil in the
event of equipment failure at elevated temperatures and pressures.
The conductance measurements were made using a flow
system. (~ The solution flow rate and pressure were set using a metering pump (Cheminert Model #301) on the intake and a fine metering
valve on the exit. Above 100 ~ the pressure was set to 20 psi above
the vapor pressure of water and a flow rate of 0.3 ml-min 1 was used.
The pump was connected to the flow conductance cell by a short length
of Teflon tubing, a 30 ft. section of 0.03 in. I.D. stainless tubing which
served as a heating coil for the surfactant solution and an 18 in. length
of Teflon tubing which electrically isolated the heating coil from the
conductance cell. The conductance cell was connected to the metering
valve with Teflon tubing which had fittings for a pressure gauge and a
pressure relief valve.
The flow conductance cells consisted (Fig. 1) of pyrex glass tubes
with electrode compartments constructed of 5 mm tubing with 2 x 6
mm rectangular platinum electrodes connected by 2 mm tubing.
Tungsten-pyrex seals were used. The electrodes were placed vertically
in order to eliminate trapping of gas bubbles, particularly when filling

Temperature Dependence of the Critical MiceUe Concentration

89

1
Fig. 1. Flow conductance cell.

the cell. The gold lead wires were soldered to the ends of the tungsten
wire and covered with shrink-fit Teflon tubing. Epoxy cement was
used to insulate the exposed tungsten wire between the end of the
Teflon tubing and the glass tungsten seals. The conductance cell was
connected to the flow system with a Teflon connector (Lyon Technology #020-BOT) with O-ring seals. In our initial studies we used Teflon
valves; however, we encountered considerable difficulty at high temperatures in keeping the valve stem in place.
The Cheminert metering pump was constructed so that only
Teflon and glass components are in contact with the surfactant solution. The stainless steel heat exchange cell was immersed in the oil
bath and insulated from all the other metal components. Thus, there
is no electrical pathway to ground from the surfactant solution. We obtained the same resistance readings when the surfactant solution was
flowing through the cell as when the flow was stopped and the cell contents isolated from the rest of the system by closing the Teflon valves
on top of the cell.
At the beginning of an experiment, the flow system was flushed

Evans, Allen, Ninham, and Fouda

90

Table I. Critical Micelle Molality Concentrations for Decyl-,

Dodecyl-, Tetradecyl, and Hexadecyltrimethylammonium Bromides in
Water at Various Temperatures

~C
25
65
95
130
160

102CloTAB
6.76
7.79
9.36
10.8
17.4

102Ct27FAB 103CI4TABa
1.54
2.19
3.42
6.12
8.66

3.79
6.69
9.83
21.4
39.4

i03CI6TAB
0.955
1.55
2.61
6.12
13.03

aCMC's for C14TABat these temperatures were obtained from data given in Table II by
interpolation.
by running surfactant solution through at a flow rate of 2.8 ml-min "~ for
20 minutes. The flow rate was then reduced to 0.3 ml-min 1 and the
resistance measured. The next surfactant solution was then used to
flush out the system. Resistances of a total of eight to nine solutions
and the solvent were measured at each temperature for each surfactant.
In several cases, we passed a concentrated sample through the
flow system, at elevated temperature, and used it to measure surface
tension at 25 ~ over a concentration range which included the CMC.
We found no evidence for surfactant decomposition (i.e., no minimum
in -/near the CMC) at the temperatures studied.
3. RESULTS AND DISCUSSION

Critical miceUe concentrations in moles per kilogram of water for

the decyl (CtoTAB), dodecyl (Ct2TAB), tetradecyl (CI4TAB) and
hexadecyl (C16TAB) trimethylammonium bromides at 25, 95, 130, and
160 ~ are given in Table I. The CMC's were determined from plots of
1 / ll (reciprocal of resistance) vs. concentration using the data given in
Table II.
At low temperatures, the CMC is readily identified by a sharp
break in the conductance plot. At higher temperatures the break is
much less pronounced, reflecting the decrease in micelle aggregation
numbers. At present there is no quantitative information on the
change of micelle size with temperature. However, tracer diffusion
measurements using the water insoluble dye, methyl yellow, in C 14TAB
solutions permit aggregation numbers tO be estimated using Stokes'
Law. These give surfactant aggregation numbers of 70, 50, and 30 at

Temperalure Dependence of the Critical Micelle Concentralion

91

Table II. Reciprocal Resistances and Molat Concentrations

of Aqueous Alkyltrimethylammonium Bromide Solutions
at Various Temperatures
102m

10612-1

C10TAB,25~
1.018
4.83
3,012
13.34
5.154
21.52
6.161
25.06
7.159
27.48
8.233
29.49
10.315
32.09
15.642
38.59
CloTAB,160~
10.315 163.5
12.03
186.88
13.47
205.09
15.64
233.22
18.08
262.92
20.00
28533
21.59
302.20
23.37
322.46
25.48
343.37
ClffAB,130~
2.016
30.848
3.032
45.097
3,216
53,967
3.927
56.900
5.081
71.866
5.138
72.487
5.911
81.597
6.784
90.909
8.228 104.05
9.332 113.50

102m

106~-1

C1oTAB,65~
3,012
25.51
5:154
41,41
5A54
41.55
6.161
48.03
7.159
55.08
8.233
61.43
10.315
69.11
15.642
88.57

102m

106~-1

CtoTAB,95~
6.161
61.05
7.159
66.00
8.233
86.18
10.315 104.31
15,642 140.50
12.03
117.18
13.47
126.74
18.08
154.23

C12TAB,25~
0.5386
2.609
0.8218
3.915
1.025
4.818
1.539
7,021
2.016
7.740
3.022
8.904
3.927
9.932
5.081
11.282

Ct2TAB,65~
0.5386
4.920
0.8218
7.364
1.025
9.014
1.539
13.39
2.016
16.995
3.032
20.867
3.927
23.207
5.081
26.451

C12TAB,160~
3.927
67.641
5.081
85.442
5.138
79.780
5.911
97.985
6.784 110.56
8.228 130.82
9.332 145,74
1 1 . 0 3 8 163.75
11.996 178:21
12.949 189.09

CI4TAB,25.2~
0 . 1 2 2 8 9 0.6568
0.15644 0.8337
0.202040 1.0685
0 . 2 5 5 9 0 1.3460
0.30183 1.5809
0.50274
2.1437
0.60819
2.2780
0.69975
2.3910
0.85754 2.5864

102m

106~-~

CloTAB,130 ~
6,013
85.81
6.997
97.97
8.233 113.27
10.315 137.73
12.03
157.73
13.47
172,19
1L642
192.19
18.08
218.83
20.00
236.46
C12TAB,95~
0.7603
9.004
2.016
23.683
3.032
33.809
3.927
41.038
5.138
47.095
5.911
51.344
6.784
55.654

C14TAB,40.3 ~
0.12264 0.8597
0.15642 1.0911
0.20267 1.4081
0.25345 1.7505
0.33853 Z3201
0.44278 2.8651
056762 3.1611
0.74256 3.501
0.99318 3.963
0.65634 3,327
0.86077 3.698
1.1024
4.168

Evans, Allen, Ninham, and Fouda

92

Table II. (Continued)

103m

106f1-1

C14TAB,73.6 oC
1.5434
1.9615
2.5512
3.3180
4.2302
5.4142
7.2831
9.6610
16.231
8.6077
11.024
12.360
14.348

103m

C14TAB,95.5Oc

1.6975 1.2264
2.1464 1.5642
2.7086 2.0267
3.5951 2.5345
4.5486 3.3853
5.8025 4.4278
7.2218 5.6762
8.2223 7.4256
10.579
9.9318
7.8028 6.5634
8.7123
8.6077
9.2003 9.9766
9.9071 1 1 . 0 2 4
12.360
14.348
15.764

CI4TAB,166.0~
4.9997
9.7305
9.9969 1 8 . 8 3 6
15.167
27.929
19.967
36.246
50.020
82.485
54.638
88.65
61.205
95.795
66.853 103.00
73.694 109.71

1061/-1

103m

C14TAB,114
oC

1.6894
1.5434
2.1445 2.5512
2.7660 3.3180
3.4441
4.2302
4.5653
5.4142
5.9287 7.2831
7.5398 9.6610
9.7761 16.231
12.598
17.994
8.6813 18.736
11.205
21.405
12.635
20.062
13.462
14.333
15.450
16.202

C16TAB,25~
0.4996 0.23878
0 . 5 9 8 3 0.27922
0 . 7 0 5 3 0.33113
0 . 8 1 0 3 0.38264
0 . 9 0 2 8 0.41873
0.9941
0.44800
1.1946
0.47628
1.4000
0.50281
1.6102
0.52323
1.8477
0.55774

106~-1

103m

CI4TAB,134.9
o

2.4990
1.9615
4.0335
3.3180
5.2087 4.2302
6.5961
5.4142
8.3659 7.2831
11.130
9.6610
14.575
16.231
22.628
17.994
19.803
12.219
24.723 21.406
26.665 20.062
25.642 23.363
26.672
29.957
34.182

C16TAB,65
~
0.4996 0.47191
0.5983 0.55177
0:7053 0.64830
0.8103 0.74547
0.9028 0.82694
0.9941 0.90872
1.1946 1.0882
1.4000 1.2636
1.6102 1.4165
1.8477 1.5251
2.1984
1.5969
2.5108
1.7553

106~ .1

3.3450
5.5529
7.0130
8.9019
11.831
15.518
25.344
27.874
19.390
32.467
30.728
34.841
38.320
41.302
44.815

C16TAB,95
~
1 . 6 1 0 2 1.9940
1 . 8 4 7 7 2.3013
2 . 1 9 8 4 2.7426
2 . 5 1 0 8 3.0842
2 . 6 9 7 7 3.2964
3 . 0 0 5 5 3.5934
3 . 3 0 9 4 3.8372
3 . 6 1 4 9 4.0103
0 . 5 9 9 6 0.6530
0 . 5 9 8 3 0.7668
0 . 7 0 5 3 0.8906
0 . 8 1 0 3 1.0230
0.9023
1.1352
0.9941
1.2216
3.2165
4.116
3.4072
4.2583

Temperature Dependence of the Critical Micelle Concentration

93

Table II. (Continued)

103m

106~-1

103m

0.5996
0.5983
0.7053
0.8103
0.9023
0.9941
4.3400
4.8313
5.3466

CI6TAB,130~
0.8839 5.8990
1.0880 5.8990
1 . 2 7 5 3 6.3611
1.4537 6.8260
1 . 6 9 1 8 7.3253
1 . 7 7 0 3 7.8833
7.4327 8.3318
8.3325 8.9636
9.1859

106f~-I

103m

9.9762
9.9762
10.754
11.368
11.974
12.489
12.904
13.773

0.4996
0.5983
0.7053
0.8103
0.9023
0.9941
8.2871
8.9864

106~-l

103m

C16TAB,160~
1.083
11.891
1.289
13.003
1.471
14.170
1.694
15.955
1.860
17.966
2.085
19.933
17.474
21.844
18.616
24.125

106~-1

23.151
25.025
26.972
29.388
31.318
33.836
35:161
38.699

25, 95, and 130~ (4) With decreasing size the CMC becomes less
sharply defined since aggregation occurs over a larger concentration
range.
In previous publications (t'6) we analyzed the change of CMC with
temperature for C~4TAB to obtain the thermodynamics of transferring
the hydrocarbon chain from water to the oil-like interior of the micelle.
We have used two models, the equilibrium model (7> and a nonlinear
Poisson-Boltzmann model. (8~ Since these models can be used to obtain
insight into the nature of micelles at high temperature and the nature
of hydrocarbon-water interactions over an extended temperature range,
they will be described below.
According to the equilibrium model, an equilibrium between
monomers S +, counterions S - a n d monodisperse micelles M +p can be
represented by
NS + + ( N - p ) A - = M +p

(1)

The equilibrium constant K is related to the standard free energy of

micelte formation per monomer unit by

RTlnK = RTlnXcMc = ~XGHp/N- (1 -/3 )RTtnXcMc

(2)

where/3 = p/N. For a typical micelle (N = 50 to 100), the term

(R T~ N)lnXcM+P is small and consequently insensitive to large errors in
the estimated M +p, and is usually dropped in going from Eq. (1) to
Eq. (2). The form of Eq. (2) emphasizes that R TlnXcMc is the experimentally measured free energy of transferring a surfactant

Evans, Allen, Ninham, and Fouda

94

200

I l l l l l t l

12

14

180
160
140
120

50

T
~c:~100
0
80
60
95
40

0
0

~
2

65

10

~02rn ( r n o l e s - k g -1)
Fig. 2. Reciprocal resistances of dodecyltrimethylammonium aqueous solutions as a function of molality at various temperatures. The CMC's are indicated by arrows.

monomer from the solvent to the micelle, A G . p / N is the free energy

per mole of monomer of transferring the hydrocarbon tail from the
solvent to the oil-like interior of the micelle and (1 -/3 )RTlnXcMc is
the contribution to the free energy arising from the electrostatic interaction at the surface of the micelle.
The enthalpy for micelle formation is given by

AH = RTI[(2-/3 )(OlnXcMc/OT)p + lnXcMc (0/3/OT)p]

(3)

In this form, the equilibrium model assumes that the micellar aggregation number does not change with temperature and that all changes in
the surface electrostatic interactions with temperatures are given by
(~/3/0 T). In our analysis of C ~4TAB we estimated/3 from the changes

Temperature Dependence of the Critical Micelle Concentration

95

Table I I I . C o m p a r i s o n of T h e r m o d y n a m i c Transfer Quantities for

Transfer of a Surfactant H y d r o c a r b o n Chain f r o m Water to the Oil-Like
Interior o f a Micelle, using the Equilibrium and Poisson-Boltzmann
Models a
~

-AG b

25

9.95
10.5
10.2
10.9
10.2
11.1
10.2
11.4
10.1
11.5
9.6
11.3
9.2
11.1
8.54
10.6

40.3
54.2
76.3
95.5
114.0
134.9
166.0

-AH b

6.8
3.0
8.6
4.4
10.2
5.6
12.9
8.2
15.9
12.4
16.6
14.7
17.9
15.6
18.3
15.6

AS c

10
25
5
20
0.1
16
-8
9.5
-16
-2.5
-18
-8
-21
-11
-22
-12

1 -~

0.75
(0.85)
0.72
(0.84)
0.68
(0.83)
0.62
(0.82)
0.58
(0.82)
0.50
(0.77)
0.45
(0.75)
0.35
(0.70)

70
65
60
55

50
35
30
20

arhe data are for C14TAB; for each temperature the first entry is calculated using the
equilibrium model, Eq. (2), the second entry is calculated using the Poisson-Boltzmann
l
c
model, Eqs. (4-9). bKcal-mol-.
Cat-mol-KI
in slope of the specific conductance a b o v e and below the CMC, and obtained a value of 0 / 3 / O T = 0.003. W e obtained the values o f A G , AH,
and AS given in Table III.
According to the nonlinear Poisson-Boltzmann m o d e l the C M C
can be expressed as
R TlnXcM c = (4x~ -/x ~ = - - A GHp + g~

(4)

where Ix ~ a n d / ~ ~ are the chemical potentials of m o n o d i s p e r s e d micelles

and m o n o m e r s and s s describes the surface contributions.
In the
model, g s is written as the s u m
g s = Y oa + g e~

(5)

where g o~ is evaluated f r o m the nonlinear Poisson-Boltzmann equation

Evans, Allen, Ninham, and Fouda

96

for spherical geometry to give

g~/2kT = [ln(1/2s + ~,/1 + (1/2s) 2) + (1 - ~ 1 + (lhs) 2) / 0/as)

- (2/KRs)(1 + , J l + ( l h s ) 2 )

...~]

(6)

where K z = (8rrn2o/ekT) and s = 4rre2/eKakT. K -~ is the Debye

length, s is the scaled charge density, and R is the radius of the micelle.
In Eq. (5), the first term is the electrostatic free energy of a flat double
layer and the second an explicit correction due to curvature of the
surface, a is the surface area per surfactant molecule and 3, o is the
surface tension at the hydrocarbon-water interface that is assumed to
be constant. Contributions to g~I arising from stericrepulsion, hydration, and entropic terms are not included in the model and consequently are implicitly included in ~ o.
For the micelle at equilibrium
3 g ~ t / O a = (yo +

y~,) =

(7)

from which
2eK
~ e l = --

rr

T
(____2_")2 [sinh2(yo/4) +
e

2
KR

In cosh(yo/4) + . ..] (8)

where the scaled surface potential Yo = etOs/kT can be determined

from the equation
S = 2sinh(yo/2) +

4
KR

tanh(Yo/4)

(9)

These equations depend on the variables K, a and R. For spherical

micelles R and a can be related geometrically by the relations

4rrR 2= Na,

(4~"/3)R 3 = N V

(10)

where V is the volume of the hydrocarbon core which is calculated

from
V ( A 3) =

27.4

+26.9nc

Here, n, is close to the number of carbon atoms per chain. The fully
extended chain length is lc(A) = 1.5 + 1.265n~.

135

90

55

21.4

15.7
14,2
12.4

18.9
17.9
16.9

16.6

14.1

64

77
85
97

64
67
72

63

63

10.00

6.21
5.94
5.53

8.16
8.02
7.85

6.76

5.27

2.47

2.18
2.19
2.18

2.47
2.50
2.54

2.27

1.98

~ a/kT

7.51

4.00
3.71
3.28

5.66
5.49
5.27

4.46

3.25

gel/kT

entries for CI4TAB illustrate the effect of aggregation number on the calculated quantities.

25

40
30
20

25

Ct4TAB

CI6TAB

70
60
50

25

C12TAB

40

25

CIoTAB

Surfact.

5,917

5,011
4,781
4,424

4,822
4,737
4,632

3,989

3,101

gs

6,495

6,373

5,682

4,851

3,975

-R TInXcMc

Table IV. Calculated Free Energies for the Alkyltrimethylammonium Bromides

at 25~ using Eqs. (4-9)o

12,412

11,384
11,155
10,798

10,504
10,419
10,314

8,840

7,076

-AGHp

0.91

0.79
0.75
0.69

0.85
0.83
0.81

0.82

0.78

(1-,8)

9"

N"

r
-i

t~
-1

t~

-4

98

Evans, Allen, Ninham, and Fouda

The Poisson-Boltzman model allows the free energy of micelle

formation to be explicitly written in terms of molecular variables which
characterize the micelle. In particular the effect of aggregation number
can be directly ascertained. However, a limitation arises from treating
the counterions as point charges. As a consequence, the specific differences among various counterions (e.g. OH-, CI, Br, I-) require the
introduction of an additional parameter. For example, the difference
between micelles with bromide and hydroxide counterions (described
below) can be accounted for by assuming that the hydroxide ion is
located 4 A from the surface of the micelle.~6)
The quantities calculated for C14TAB at 25 ~ with N = 80 to 40
and at 130~ with N = 50 to 10 are given in Table IV. For a typically
large micelle at room temperature the change in A GHp is small. For
example the change in AGup from N = 70 to N = 60 is 140 cal-mol-~i
For the smaller micelles encountered at higher temperatures, A G,p is
much more sensitive to changes in N, e.g. from N = 30 to 20 the
change is 425 cal-mol ~, inspection of Table IV shows that the decrease
of y and the increase of a with N almost compensate one another in
y a/K T. Consequently, it is the variation of y e~with changing curvature
that is responsible for the dependence of gs and consequently /~GHp
upon aggregation number. Also given in Table IV are values for the
other alkyltrimethylammonium bromides using the measured aggregation numbers. With the aggregation numbers estimated from the dye
diffusion measurements, the free energy for transferring the tetradecyl
hydrocarbon chain from water into the micelle are given in Table III.
The values of A H a n d AS were determined from a plot of AGHp vs. T.
The equilibrium model and the Poisson-Boltzmann models can be
compared in terms of Eqs. (2) and (4) which show that they are equivalent provided
gs = RT(1 -/3 )In XcMc

(11)

It is clear that the ion binding paramter (1 -/3) must account for
all changes in g~, y o and N with temperature. It is not surprising that
the thermodynamic quantities AH and AS differ somewhat as determined by the two models. In fact, Eq. (11) in the form
(1 -/3) = g s / R T l n XCMc

(12)

provides a way of calculating this parameter from theory. The 313 / ~ T

used for the equilbrium model is 3 10 3 while that obtained from Eq.

]-emperature Dependence of the Critical Micelle Concentration

-2

O-- ~
,.. ~ #~ ; ~ ^

~-...

"-~.

99

-CH 2-

25oc
60~
95~
150~

-781 ( c a l / m o ] )
-796
-819
-815
"

-4

-6

-8

I
10

J
I2

I
t6

"14

iilii
18

nc

Fig. 3. The dependence Of In CMC on the carbon number n c at various temperatures and
the free energies of transfer of a methylene group from water to the micelle as determined from Eq. (12).

(12) is 7 x 10 -4. These differences reflect, at least in part, an implicit

inclusion of 3r / ~)T in 3/3 / ~1T for the equilibrium model.
The change of lnXcMc vs. carbon number for all the surfactants at
the various temperatures is shown in Fig. 3. At 25 and 65 ~ all of the
data points lie on a straight line, however, the values (with increasing
temperature) for C 10TAB fall progressively below the straight line.
The straight lines can be represented by
In Xcc = ao +

aln c

(13)

which in terms of the equilibrium model [Eq. (2)] can be given as

O A G / O n ~ = R T ( 1 - ~ )al

(14)

This permits the free energy of transferring a methylene group from

100

Evans, Allen, Ninham, and Fouda

the solvent to the micelle to be calculated. We have employed the

value of (1-/3) calculated from Eq. (12). The free energies show a
maximum near 100~ which corresponds to a minimum in the
solubility. Above this temperature the free energy decreases corresponding to the usual behavior of increasing solubility with increasing
temperature. Below 100 ~ the solubility of hydrocarbons is increased,
not decreased, by the unique structural properties of water around nonpolar groups. Similar behavior was observed by Shinoda (3) from an
analysis of the solubility of alkylbenzenes and alcohols as a function of
temperature.
The anomalous behavior of C10TAB with increasing temperature
can be understood in the following way. At 25 ~ N=39. With increasing temperature N decreases and more of the hydrocarbon chain is
exposed to water. Parallel behavior is shown by the alkyltrimethylammonium hyroxide at 25 ~ The CMC's for the hydroxides are twice as
large as those for the bromides while the aggregation numbers are considerably smaller. (9m For C~4TAOH, CMC = 7.2x 103M, N = 4 4 and
(1,/3) = 0.40 compared to the CMC = 3.6x 103M, N = 70 and (1-/3)
= 0.75 for C14TAB. The differences reflect the strongly hydrophilic
nature of the hydroxide ion which takes a position further away from
the micelle surface than the bromide ion.(67 This results in an increased
electrostatic repulsion between the headgroups, a larger a and a corresponding decrease in N. The free energy of transferring a methylene
group from water to the micelle are very different for these two
couterions. Equation (14) gives -520 cal-mol ~ for the hydroxide surfacrants compared to -780 cal-mol ~ for the corresponding bromides. This
corresponds to approximately two more methylenes groups of the
hydrocarbon chain being exposed to water when the counterion is
hydroxide.
The discussion given above clearly illustrate that any detailed
analysis of the themodynamics of micelle formation will require aggregation numbers as a function of temperature. However, the analysis
of dependence on chain length for all the surfactants studied and for
C~4TAB with the activated aggregation numbers provide a consistent.
The free energy of transferring a hydrocarbon chain from water into
the micelle shows a minimum in hydrocarbon solubility near 100~
The entropy (AS = ~AG/~T) at low temperatures is positive,
decreases to zero near 100~ and becomes increasingly negative at
higher temperatures. The enthalpy becomes progressively more negative with increasing temperature. These compensating changes in ~ H
and AS demonstrate that the changes in water around hydrocarbon

Temperature Dependence of the Critical Micelle Concentration

101

chains have only a small effect on the solubility of nonpolar groups in

aqueous solutions. ~12)
ACKNOWLEDGMENT
T h i s w o r k was s u p p o r t e d by t h e N a t i o n a l S c i e n c e F o u n d a t i o n a n d
U.S. A r m y C o n t r a c t N o . D A A G 2 9 - 8 1 - K - 0 0 9 9 .
REFERENCES
1. D. F. Evans, and P. J. Wightman, J. Coll. and Interf Sci. 86, 515 (1982).
2. P. Mukerjee and K. J. Mysels, Nat. Stand. Ref. Data Serv., Nat. Bur. Stand.
U.S. 36.
3. K. Shinoda, J. Phys. Chem. 81, 1300 (1977).
4. D. F. Evans, S. Mukherjee, D. J. Mitchell, and B. W. Ninham, J. Coll. and
lntecf. Sci. 93, 184 (1983).
5. S. Mukherjee and D. F. Evans, J. Solution Chem. 11, 871 (1982).
6. D. F. Evans, and B. E. Ninham, J. Phys. Chem. 87, (Nov. 1983).
7. P. Mukerjee, J. Phys. Chem. 66, 1375 (1962).
8. D. J, Mitchell and B. W. Ninham, J. Phys. Chem. 87, 2996 (1983).
9. P. Lianos and R. Zana, J. Phys. Chem. 87, 1289 (1983).
10. S. Hashimoto, J. K. Thomas, D. F. Evans, and S. Mukherjee, J. Coll. and
Interf Sci., (Oct. 1983).
11. P. Lianos and R. Zana, J. Colloidand InterfacialSci. 84, 100 (1981).
12. M. Ramadan, D. F. Evans, and R. L. Lumry, J. Phys. Chem. 87, (Oct. 1983).