Colloids and Surfaces A: Physicochem. Eng.

Aspects 497 (2016) 4144

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Langmuir isotherm explains maximum foamability

Oscar Arciniega Saavedra, Jess Gracia Fadrique
Departamento de Fisicoqumica, Facultad de Qumica, Universidad Nacional Autnoma de Mxico, Ciudad de Mxico 04510, Mexico

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Foamability was evaluated as elastic-

ity.
Maximum foamability is found at the
critical micelle concentration.
Gibbs adsorption equation coupled
with Langmuir equation explains
foamability.
Foamability. Cause: gradient in
surface pressure; effect: maximum
foamability at cmc.
The results are valid too in transient
foams behavior.

a r t i c l e i n f o a b s t r a c t

Article history: The relevant and promising empirical observation of M. Rosen regarding the maximum foam height in a
Received 18 November 2015 column at the critical micelle concentration is explained using basic thermodynamic analysis. Elasticity
Received in revised form 8 February 2016 determined isothermally from the equilibrium  A curve and Gibbs elasticity modulus, is evaluated by
Accepted 9 February 2016
means of the Langmuir isotherm and the corresponding surface equation of state. Beyond surface ten-
Available online 11 February 2016
sion, relevant variables on foam behavior were found on rst and second derivatives of surface pressure
in relation to bulk composition. This maximum foamability related to elasticity is predicted from the
Keywords:
Gibbs elasticity modulus and it shows that the maximum formability is reached in the vicinity of surface
Foam
Foamability saturation conditions and therefore in the neighborhood of critical micelle concentration.
Surfactant 2016 Elsevier B.V. All rights reserved.
Elasticity
Surface

1. Introduction Permanent foams show a maximum foamability at critical

micelle concentration [2]. This signicant empirical observation
Foam height generally increases with increasing surfactant con- made by M. Rosen, relative to the maximum foam height in a col-
centration, from highly dilute regions up to the critical micelle umn at the critical micelle concentration is explained using basic
concentration. In the neighborhood of the critical micelle concen- thermodynamic analysis. The present theoretical approach con-
tration foam height reaches a maximum value or increases slowly cerns to the relationship among the maximum foam height and
to a maximum value somewhat above the critical micelle concen- factors such as surfactant concentration, critical micelle concentra-
tration [1]. The present article shows, based on the Langmuir model, tion and surface tension. The theoretical results are in agreement
the theoretical fundamentals behind this experimental facts. with the factors which affect the initial foam height as determined
by the Ross-Miles pour method [3].
At the present work, the Gibbs elasticity modulus is used
as synonymous of foamability. The Gibbs elasticity is expressed
throughout the Langmuir isotherm and the corresponding surface
Corresponding author. equation of state, which shows a divergence in surface coverage
E-mail address: [email protected] (J. Gracia Fadrique). at the neighborhood of critical micelle concentration. Additionally,

http://dx.doi.org/10.1016/j.colsurfa.2016.02.015
0927-7757/ 2016 Elsevier B.V. All rights reserved.
42 O.A. Saavedra, J. Gracia Fadrique / Colloids and Surfaces A: Physicochem. Eng. Aspects 497 (2016) 4144

the Gibbs elasticity module can be expressed as a relation between This allows us to express the elasticity through the surface equation
the rst and second derivative of surface pressure at any particular of state, and the corresponding adsorption isotherm by the surface
molar fraction; this quotient is independent of the surface equation concentration or the surface coverage leading to
of state proposed. In the vicinity of critical micelle concentration,
d d d
d/dlnx tends to the maximum value and the second derivative = 2 =2 =2 (4)
tends to zero, so the quotient shows maximum elasticity and hence dlnA dln dln
maximum foamability. Therefore, the two terms in Eq. (4) expressed in relation to bulk
This treatment is also valid for transient foams, where in the concentration, dlnx, allow to introduce the corresponding Lang-
surroundings of saturation conditions, the foamability shows a muir surface equation of state (SEOS) and Langmuir isotherm as
lambda shape or divergence. The studies of S. Ross and G. Nish- explained in the discussion section
ioka about foamability of binary and ternary systems are pioneers
in this eld and are referenced to this behavior [4]. In our previous ddlnx
= 2 (5)
publication, we found the samelambda-type behavior at saturated d dlnx
conditions in phenol-water mixtures through the determination
of transient foam stability [4]. Therefore, the observation and con- The studies of surface tension variation with surfactant concentra-
tribution of Milton Rosen [5] is also true in the case of transient tion are the most common methods to calculate the critical micelle
foams of aqueous alcohol solutions [7] as 2-butoxyethanol-water. concentration. According to Gibbs adsorption equation
In our previous publication, we reported the behavior of the surface
d = 1 d1 + 2 d2 (6)
tension, composition and foaming capacity of the binary system
butoxyethanol-water at three different temperatures (4 C, 25 C) Where  2, d2, are the surface concentration and the solute
and at the vicinity of the lower critical solution temperature 48 C, chemical potential, respectively, and  1 , d1, are the surface con-
the maximum foaming (lambda shape) occurs just at the critical centration and solvent chemical potential, respectively.
micelle [6]. Boundary conditions on the vicinity of critical micelle concen-
Maximum foamability is measured with a method that nowa- tration [13,14].
days is ASTM procedure [3]. It is important to underline that this
work provides thermodynamic fundamentals for this observation x xcmc  s (7)
and it is described in an easy and simple way. Therefore, it is shown
1 02 s  1 (8)
that an isotherm and equation of state derived from equilibrium
conditions can be used. This is a crucial point of this analysis due to At this saturated region, the Gibbs adsorption Eq. (6) gives
the possibility of linking isotherm equations to equations of state
and elasticity modulus, leading to more stable and elastic lms: d = s d (9)
when a surface is expanded, surfactant concentration on the sur-
face decreases and surface tension increases; on the opposite case, Based on an ideal chemical potential at the bulk phase, and
when a surface is compressed surface concentration increases and eliminating the subscript 2 of the solute (amphiphile), Eq. (6) is
surface tension decreases. reduced to

d = s RTdlnxx xcmc (10)

2. Background Thus, the derivative nds a maximum before saturation, at the crit-
ical micelle concentration:
The Gibbs elasticity modulus relates the variations of surface  d max
tension to the surface area when it is expanded or compressed. It = s RT (11)
dlnx T
comes from the differential equation of Young-Laplace [79]. The
Gibbs elasticity [10] is dened as In a previous work, it has been reported that based on a
thermodynamic model, the adsorption process, and thus, surface
d saturation, proceeds before micellization [12]. The integral form of
=2 (1)
dlnA Eq. (11) between the intervals ( max ) and (x-xcmc ), identied
by the linear behavior of vs lnx in the vicinity of critical micelle
where is the surface tension and A is the molar surface area. concentration is
Elasticity is the ratio of the increase in the surface tension result-
ing from an innitesimal increase in area [11]. Surface tension can  = max s RTlnxcmc + s RTlnx (12)
be expressed in terms of surface pressure, dened as ( = ),
Eq. (12) provides a linear surface equation of state with  s RT as
where is the surface tension of pure solvent and is the surface
the slope and max  s RT lnxcmc as the intercept which contains
tension of the solution, so,
the critical micelle concentration value [13,14].

d = d (2)
3. Discussion

The essence of the Gibbs elasticity concept is determined In order to understand the methodology followed on this sec-
isothermally from the equilibrium -A curve [4]. The surface cover- tion, it is important to mention that the Gibbs adsorption isotherm
age  is related to the surface concentration  dened by (= / s ) allows us to transform an isotherm into a surface equation of state.
and the Gibbsian surface concentration  is related to the molar Surface pressure  and surface coverage  can be expressed as
area ( = 1/A); s is the maximum or saturation surface concentra- a function of composition for a surface equation of state and an
tion. Then, the Gibbsian surface concentration or supercial density isotherm, respectively. Assuming initially that the adsorbed surface
can be expressed by the surface coverage , lm is described by a two-dimensional equation of state, elasticity
is determined isothermally by the equilibrium  A curve [11]. In
dlnA = dln = dln (3) the following discussion of the theory, equations are rst devel-
 O.A. Saavedra, J. Gracia Fadrique / Colloids and Surfaces A: Physicochem. Eng. Aspects 497 (2016) 4144 43

oped for the case of the numerator of the right-hand side of Eq. (5). foamability region by identifying the interval at which the slope of
The Langmuir isotherm coupled to the Gibbs equation leads to the function is maximal and constant because:

x x
 d  d d2 
= = x xcmc (13) max 0 (21)
1 + x s RT dx T
dlnx dlnx2
According to Eq. (20), in the vicinity of critical micelle concen-
Where R is the gas constant, T is the absolute temperature, x
tration where conditions given by Eq. (21) are fullled, the surface
is the bulk molar fraction of the surface- active solute, and is a
coverage tends to the unit, 1, so the elasticity diverges and the
constant equivalent to Henrys constant in two dimensions [15]. In
foamability is maximum. Note that to analyze divergence at this
this case, the integral form leads to the corresponding Langmuir
point there was no need to use a surface equation of state; Gibbs
surface equation of state (SEOE):
adsorption equation was fair enough. Summarizing, on the basis
  of the previous arguments, the calculation of the ratio of rst and
 = s RTln 1 + x x xcmc (14)
second derivatives of vs lnx and the ratio of surface coverage pro-
The strategy which is suggested here for dealing with the term vided by Eq. (18) are valid as an important tool to identify maximum
d/dlnx of Eq. (5) is solved with the derivative of Eq. (14), shown as foamability.
Eq. (15). The rst derivative of numerator on the right-hand side of On the Langmuir model, Eq. (18) is a function of the bulk com-
Eq. (5) can be calculated from the surface equation of state (SEOE) position (x) expressed as
and is given by
= 2s RTx, x xcmc (22)
d x
= s RT = s RTx xcmc (15) If Eq. (22) is evaluated at the critical micellar concentration, the
dlnx 1 + x
maximum elasticity max is obtained
Eq. (15) can be conrmed by Eq. (11) when  1. To be consis-
m?x = 2RTxcmc (23)
tent with the above modication of the surface equation of state,
adsorption isotherm must be modied as well in order to obtain However, Eq. (23) is not very close or related to foamability
the denominator of Eq. (5): d/dlnx. It can be calculated from Eq. originated by the volume or foam height. It does not represent a
(13) and is given by lineal growth as a function of bulk composition. Therefore, critical
micelle concentration cannot be chosen as a measure of foamabil-
d x 2 x2 ity, critical micelle concentration just points out how composition
=  2 (16)
dlnx 1 + x 1 + x reaches a maximum. Behind this contradiction, the real meaning
of foamability correspond to rst and second derivatives of surface
where; pressure vs lnx in the neighborhood of critical micelle concentra-
d   tion equations (20,21). This analysis is valid for permanent foams in
=  2 =  1  (17) anionic, cationic and nonionic surfactants and for transient foams
dlnx
in ordinary liquids [5,6,19,20].
Substituting Eqs. (15) and (17) into Eq. (5), the functional depen-
dence of the Gibbs elasticity modulus on the surface coverage is 4. Conclusions
given by
Based on experimental facts it is shown that the maximum

= 2s RT (18) foamability in permanent and transient foams occurs at the critical
1
micelle concentration and at surface saturation conditions, respec-
It is important to point out from Eq. (18) that for  1, 1  tively. The background lies on the Gibbs elasticity of the lm as a
approaches to zero, so enhanced elasticity diverges (foamability is direct and principal promoter of foamability. The maximum foam-
maximum) at the critical micelle concentration as told by M. Rosen ability is interpreted under the Gibbs elasticity modulus, which
based on an experimental and empirical approach. Maximum sur- was coupled to the Langmuir isotherm and the Langmuir surface
face pressure cmc and critical micelle molar fraction xcmc can be equation of state, and hence, to the equilibrium behavior between
obtained from boundary conditions, in the vicinity of the critical lamellar liquid and surface concentration in the vicinity of the
micelle concentration [16]. It is necessary to emphasize that the critical micelle concentration. It has been demonstrated with this
Gibbs elasticity of the lm is a direct and principal measure of foam- equilibrium model that maximum formability depends on the gra-
ability given by Eq. (18).The surface coverage  which is related to dient of surface concentration and pressure in the vicinity of the
the surface concentration  dened by ( =  / s ) and the Gibbs critical micelle concentration. This is also true in transient foams
adsorption equation can be written in the following form where a maximum foamability exists in the vicinity of saturation

1
 d  conditions. This model explains the empirical observation of Mil-
= (19) ton J. Rosen, who rst noticed the relationship between the critical
s RT dlnx T micelle concentration and the maximum foamability.
Substitution of Eq. (19) and its derivative in Eq. (5) leads to a Foams are always formed under dynamic conditions, so the
form of the Gibbs elasticity modulus expressed in terms of rst equilibrium adsorption coverage will usually not be attained [21].
and second derivatives of the surface pressure with respect to the However, in aqueous systems and many ordinary liquids of low
logarithm of the solute concentration. viscosity, the interlamellar ow derived from gravity effects and
Plateau borders pressure difference provide a better transport
 d 2
mechanism than the pure diffusion process and so, this Marangoni-
= 2 
dlnx
(20) Gibbs effect provides a close approach to equilibrium conditions.
d2 
dlnx2
The application of surface thermodynamics to Gibbs elasticity is
not new [22] and our proposal is supported on surface equations
It was proved by Eq. (12), that  vs lnx shows a linear behav- of state and therefore we assume implicitly equilibrium conditions
ior in the vicinity of critical micelle concentration, so this form of between the surface and the bulk phase (lamellar uid). For these
the Gibbs elasticity modulus allows us to recognize the maximum reasons, we can consider as a reasonable approach the equilibrium
44 O.A. Saavedra, J. Gracia Fadrique / Colloids and Surfaces A: Physicochem. Eng. Aspects 497 (2016) 4144

condition in foam formation; if these hypothesis failed, then the [5] J. Gracia, C. Guerrero, J.G. Llanes, A. Robledo, Transient foaminess, aggregate
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(1986) 13501353.
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surfactant is a good measure of its efciency as a foaming agent; the 2-butoxyethanol + water, J. Phys. Chem. 92 (1988) 35653568.
[7] Remco Tuinier, Chris G.J. Bisperink, Cor van den Berg, Albert Prins, Trasient
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factant as a foamer [1]. However, this conclusion of Milton J. Rosen surface properties, J. Colloid Int. Sci. 179 (1996) 327334.
is contrary to Eq. (21). The critical micelle concentration does not [8] Josena Viades-Trejo, Jess Gracia-Fadrique, Curvatura y termodinmica,
Educ. qum. 18 (2007) 128132.
provide information about the elasticity or foamability; the critical
[9] E. Hernndez-Baltazar, J. Gracia-Fadrique, Elliptic solution to the
micelle concentration is the composition at which the maximum Young-Laplace differential equation, J. Colloid Int. Sci. 287 (2005) 213216.
amount of foam is obtained (maximum volume or height in a col- [10] J.W. Gibbs, The Scientic Papers of J. Williard Gibbs, Dover, New York, 1961.
[11] Sydney Ross, Ian D. Morrison, Colloidal Systems and Interfaces, John Wiley &
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Sons Inc, New York, 1988.
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as demonstrated by Eq. (20). The reader will notice that Eq. (20) adsorption equation and thermodynamic relation between Gibbs standard
is a general equation, independent of the surface equation of state energies of adsorption and micellization through a surface equation of state, J.
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position data, and so it is applicable with other surface equations of micelle concentration of poly(Oxy-1,2-Ethanediyl), alpha-Nonyl
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