UNIVERSIDAD NACIONAL AUTÓNOMA

DE MÉXICO
FACULTAD DE QUÍMICA

Butler-Lucassen-Reynders

AAGF

SPQS, Facultad de Quı́mica

Universidad Nacional Autónoma de México

4 de agosto de 2021

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CHEMICAL POTENTIAL

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Chemical potential
For a L-s-V system at T, p, nj6=i and m components
m
X
dGs = µsi dnsi + σdA (1)
i=0

dGs = µsi dnsi + σdA (2)

µsi dnsi s
= dG − σdA (3)
∂Gs
     
∂A ∂A
µsi(T,p,A) = −σ ; ωi =
∂nsi T,p,nj6=i
s
∂ni T,p,nj6=i ∂nsi T,p,nj6=i
(4)
µsi(T,p,A) = µsi(T,p) − σωi (5)
E,s
µsi(T,p) = µs◦ s
i(T,p) + RT ln(xi ) + Gi ; GE,s
i = RT ln(γis ) (6)
µsi(T,p,A) = µs◦ s s
i(T,p) + RT ln(xi ) + RT ln(γi ) − σωi (7)

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Chemical Potential

µsi = µ∗,s s s
i (T, p, σ) + RT ln(γi xi ) (8)
at (T,p)=const X
dG = −Adσ + µsi dnsi (9)
Maxwell relationship
 s    
∂µi ∂A ∂A
=− ; ωi = (10)
∂σ ns ∂nsi σ ∂nsi σ
j6=i

Therefore
µsi = µ∗,s s s
i (T, p) + RT ln(γi xi ) − ωi σ (11)

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Corollary

Z µ Z a
dµ = RT d ln a ? (12)
µ∗ 1
Z µ Z a Z σ
s s
dµ = RT d ln a + ωdσ ? (13)
µ∗ 1 0

γis = f (His , Sis ) (14)

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GENERAL ADSORPTION EQ

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Adsorption

In a two phase system with s and b phases and i components, 0

for solvent and i for solute, at equilibrium

µ∗,s s s ∗,b b b
i + RT ln(γi xi ) − ωi σ = µi + RT ln(γi xi ) (15)

Where the standard state for the solvent in the surface µs0 and
liquid µb0 are defined by

xs0 = 1 ; xb0 = 1 ; σ = σ0 and γ0s = γ0b = 1 (16)

And for the solute the standard state in the surface µsi and
liquid µbi are defined by

xbi = xb,∞
i ; xsi = xs,∞
i ; σ = σ0 (17)

γi s = γis,∞ ; γib = γib,∞ (18)

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Adsorption

For the solvent

µ∗,s ∗,b
0 + RT ln(1 × 1) − ω0 σ0 = µi + RT ln(1 × 1) (19)

µ∗,s ∗,b
0 − ω0 σ0 = µi (20)
Therefore

µ∗,b s s ∗,b b b
0 + ω0 σ0 + RT ln(γ0 x0 ) − ω0 σ = µ0 + RT ln(γ0 x0 ) (21)

ω0 (σ0 − σ) + RT ln(γ0s xs0 ) = RT ln(γ0b xb0 ) (22)

 b b
ω0 (σ0 − σ) γ0 x0
= ln (23)
RT γ0s xs0

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Adsorption

For the solute

µ∗,s
i + RT ln(γi xi ) − ωi σ0 = µ∗,b
s,∞ s,∞ b,∞ b,∞
i + RT ln(γi xi ) (24)

µ∗,s ∗,b b,∞ b,∞

i = µi + RT ln(γi xi ) − RT ln(γis,∞ xs,∞
i ) + ωi σ0 (25)
Therefore

µ∗,b b,∞ b,∞

i + RT ln(γi xi ) − RT ln(γis,∞ xs,∞
i )
+ωi σ0 + RT ln(γis xsi ) − ωi σ (26)
= µ∗,b b b
i + RT ln(γi xi )
!
γis xsi γib xbi
 
RT ln s,∞ s,∞ + ωi (σ0 − σ) = RT ln (27)
γi xi γib,∞ xb,∞
i

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Adsorption

For the solute

!
ωi (σ0 − σ) γib xbi γis,∞ xs,∞
i
= ln (28)
RT γis xsi γib,∞ xb,∞
i
!
ωi (σ0 − σ) γis xsi γib,∞ xb,∞
i
− = ln s,∞ s,∞ (29)
RT γib xbi γi xi

Where K = xs,∞
i /xb,∞
i
!
ωi (σ0 − σ) γis xsi γib,∞ 1
− = ln s,∞ (30)
RT γib xbi γi K

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Adsorption

The main equations for adsorption are

 s s
ω0 (σ0 − σ) γ0 x0
− = ln (31)
RT γ0b xb0
!
ωi (σ0 − σ) γis xsi γib,∞ 1
− = ln s,∞ (32)
RT γib xbi γi K

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SEoS AND ISOTHERM
FOR IDEAL BULK AND SURFACE

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Ideal behavior

In the bulk
γ0b = 1 ; γib = 1 ; γib,∞ = 1 (33)
In the surface

γ0s = 1 ; γis = 1 ; γis,∞ = 1 (34)

For the partial molar area

ω0 = ωi = ω (35)

Therefore  s
ω(σ0 − σ) x0
− = ln (36)
RT xb0
 s 
ω(σ0 − σ) xi 1
− = ln (37)
RT xbi K

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Ideal behavior Isotherm

xs0 xsi 1
= (38)
xb0 xbi K
In the ideality xb0 = 1 because a0 = 1?
Definition
xsi = θi = Γi ωi (39)
And using xbi = ci
θi
θ0 = (40)
Kci
As X
θ0 = 1 − θi ; if i = 1 then θ0 = 1 − θ1 (41)
θi Kci
1 − θi = ; θi = (42)
Kci 1 + Kci

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Ideal behavior SEoS

xsi 1
 
ω(σ0 − σ)
− = ln (43)
RT xbi K
Substituting π = σ0 − σ, θi and ci and approximating ω = Γ−1
 
π θ1
− = ln (44)
ΓRT Kci

Rearranging
π = ΓRT ln(1 + Kci ) (45)

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SEoS(s) AND ISOTHERM(s)
FOR IDEAL BULK

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Adsorption

The main equations for adsorption are

 s s
ω0 (σ0 − σ) γ0 x0
− = ln (46)
RT γ0b xb0
!
ωi (σ0 − σ) γis xsi γib,∞ 1
− = ln s,∞ (47)
RT γib xbi γi K

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Ideality on the bulk

γ0b = 1 ; γib = 1 ; γib,∞ = 1 (48)

Therefore
ω0 (σ0 − σ)
− = ln (γ0s xs0 ) (49)
RT
 s s 
ωi (σ0 − σ) γi xi 1 1
− = ln s,∞ (50)
RT xbi γi K

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Ideality on the bulk SEoS

ω0 (σ0 − σ)
− = ln (γ0s xs0 ) (51)
RT
xsi = θi = Γi ωi ; π = σ0 − σ (52)
" ! #
RT X
s
π=− ln 1 − θi + ln(γ0 ) (53)
ω0
i=1

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Ideality on the bulk Isotherm

RT
π=− ln (γ0s xs0 ) (54)
ω0
 s s 
RT γi xi 1 1
π=− ln s,∞ (55)
ωi xbi γi K
Therefore
γis xsi 1 1
 
ωi
ln (γ0s xs0 ) = ln s,∞ (56)
ω0 xbi γi K
Ω = ωi /ω0
γis xsi
 
(γ0s xs0 )Ω= (57)
γis,∞ xbi K
xbi = ci; xsi = θi ; xs0 = θ0 = 1 − θi
P

γis
θi γis,∞
Kci = (58)
Ωi (γ0s )Ωi
P
(1 − i=1 θi )

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Ideality on the bulk SEoS and Isotherm

General equation for adsorption with ideal bulk

" ! #
RT X
s
π=− ln 1 − θi + ln(γ0 ) (59)
ω0
i=1

γis
θi γis,∞
Kci = P Ωi (γ s )Ωi
(60)
(1 − i=1 θi ) 0

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Activity Coefficient Contributions

To account for the i component non idealities in the surface for

a two surfactant aqueous mixture

ln(γis ) = ln(γis,H ) + ln(γis,S ) (61)

s,H
XX 1 s

s
RT ln(γi ) = Ai,k − Ai,j θi θj (62)
2
i=1 j=1

s,S
X  θi 
ln(γi ) = 1 − Ωk (63)
Ωi
i=1

Where Ai,j = Ui,i + Uj,j − 2Ui,j and Ui,j are the energies of
interaction between species. Ω0 = 1.

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Ideality on the bulk SEoS and Isotherm

Where a1 = A01 ; a2 = A02 ; a12 = (A01 + A02 + A12 )/2;

bi = Ki exp(ni − ai − 1); i = 1, 2; j = 1, 2; i 6= j.

" 2
! 2     #
RT X X 1
π=− ln 1 − θi + θi 1 − + βi θi2 + β12 θ1 θ2 (64)
ω0 i=1 i=1
Ωi

θi
bi c i = exp[−Ωi −2βi θi −2β12 θi +(1−Ωi )(β1 θ12 +β2 θ22 +β12 θ1 θ2 )]
(1 − θ1 − θ2 )Ωi
(65)
bi = f (K) (66)

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Corollary

The Gibbs surface is where

Γ0 = 0 (67)

The Lucassen-Reynders surface is where

X
ω0 = ω̄ ; Γi = Γi,sat (68)
i=0

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Generalized von Szyszkowski-Langmuir

s
∆Hmix = 0, β1 = β2 = β12 = 0
Two surfactant aqueous mixture
2 2  
" ! #
RT X X 1
π=− ln 1 − θi + θi 1 − (69)
ω0 Ωi
i=1 i=1

θi
bi ci = exp[−Ωi ] (70)
(1 − θ1 − θ2 )Ωi
Our β is related to bi × e

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Generalized Frumkin

s
Only the ideal component of the ∆Smix is considered, therefore
Ω1 = Ω2 = 1
Two surfactant aqueous mixture
2 2
" ! #
RT X X
βi θi2 + β12 θ1 θ2


π=− ln 1 − θi + (71)
ω0
i=1 i=1

θi
bi ci = exp[−1 − 2βi θi − 2β12 θi ] (72)
1 − θ 1 − θ2

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Ideality on the bulk SEoS and Isotherm without SAC

" 2
! 2     #
RT X X 1
π=− ln 1 − θi + θi 1 − + βi θi2 + β12 θ1 θ2 (73)
ω0 i=1 i=1
Ωi

θi
bi c i = exp[−Ωi −2βi θi −2β12 θi +(1−Ωi )(β1 θ12 +β2 θ22 +β12 θ1 θ2 )]
(1 − θ1 − θ2 )Ωi
(74)
bi = f (K) (75)

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REORIENTATION

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Reorientation

For i possible orientation states for one surfactant and assuming

surfactant-surfactant and solvent-surfactant intermolecular
interactions independent from orientation state.
Enthalpic:
ln(γ0s,H ) = aΓ2Σ ωΣ
2
(76)
ln(γis,H ) = a(1 − ΓΣ ωΣ )2 , i ≥ 1 (77)
Entropic:
ln(γ0s,S ) = 1 − ω0
X
Γj = 0 (78)
j≥0

ln(γis,S ) = 1 − ωi
X
Γj = 1 − Ωi , i ≥ 1 (79)
j≥0

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Reorientation

Where P
i≥1 Γi ωi
ωΣ = P (80)
i≥1 Γi
X
ΓΣ = Γi (81)
i=0

Therefore
RT h i
π=− ln (1 − ΓΣ ωΣ ) + a (ΓΣ ωΣ )2 (82)
ωΣ
Γi ωΣ
exp −Ωi − 2aΓΣ ωΣ + a(1 − Ωi )(ΓΣ ωΣ )2


bc =
(1 − ΓΣ ωΣ ) Ωi
(83)

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AGGREGATION

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Aggregation
For 1 surfactant and 1 molecular aggregate

µsNagg = Nagg µs1 (84)

And
µsi = µ∗,s s s
i (T, p) + RT ln(γi xi ) − ωi σ (85)
Assuming ideal mixing
 
−π∆ω
xsNagg = KNagg (xs1 )Nagg exp (86)
RT

Where KNagg is the aggregation constant and

∆ω=Nagg ω1 − ωNagg
 
Nagg Nagg −1 −π∆ω
ΓNagg = KNagg Γ1 ωΣ exp (87)
RT

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Aggregation

Assuming
∆ω = Nagg ω1 − ωNagg ≈ 0 (88)
And evaluating KN agg in Γ1 = ΓNagg = Γsat
( " #)
Γ1 Nagg −1
 
RT
π=− ln 1 − Γ1 ωΣ 1 + (89)
ωΣ Γsat

Γ1 ωΣ
bc =    Nagg −1 ω1 /ωΣ (90)
Γ1
1 − Γ1 ωΣ 1 + Γsat

Where
1 + Nagg (Γ1 /Γsat )Nagg −1
ωΣ = ω1 (91)
1 + (Γ1 /Γsat )Nagg

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IONIC SURFACTANTS

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Ionic surfactants

1. Gouy–Chapman theory is used to model the double layer.

2. Interfacial properties determined by Gibbs adsorption.
XN
dσ = −RT Γ̃i d ln(asoln
i ) (92)
i=1

Where
asoln
i = γi csoln
i ; γi = f (I) (93)
Where asoln
i is the activity in solution of i and I is the solution
ionic strength.

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Ionic surfactants

Figura: Electric Double Layer

https://agupubs.onlinelibrary.wiley.com/doi/full/10.1029/2019JB017679

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Ionic surfactants

Z soln h i
Γ̃i = Γi + ci (d) − csoln
i d(d) (94)
s

1. Where Γi is the adsorption at the Stern Layer.

R soln 
ci (x) − csoln

2. And s i dx is the adsorption in the diffuse
electric layer.
According to the Boltzmann distribution
 
soln −zi eΨ(d)
ci (d) = ci exp (95)
kB T

Where d is the distance from the bulk to the surface, zi is the

valence, e is the electron charge, kB is the Boltzmann constant
and Ψ(d) is the electric potential.

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Ionic surfactants

Additionally
asoln
i = asi exp(zφs ) (96)
Where φs is the scaled surface potential.
φ
φs = (97)
φ0
eΨ
φ= (98)
kB T

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Ionic surfactants

N
X N Z
X soln 
dσ u RT Γi d ln(asi ) − RT asoln
i [exp(−zi φ) − 1]dd d ln(asi )
i1 i=1 s

(99)
Using the Boltzmann-Poisson distribution
2 N
2000F 2 X soln

dφ
= ci [exp(−zi φ) − 1] (100)
dd εε0 RT i=1
s )1/2
N Z asoln
(N
X i εε0 (RT )3
Z φs X
π = RT Γi d ln(asi )+ asoln
i [exp(−zi φ) − 1] dφ
i=1 0 500F 2 0 i=1
(101)

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Ionic surfactants

Using the approximation asoln i = csoln

i (I → 0) the Graham
equation for 1:1
r
εε0 RT asoln
Γionic surfactant + Γcounter ion = sinh(φs /2) (102)
125F 2
And solving the integral of the EDL
(N )1/2
Z φs X √  
φs

asoln
i [exp(−zi φ) − 1] dφ = 2 2asoln cosh −1
0 2
i=1
(103)

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Ionic surfactant SEoS and isotherm

8RT √ soln
  
φs
π = RT Γsat [ln(1 − θ1 ) + βθ12 ] − a cosh −1
κ 2
(104)
For the ionic surfactant (1)

θ1
Kas1 = exp(−2βθ1 ) (105)
1 − θ1
For the counter ion (2)

K2 as2
θ2 = θ 1 (106)
K
Where
K = K1 + K2 as2 (107)
Being Ki the equilibrium adsorption constants
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PROTEINS

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Proteins

1. Proteins molecules can exist in a number of states with

different molar.
2. Non-ideality enthalpy from adsorbed proteins does not
depend on the state of adsorbed molecules (76)-(81).
3. Enthalpic Frumkin contributions are assumed

RT   4RT
π=− ln(1 − ΓΣ ωΣ ) + a(ΓΣ ωΣ )2 + (2εRT csoln )1/2 [cosh(phi) − 1]
ωΣ F
(108)
θi fis
Ki c =  Ωi exp(2φ) (109)
(f0s )Ωi
P
1 − i≥1 θi

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Proteins

Considering: csoln ≥ 0,1 molL−1 , and

zF Ψ
φ= (110)
2RT
zΓΣ F
sinh(φ) = (111)
(8εRT csoln )1/2
sinh(φ) = φ + φ3 /6 (112)
2
cosh(φ) = 1 + φ /2 (113)
2
exp(2φ) = (sinh(φ) + cosh(φ)) (114)
And introducing

z2F
ael = (115)
ωΣ (8εRT csoln )1/2

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Proteins

RT 
ln(1 − ΓΣ ωΣ ) + (a − ael )(ΓΣ ωΣ )2

π=− (116)
ωΣ
h  
2 i
2 i ω1
Γi ωΣ exp −aΓ2Σ ωΣ ω −1
− i ωω1 − 2aΓΣ ωΣ + 2 azel ΓΣ ωΣ + ael
z
ΓΣ ωΣ
Σ Σ
b1 c =
iα (1 − ΓΣ ωΣ )iωi /ωΣ
(117)
Where α is a constant that determines the variation in surface activity of the
protein molecule in the ith state with respect to state 1 characterized by a
minimum partial molar area ω1 .

bi = b1 iα ; ∆i = ∆ω/ω1 (118)

If ωΣ = 6 × 106 m2 mol−1 , z = 30, cΣ = 2 molL−1 then ael = 100

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THANK YOU

SPQS
SE
NA ES
TUS ICI
POPULUSQUE SUPERF

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