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Introduction

First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

The Hydrophobic Aggregation of Two


Colloids: A Thermodynamic Model
Bimal Chandra Sinha
School of Physical Sciences,
NISER

April 5, 2016

Outline

Introduction

1 Introduction

First law:
Energy
Conservation

2 Energy conservation along the aggregation processes:

2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility

Application of the first law


3 Aggregation Produces Entropy: Application of the Second

Law

Conclusion

4 Source of irreversibility
5 Conclusion

Introduction

Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

The objective of the paper is to propose thermodynamic equations describing the aggregation process of two colloids through
hydrophobic effect.
This has been done according to a very simple scheme of aggregation of two colloids s and p suspended in a liquid phase
l.

Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

Two colloids s and p are aggregating into a liquid phase l.


Those two colloids are surrounded by superficial phases sl
and pl coarsely represented by dotted belts around them.
Dashed lines are for open phases (energy and matter exchanges) and solid for closed ones (no matter exchange).
System is delimited by the external dashed line because it
is open to its environment.

Introduction

In the first section, well known equations for energy conservation based on the first law of thermodynamics will be
developed.

First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

In the second section, the second law will be introduced


and the entropy production will allow us to obtain equations
remaining valid for out-of-equilibrium situations.

Finally, the obtained equations will allow us to discuss about


equilibrium conditions and stability conditions based on chemical potentials.

1. Energy conservation along the aggregation


processes: Application of the first law
dE = dW + dQ
Introduction

First, we can use the fact that v =

First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

dW

vl

(1)
vp

vs

to obtain

= p l dv l p l dv p p l dv s
= p l dv l p p dv p p s dv s + (p p p l )dv p + (p s p l )dv s

Using Young-laplace equation which gives the pressure differences across curved liquid surfaces,
1
1
p 1 p 2 = (
+
)
R1 R2
For spherical phases s and p, the laplace equation gives
2
2
p p p l = pl p and p s p l = sl s
(2)
R
R
Using d = R2 dv and (2), we obtain

dW = p l dv l p p dv p p s dv s + pl d p l + sl d sl

(3)

Introduction

2nd Law:
Aggregation
Produces
Entropy

This is a new expression for expansion work.


But, our interest is not really expansion but a specific change:
aggregation between colloidal phases s and p. If supposing that
volumes are exactly counterbalanced such that

Source of
irreversibility

p l dv l p p dv p p s dv s = 0

First law:
Energy
Conservation

Conclusion

and that the aggregation phenomena results in the creation of a


new interface between phases s and p associated with a surface
tension ps and an area sp .
Further, if aggregation destroys as much pl and sl interfaces
separately as it creates sp interface such that
d pl = d sl = d sp

Substituting these changes on aggregation, we get the adhesion


or aggregation work also known as Dupre equation,
Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

dW = ( sp sl sp )d sp

(4)

Injection of Dupre equation (4) into first law gives


X
dE = dQ + ( sp sl sp )d sp +

elj de njl

(5)

The extra term gives the amount of matter exchanged during


the transformation of the open system. de njl is the variation of
the number of mole of chemical species j in the liquid phase l.

elj , the Electrochemical potential is the sum of lj , the true


chemical potential, and of zj F l , the electrostatic effect.
When dealing with colloidal surfaces, it is important to consider
zj F l because these surfaces may be more or less charged,
thereby affecting the quantity of ions situated near the surface.

Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

Indeed, to fulfil Gibbs equilibrium conditions, electrochemical


potentials of the species j must be equivalent everywhere in the
system, so we have the equality between species located in the
bulk and superficial phases,

elj =
eslj =
epl
j
The consequence of this equality is that the quantities of chemical species will be discontinuous near the interfaces to satisfy
equilibrium conditions. These spacial heterogeneities near the
surfaces lead to the concept of adsorption given by Gibbs.

Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

Adsorptions of j at pl and sl interfaces are respectively defined


so that
njpl
njsl
pl
j = pl and, slj = sl
(6)

2. Aggregation Produces Entropy: Application of


the Second Law
Clausius Inequality:
Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

dQ
dQ
dQ 0
and dS =
+
= de S + di S
(7)
T
T
T
Injecting dQ = Tde S and de S = dS di S in (5), we get the first
relation for the total variation of entropy during aggregation:
1
1 X l
1

ej de njl +di S (8)


dS = dE ( sp sl sp )d sp
T
T
T
dS >

If for each separate phase (three bulk phases p, s, and l and three
superficial phases sl, pl, and ps), the transformation remains
reversible, that is dS = de S(di S = 0), it is possible to obtain
the entropy variation of the whole system dS by adding all dS
obtained for each part (each and phases composing the system):
1
1
1 X X , ,
dS = dE ( sp sl sp )d sp

ej dnj
(9)
T
T
T
,

By equalizing right parts of equations (7) and (8),


Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

di S =

1 X l
1 X l l
1 XX

ej de njl

ej dnj

ej dnj (10)
T
T
T
j

Variation of the amount of matter contained in the liquid phase


is linked to the amount exchanged with the environment of the
system but also to amount coming from sp and pl superficial
phases:
dnjl = de njl dnjp l dnjp l
Substituting, we get
di S =

1X l
1X l
pl
(e
j
epl
(e
j
eslj )dnjsl
j )dnj +
t
t
j

(11)

Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy

Quantities dnjp l and dnjs l are amounts exchanged between liquid


phase and interfaces pl and sl. In other words, they are quantities
which are adsorbed or desorbed at/from pl and sl interfaces.
Adsorption of chemical species j at interface defined from
equation (6) gives us the final relation allowing to describe the
out-of-equilibrium aggregation process:

Source of
irreversibility
Conclusion

di S =

1X l
1X l
pl
sp
epl
eslj )slj d sp (12)
(e
j
(e
j
j )j d +
t
t
j

When injected into (8), it provides the full expression for entropy
derivative during a time interval dt of an aggregation process.

3. Source of irreversibility

Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

Aggregation of s and p colloids means that they stick together but do not merge, the latter being coalescence. The
consequence of aggregation is the increase of contact area
between the two colloids; that is, d sp > 0.
If d sp > 0 aggregation is processing and if d sp = 0,
the system has reached a stable state, but not necessarily
equilibrium. Conversely, a system for which d sp < 0 is
said to be peptizing.
During these processes, adsorptions j remain constant because they are intensive variables. For species in excess at
the interface j > 0, aggregation requires that
ej >
elj to
fulfil the second law; that is, di S > 0. For j < 0, we have

the opposite,
ej <
elj . If these conditions are met, then
the aggregation of colloids may provoke desorption and in
consequence, entropy production.

Conclusion

Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion

With the aim to reach a better understanding of hydrophobic effect, equations describing the aggregation of two hydrophobic colloids have been shown. This description is
based on purely thermodynamic considerations and specifically on classical irreversible thermodynamics.
Entropy production (di S) is linked to the contact area variation (d sp ) between colloids s and p. Due to this entropy
production, we conclude that aggregation is then irreversible
and spontaneous.
THANK YOU!

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