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First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion
April 5, 2016
Outline
Introduction
1 Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
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
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
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
Source of
irreversibility
p l dv l p p dv p p s dv s = 0
First law:
Energy
Conservation
Conclusion
dW = ( sp sl sp )d sp
(4)
elj de njl
(5)
Introduction
First law:
Energy
Conservation
2nd Law:
Aggregation
Produces
Entropy
Source of
irreversibility
Conclusion
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
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
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
,
di S =
1 X l
1 X l l
1 XX
ej de njl
ej dnj
ej dnj (10)
T
T
T
j
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
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.
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