JJ
estr
estr
estr
Lecture Note
Lecture Note
JOURNAL OF
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A. Ch. Mitropoulos*
A. Ch.
Mitropoulos*
Department of Petroleum Technology, Cavala
Institute
of Technology, St. Lucas 65 404 Cavala.
Department of Petroleum Technology, Kavala Institute of Technology, St. Lucas 65 404 Kavala.
19Technology,
October 2007;
Accepted
14 January
2008 St. Lucas 65 404 Kavala.
Department ofReceived
Petroleum
Kavala
Institute
of Technology,
Received 19 October 2007; Accepted 14 January 2008
_______________________________________________________________________________________________
_______________________________________________________________________________________________
Received 19 October 2007; Accepted 14 January 2008
_______________________________________________________________________________________________
Abstract
Abstract
Abstract
J. Willard
Gibbs in his pioneering work on the influence of surfaces discontinuity upon the equilibrium of heterogeneJ.ous
Willard
Gibbs
in his pioneering
work on the
of surfaces
discontinuity
upon the
equilibrium
heterogenemasses
suggested
for the measurement
of influence
the quantities
of a system
a geometrical
surface
dividingofthe
interfacial
ous
masses
suggested
for
the
measurement
of
the
quantities
of
a
system
a
geometrical
surface
dividing
the
interfacial
J.
Willard
Gibbs
in
his
pioneering
work
on
the
influence
of
surfaces
discontinuity
upon
the
equilibrium
of
heterogenelayer. Surface excess is the difference between the amount of a component actually present in the system,
and
that
layer.
Surface
excess
is
the
difference
between
the
amount
of
a
component
actually
present
in
the
system,
and
that
ous
masses
suggested
for
the
measurement
of
the
quantities
of
a
system
a
geometrical
surface
dividing
the
interfacial
which would be present in a reference system if the bulk concentration in the adjoining phases were maintained up
to
which
wouldSurface
be
present
in
a is
reference
system between
if position
the bulk
concentration
the adjoining
phases
were maintained
up to
layer.
excess
the determined
difference
thedividing
amountsurface.
of a incomponent
actually
present
in the system,
and that
the arbitrary
chosen
but
precisely
in
the arbitrary
butpresent
precisely
position
dividing
surface.
which chosen
would be
in determined
a reference in
system
if the
bulk concentration
in the adjoining phases were maintained up to
the
arbitrary
chosen
but
precisely
determined
in
position
dividing
surface.
Keywords: surface excess, Gibbs adsorption.
Keywords:
surface excess, Gibbs adsorption.
_______________________________________________________________________________________________
_______________________________________________________________________________________________
Keywords: surface excess, Gibbs adsorption.
_______________________________________________________________________________________________
volumes V +V =V each one assumed to contain CiV =ni and
Adsorption of a component at the phase boundary of a system
+V =V each one assumed
to contain
Ci V =ni inand
volumes
Adsorption
of
a
component
at
the
phase
boundary
of
a
system
moles with Ci and Ci the bulk
concentrations
the
CiV =niV
results to a different concentration in the interfacial layer than
V
=n
moles
with
C
and
C
the
bulk
concentrations
C
results
to
a
different
concentration
in
the
interfacial
layer
than
+V
=V
each
one
assumed
to
contain
Cin
=ni and
volumes
V
Adsorption
of
a
component
at
the
phase
boundary
of
a
system
i
i
i
i
i Vthe
real system
[5],
respectively.
More
formally:
that in the adjoining bulk phases. The adsorbate density and
real
system
[5],
respectively.
More
formally:
that
in
the
adjoining
bulk
phases.
The
adsorbate
density
and
V
=n
moles
with
C
and
C
the
bulk
concentrations
in the
C
results
to
a
different
concentration
in
the
interfacial
layer
than
i
i
i
i
composition profiles within that layer cannot be measured by
composition
within
thatamounts
layer
cannot
measured
by and
real system [5], respectively. More formally:
that
inprofiles
the adjoining
bulk
phases.
The be
adsorbate
density
todays
technology;
the
actual
adsorbed
are not meantodays
technology;profiles
the
actual
amounts
adsorbed
are not
meanwithin
layerthis
cannot
be measured
ingfulcomposition
experimental
variables.
To that
resolve
problem
Gibbs by
ingful
experimental
variables.
To
resolve
this
problem
Gibbs
todays
technology;
the
actual
amounts
adsorbed
are
not mean[1] suggested that: it will be convenient to be able to refer
[1]
that: surface,
it will
be convenient
to bethis
ablecoincident
to refer Gibbs
ingful experimental
variables.
To be
resolve
problem
to suggested
a geometrical
which
shall
sensibly
towith
a geometrical
which
shall
be sensibly
[1]
that: it
be convenient
tocoincident
be have
able toa refer
the suggested
physicalsurface,
surface
of will
discontinuity,
but shall
with
the
physical
surface
of
discontinuity,
but
shall
have
a
to
a
geometrical
surface,
which
shall
be
sensibly
coincident
precisely determined position. For this end, let us take some
precisely
determined
Forofthis
end, letofus
takeshall
somehave a
the
discontinuity,
but
point with
in or
veryphysical
nearposition.
to surface
the physical
surface
discontinuity,
point
in
or very
near to the position.
physical
surface
ofend,
discontinuity,
precisely
thisthrough
letthis
us point
take some
and imagine
a determined
geometrical
surface toFor
pass
and
imagine
a
geometrical
surface
to
pass
through
this
point
point
in
or
very
near
to
the
physical
surface
of
discontinuity,
and all other points which are similar situated with respect to
and
other
points
are matter.
similar
situated
withthrough
respectthis
to point
and
imagine
geometrical
surface
to pass
the all
condition
of theawhich
adjacent
Let
this
geometrical
surthe
condition
of
the
adjacent
matter.
Let
this
geometrical
surand
all
other
points
which
are
similar
situated
with
respect
to
face be called the dividing surface.
face be
called
the
dividing
surface.
the
condition
of
the
adjacent
matter.
Let
this
geometrical
surSurface excess [2] is the difference between the amount of
Surface
[2]
the difference
betweenand
the amount
of
face beexcess
called
theispresent
dividing
a component
actually
insurface.
the system,
that which
awould
component
actually
present
in
the
system,
and
that
which
Surface
excess
[2]
is
the
difference
between
the
amount
be present in a reference system if the bulk concentra- of
would
be
present
in actually
a reference
system
bulk
concentraa
component
in ifthethesystem,
and
that which
tion in the
adjoining
phases present
were
maintained
up to
a chosen
tion
inwould
the adjoining
phases
were
upthe
to
a interface
chosen
be
present
in a reference
if
concentrageometrical
dividing
surface
[3]; maintained
i.e. system
as though
thebulk
geometrical
surfacephases
[3]; i.e.
as maintained
though the up
interface
individing
the
adjoining
were
to a chosen
had notion
effect.
Schematically:
had nogeometrical
effect. Schematically:
dividing surface [3]; i.e. as though the interface
had
no
effect.
]surface==[n[ni]]realSchematically:
(1)
[n i ]reference .
Figure 1. Concentration profiles of a binary system as a function of dis[n[ni i]surface
[ni ]reference .
(1)
Figure
1. Concentration
of aBold
binary
system
as ainfunction
of disi real
tance normal
to the phaseprofiles
boundary.
curved
lines,
both frames,
are
normal
theConcentration
phase boundary.
Boldand
curved
lines,
ininboth
are of dis[ni ]surface =[ni ]real [ni ]reference .
(1)tance
the concentration
profiles
of theprofiles
solute
solvent
the
real
system,
Figureto 1.
of
athe
binary
system
asframes,
a function
where [ni]surface=ni is the surface excess amount [4] of compo- the
concentration
profiles
of
the
solute
and
the
solvent
in
the
real
system,
respectively,
and again
vertical
lines
are curved
the concentrations
the are
tance normal
to the
phase broken
boundary.
Bold
lines, in bothinframes,
=ni is the surface excess amount [4] of compowhere
[ni][n
surface
respectively,
and again
broken
lines
thethe
concentrations
the
nent (i);
i]real=ni is the total amount of that component in the
reference
(beingvertical
actually
thethe
extend
ofand
the
bulk
concentrations
upsystem,
the system
concentration
profiles
of
soluteare
solvent
in theinreal
a
=n
amount
that component
thecomponent
[ni]real[nand
=ni total
is =n
the
surfaceofexcess
amount [4]inof
where
i is
reference
systemsurface).
(being
the extend
of
the
i]surface
to the dividing
Chainvertical
dotted
lines
indicate
theconcentrations
boundaries
of up
the in the
real (i);
system;
[nthe
respectively,
and actually
again
broken
linesbulk
are
the
concentrations
i]reference
ai +ni is the amount of the same
tointerfacial
the dividing
surface).
Chain
indicate
thethe
boundaries
the
]=n
+n
the amount
theequal
sametoin the
real
system;
and
]arealireference
theisystem
total
amount
of
thatofcomponent
nent (i);
[n
reference
i is
layer.
Bold horizontal
linelines
isthethe
dividing
surface
and ofdotted
i is =n
reference
system
(beingdotted
actually
extend
of
bulk concentrations
up
component
(i)
ini[n
having
volume
V
a
interfacial
layer.
Bold
horizontal
line
is
the
dividing
surface
and
dotted of the
component
(i)
in
a
reference
system
having
volume
V
equal
to
horizontal
line
is
another
choice
for
the
location
of
the
dividing
surface.
to
the
dividing
surface).
Chain
dotted
lines
indicate
the
boundaries
]
=n
+n
is
the
amount
of
the
same
real
system;
and
[n
i reference byi a hypothetical
i
the real system which is divided
surface into horizontal line is another choice for the location of the dividing surface.
surface
excess
is the
sumhorizontal
of the shaded
above and
underand
the dotted
interfacial
layer.
Bold
line isareas
the dividing
surface
the realcomponent
system which
bysystem
a hypothetical
surface V
into
(i) inisadivided
reference
having volume
equal The
toThesurface
excessline
is the
sum inofchoice
the case
shaded
areas
aboveof
and
under
the
dividing
surface.
Notice
that
the
ofthe
the
solvent
by
choosing
thesurface.
horizontal
is
another
for
location
the
dividing
the real system which is divided by a hypothetical surface into
______________
dividing surface. Notice that in the case of the solvent by choosing the
upper dividing
surface
(a suitable
one)of
thethe
resulted
is zero,
The surface
excess
is the sum
shadedsurface
areas excess
above and
under the
upper
dividing
surface
(a Notice
suitable
one)
excessbyis choosing
zero,
whereas
by choosing
the
lower one
surface
excess
not zero.
dividing
surface.
that
inthe
theresulted
case ofissurface
the
solvent
the
whereasupper
by choosing
lower (a
onesuitable
surfaceone)
excess
not zero.
dividingthesurface
theisresulted
surface excess is zero,
______________
* E-mail address: amitrop@teikav.edu.gr
* E-mail
address:
ISSN:
1791-2377
amitrop@teikav.edu.gr
2008 Kavala Institute of Technology. All rights reserved.
______________
ISSN: 1791-2377
2008
Kavalaamitrop@teikav.edu.gr
Institute of Technology. All rights reserved.
* E-mail
address:
ISSN: 1791-2377 2008 Kavala Institute of Technology. All rights reserved.
1
1
11
A. Ch. Mitropoulos/ Journal of Engineering Science and Technology Review 1 (2008) 1-3
A. Ch. Mitropoulos/ Journal of Engineering Science and Technology Review 1 (2008) 1-3
A. Ch. Mitropoulos/ Journal of Engineering Science and Technology Review 1 (2008) 1-3
ni = ni C iaaV aa C i V .
ni = ni C i V C i V .
(2)
(2)
ni
i = ni .
i = As .
As
d = 1 d 2 d 2 .
d = 1 d 2 d 2 .
(3)
(3)
(6)
(6)
d = 211 d 2 .
d = 2 d 2 .
(7)
(7)
2
2
this was
note given.
an elementary
review out,
on the
concept
of even
surcate the dividing surface, 21 may still be calculated by rearface In
excess
It must pointed
however,
that
may
still
be
calculated
by
rearcate
the
dividing
surface,
2
face
excess
was
given.
It
must
pointed
out,
however,
that
even
ranging eq.(4) such as:
in the frame of formal surface thermodynamics the characterisranging eq.(4) such as:
in
frame ofinvolved
formal surface
thermodynamics
the characteristic the
quantities
need further
specification
in order to
a
tic
quantities
involved
need
further
specification
in order for
to
a
a
became
operational
and
again
need
different
specification
n 2 C 2a V n1 C1aV C 2a C 2
1
became
operational
and
again
need
different
specification
for
(5)
21 = n 2 C 2 V n1 C1 V C 2a C 2 .
each different type of interface (e.g. sold/gas [14], etc).
(5)
2 =
C1a C1 .
As
As
each different type of interface (e.g. sold/gas [14], etc).
As
As
C1 C1
Acknowledgments: The author would like to thank Archimedes
Acknowledgments:
The
author would
to thank
Archimedes
The quantities on the right hand side of eq.(5) are all directly
research Project and
INTERREG
III like
Hybrid
Technology
for
The
quantities
on
the
right
hand
side
of
eq.(5)
are
all
directly
research
Project
and
INTERREG
III
Hybrid
Technology
for
measurable, provided that As is known.
Separation for funding this work
measurable, provided that As is known.
Separation for funding this work
______________________________
______________________________
References and Notes
References and Notes
C 2a
C a
2 1 C12aa
C1
2
C 2
C 2
C1
C1
C a
= 2 1 C 22a
= 2 1 C1aa
C1
C 2
C 2
C1
C1
.
.
5.
5.
6.
6.
A. Ch. Mitropoulos/ Journal of Engineering Science and Technology Review 1 (2008) 1-3
A. Ch. Mitropoulos/ Journal of Engineering Science and Technology Review 1 (2008) 1-3
8.
9.
10.
11.