TERMODINAMIKA

MATERIAL
Helena Septian (1206239182)
David Jendra (1206238803)
TEKNIK
METALURGI &
MATERIAL FTUI
SAP 9

Campuran Termodinamik:
Larutan Ideal dan Non Ideal
Excess Function
Larutan Reguler
Lautan Ideal
Pada pencampuran, asumsi larutan campuran
yang ideal mencakup
Antara terlarut dan pelarut tidak terpisahkan
Pembentukan komposisi
mengikuti hukum Raoult
Efek temperatur dan volume
ketika pencampuran dapat
diabaikan
Lautan Ideal

Karakter General dari Larutan campuran (Ideal)
0
mix
= A V (1)
0
mix
= A H
(2)
0
mix
> A S
(3)
0
mix
< A G (4)
B B
*
B B
x k x p p
x
= =
x
k p =
*
B
Lautan Ideal
Chemical Potential pada Larutan campuran

B
*
B B
ln ) , ( x RT p T + =
B B B B
( ) ln d
p
p
T RT x V p = + +
}
$
$
atau
(1)
(2)
B B B
( ) ln T RT x = +
$
Hal ini merupalan ekpresi untuk
chemical potential dari pencampuran
larutran (Mixing Solution)
Lautan Non Ideal
Pada Larutan non ideal , hukum Raoult
harus terlebih dahulu dimofidikasi


Konsep Aktivitas pada larutan non ideal
B B
*
B B
x p p =
,B ,B B x x
a x =
B
B
,B
,B
1
1
B
lim( ) 1
lim
x
x
x
x
a
x

= =
Merupakan aktivitas relatif dengan
dimensi 1
Merupakan faktor aktivitas, berfungsi
untuk menentukan kedekatan lautan terhadap
laurtan ideal, dengan dimensi 1
Menetukan chemical potential
larutan non iedal
(1) gunakan fraksi mol x
B
untuk
menyatakan konsentrasi
B B B ,B B
ln( / ) ( ) ln ( / ) ln
x x
RT p p T RT k p RT a = + = + +
$ $ $ $
*
B ,B
= ( , ) ln
x
T p RT a +
Dimana 1 , 1 , 1
B , B , B
= = =
x x
a x
Dengan kondisi T,
P
(2) gunakan fraksi mol untuk menyatakan
konsentrasi

B ,B B
**
B ,B
( ) ln ln
( , ) ln
m
m
m
T
k m
T RT
p R
R a
T a
T
p

= +
= +
+
$
$
$
B
m,B m,B
m
m
a =
$
adalah chemical potential
dari hipotesus yang masih
mengikuti hukum Raoult ketika
**
B
( , ) T p
B m,B m,B
, 1, 1 m m a = = =
$

Dalam kondisi TP
1
1mol kg m

=
$
(3) Gunakan konsentrasi mol untuk
menyatakan konsentrasi
B ,B B
***
B ,B
( ) ln ln
= ( , ) ln
c
c
c
k c
T R
T p RT
T T
p
a
R a

+
= + +
$
$
$
B
,B ,B c c
c
a
c
=
$
Excess Function
Pada penggambungan laruran dengan
mol n
1
dan n
2 ,
Jika larutran adalah
larutan ideal maka :
mix mix
mix mix
0, 0
0, 0
V H
G S
A = A =
A < A >
Excess Function
Namun jika larutan bukanlah larutan ideal,
maka smua nilai tidak bernilai 0 , tapi
hukum termodinamika tetap berlaku
(1) Energi Gibbs berlebvih

Energi gibbs berelebih menyatakan
perbedaan
mix
G
r
pada pencampuran
sebenarnya dan
mix
G
id
pencampuran
ideal
E
mix re mix id
def
G G G A A
Excess Function
(2)Entalpi berlebih

E
H
re mix id mix re mix
E
H H H H A = A A =
) 0 ( = A
id mix
H karena

14
Excess Functions
A
i
= kTln a
i
= kTln
i
X
i
( )= kTln
i
+ kTln X
i
Remember that:
For an ideal solution:

i
= 1
A
i
ideal
= kT ln X
i
A
i
x
= A
i
A
i
ideal
= kT ln
i
AGi
x
= NA
i
x
= RTln
i
AG'
M
x
= AG'
M
AG'
M
ideal
AG
M
x
= RT X
A
ln
A
+ X
B
ln
B
( )
AM
i
x
= AM
i
AM
i
ideal
AM
x
= AM AM
ideal
We define the excess function as the
difference between the actual value
of the mixture and the value for an
ideal mixture:
AH
M
ideal
= 0 AH
M
x
= AH
M
AV
M
ideal
= 0 AV
M
x
= AV
M

15
Excess Functions
AG
M
= AH
M
TAS
M
AG
M
ideal
+ AG
M
x
= AH
M
ideal
+ AH
M
x
T AS
M
ideal
+ AS
M
x
( )
AG
M
ideal
+ AG
M
x
= AH
M
x
T AS
M
ideal
+ AS
M
x
( )
AG
M
ideal
= TAS
M
ideal
AG
M
x
= AH
M
x
TAS
M
x
The entropy of mixing is usually assumed
to be ideal so that the excess Gibbs free energy
of mixing is the excess enthalpy of mixing
AG
M
x
= AH
M
x
AG
M
ideal
+ AG
M
x
= AH
M
x
TAS
M
ideal
The Gibbs free energy of mixing is then
The excess enthalpy of mixing minus T
times the ideal entropy of mixing.
Lets take a closer look at the
Gibbs free energy of mixing using
the concept of excess mixing functions:
Larutan Regular
Pada larutan regular S
E
=0
Sehingga
0 =
|
|
.
|

\
|
c
c
p
B
E
n
S
p
E
E
T
G
S karena
|
|
.
|

\
|
c
c
=
2 E
B
( ) 0
p
G
n T
c
=
c c
B
E
B
p
B
E
RTInr
n
G
= =
|
|
.
|

\
|
c
c

E
B

( adalah excess chemical potential )

Larutan Regular








Pada larutan regular,, T dan logaritma dari tiap koefisien
aktivitas komponen dinyatakan dalam rasio invers
T
t con RT
T
RT
B
B
p
B
1
ln
tan ln
0 ]
ln (
[

=
=
c
c

18
Regular Solutions
The Regular Solution Model is a simple example of a non-ideal solution.
Recall that for a mixture:
AG
M
= X
i
AGi
i
AG
M
= RT X
i
ln a
i
i

AGi = RTlna
i
The partial molar Gibbs free energy
of mixing (the difference between
component is contribution to G in
the mixture versus pure i) is related
to the activity.
The Gibbs free energy of mixing
is the weighted sum of the
contributions from each
component.
The Gibbs free energy of mixing
is then related to the activities as
shown.
In the ideal case the activities were just the mole fractions:
AG
M
= RT X
i
ln X
i
i

The excess Gibbs free energy of mixing is the difference between the non-ideal and ideal G of mixing:
AG
M
x
= RT X
i
ln a
i
i
RT X
i
ln X
i
i
= RT X
i
ln
i
i

Lecture 18

Multicomponent Phase
Equilibrium

19
Regular Solutions
And substituting the Regular Solution excess G of mixing:
Notice that the first two terms are the negative ideal entropy of mixing multiplied by T:
AG
M
= AG
M
ideal
+ AG
M
x
= RT X
i
ln X
i
i
+ RT X
i
ln
i
i

The Gibbs free energy of mixing is the sum of the excess and ideal Gibbs free energies of mixing :
AG
M
= RTX
A
ln X
A
+ RTX
B
ln X
B
+eX
A
X
B
AS
M
ideal
= RX
A
ln X
A
RX
B
ln X
B
Thus, the last term is the enthalpy of mixing (and also the excess enthalpy of mixing since the ideal
enthalpy of mixing is just zero):
AH
M
= AH
M
x
=eX
A
X
B
The enthlapy of mixing
of the Regular Binary Solution
with e = 10 J/mol.
SEKIAN DAN
TERIMAKASIH

Referensi
Gaskell,