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601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field
Lecture #9
page 1
G
,
T p
p T
S =
V =
T p
H = G +TS
H = G T
U = H pV
U = G T
A = U TS
A =G p
S
C p =T
T p
G
G
p
T p
p T
p T
2G
C p = T
2
T p
p-dependence of G(T,p)
From
p T
V =
p2
G (T , p2 ) = G (T , p1 ) + Vdp
p1
Lecture #9
V is small
G (T , p2 ) = G (T , p1 ) +V ( p2 p1 ) G (T , p1 )
page 2
G (T
Ideal gases
G (T , p2 ) = G (T , p1 ) +
p2
p1
p
RT
dp = G (T , p1 ) + RT ln 2
p
p1
Take p1 = p o = 1 bar
G (T , p ) = G o (T ) + RT ln
From
p
p0
T p
S =
or G (T , p ) = G o (T ) + RT ln p
(p in bar)
S (T , p ) = S o (T ) R ln p
dA = SdT pdV
dH =TdS +Vdp
dG = SdT +Vdp
G (T , p ,n1 ,n2 )
Lecture #9
page 3
G
G
G
G
dG =
dT +
dp +
dn1 +
dn2
p T ,n ,n
n1 T , p ,n
n2 T , p ,n
T p ,n ,n
We define
2
1
2
ni T , p ,nj i
1
2
i (T , p , nj ) is an intensive variable
G
H
U
A
=
=
=
i =
Lecture #9
page 4
1(b ) < 1( a )
dG < 0
1( a ) < 1(b )
dG > 0
ice (T , p ) = water (T , p )
at coexistence equilibrium
For the cell in a salt water solution, water (cell ) (T , p ) > water (solution ) (T , p ) and
the cell dies as the water flows from the cell to the solution (this is
what we call osmotic pressure)
Lecture #9
page 5
ni T , p ,nj i
G = n1 1 + n2 2 + " + ni i = ni i = ni Gi
i
n1
n2
n1 1 + n2 2 = G
n
i T , p ,nj i
ni T , p ,n j i
= i
j i
Lecture #9
page 6
ni T , p ,n j i
G (T , p ) = G o (T ) + RT ln
p
p0
(T , p ) = o (T ) + RT ln
mixed pure
A
A,B
p'A, p'B pA
Fixed Partition
At equilibrium
Also
Daltons Law
So
p
p0
Lecture #9
page 7
ptot
+ RT ln XA
p0
A ( pure ,T , ptot )
Note