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Chemical Thermodynamics Notes
Chemical Thermodynamics Notes
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5.60 Spring 2008 Lecture #1 page 1
Thermodynamics
Thermodynamics:
Entirely Empirical
Definitions:
Surroundings
V = f (n, p, T) or p = g(n, V, T)
Notation:
Notation:
5
p (bar)
50 100
T (K)
A B A B A B
lim pV
p 0
( )t
= constant = f (t )
p 0
f(t)=f(0 C)(1+At)
Experimental result:
A = 0.0036609 = 1/273.15
-273.15 0 100 C
Note: (t = 273.15 C ) is special
=======
T (K ) = t ( C ) + 273.15
=======
Better reference points used for the Kelvin scale today are
f (Ttp )
f (T ) = T
p 0 273.16
or
(
lim pV )
lim pV
p 0
( )
T
= p 0 tp
273.16
T
f(Ttp)
0 T(K)
0 273.16= Ttp
5.60 Spring 2008 Lecture #1 page 8
Ideal Gases
(
lim pV )
lim pV
p 0
( )
T
= p 0 tp
273.16
T RT valid for all gases for p 0
define
the gas constant
lim ( pV )
R=
p0 tp
= 8.31451 J (gas constant)
273.16 K mol
pV = RT or pV = nRT
V = f (n , p ,T )
Equations of state
ni RT
ni
pi = p = Xi p Daltons Law
n
pV = ZRT Z= real
Videal
generally neglect
pV B (T ) C ( T )
= Z (T ) = 1 + + +"
RT V V 2
pV = RT becomes p ( V b ) = RT
RT RT a
So p = becomes p = 2
V b V b V
p + a V b = RT
Rearranging
V 2
( )