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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=⎢
p→0 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 Dalton’s 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⎠
( )