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Enthalpy H(T,p) H ! U + pV
reversible
gas (p, T1, V1) "
const . p
gas (p, T2, V2)
U1 U2
) +H * ) +H *
Choose H #T , p $ ( dH " , - dT & , - dp
. +T / p . +p /T
+H ) +H *
What are ), *
- and , - ?
. +T / p . +p /T
) +H *
• , - ( for a reversible process at constant p (dp = 0)
. +T / p
) +H *
dH " !q p and dH " , - dT
. +T / p
+H *
( !q p " ,) - dT but !qp " C p dT also
. +T / p
) +H *
0 , - " Cp
. +T / p
5.60 Spring 2007 Lecture #4 page 2
) +H *
• , - ( Joule-Thomson expansion
. +p /T
adiabatic, q = 0
porous partition (throttle)
w " pV
1 1 ' pV
2 2 ( %U " q & w " pV 2 2 " '% # pV
1 1 ' pV $
0 %U & % # pV $ " 0 ( % #U & pV $ " 0
0 %H " 0
) +H * ) +H *
dH " C p dT & , - dp ( C p dT " ' , - dpH
. +p /T . +p /T
) +H * ) +T * ) %T *
( , - " 'C p , - 1 can measure this , -
. +p /T . +p /H . %p / H
) %T * ) +T *
Define lim , - ", - ! 2JT 1 Joule-Thomson Coefficient
%p 3 0
. %p /H . +p /H
) +H *
0 ,, -- " 'C p 2JT and dH " C p dT ' C p 2JT dp
. +p /T
5.60 Spring 2007 Lecture #4 page 3
) +H * a a a
,, -- 4 b ' ( 2JT 4 'b " 0 when T "T inv"
. +p /T RT RT Rb
a a
1. If 5b ( T 6 "T
RT Rb inv
) %T * so if %p 5 0 ( p2 5 p1 )
then ,, -- 5 0
. %p /H then %T 6 0
gas heats up upon expansion.
a a
2. If 6b ( T 5 "T
RT Rb inv
) %T * so if %p 5 0
then ,, -- 6 0
. %p /H then %T 5 0
gas cools upon expansion.
) +H * ) +U *
Cp " , - , CV " , -
. +T / p . +T /V
H " U & pV , pV " RT
!""#""
$
7
%""""" "&"""""
8
"
'
) +H * ) +U * ) +V *
, - ", - &p, -
. +T / p . +T / p . +T / p
%""""&""""8
'
) +U * ) +V * )R *
C p " CV & , - , - & p ,, --
. +V /T . +T / p . p /
" 0 for ideal gas
0 C p " CV & R