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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #4

Enthalpy

H(T,p)

page 1

H U + pV

Chemical reactions and biological processes usually take place under

constant pressure and with reversible pV work. Enthalpy turns out
to be an especially useful function of state under those conditions.
reversible

gas (p, T1, V1)

gas (p, T2, V2)

const . p

U1

U2

U = q + w = qp p V
U + p V = qp

U + ( pV ) = qp

H U + pV
Choose

H (T , p )

define as H
(U + pV ) = qp

H = q p

for a reversible constant p process

H
H
dp
dT +
T p
p T

dH =

H
H
What are
?
and
T p
p T

T p

for a reversible process at constant p (dp = 0)

dH = q p

H
and dH =
dT
T p
H
dT
T p

q p =

but

= Cp
T p

q p = C p dT

also

5.60 Spring 2008

Lecture #4

p T

page 2

Joule-Thomson expansion

adiabatic, q = 0
porous partition (throttle)

gas (p, T1)

w = pV
1 1 p2V2

gas (p, T2)

U = q + w = pV
1 1 p2V2 = ( pV
U + ( pV ) = 0

)
(U + pV ) = 0

H = 0

Joule-Thomson is a constant Enthalpy process.

H
dp
p T

dH = C p dT +

H
T

= C p

p T
p H

Define

H
dpH

p T

C p dT =

can measure this

p H

T
T
=
lim

JT Joule-Thomson Coefficient
p
0
p H p H

= C p JT
T

and

dH = C p dT C p JT dp

5.60 Spring 2008

Lecture #4

U(T),

For an ideal gas:

page 3

pV=nRT

H U (T ) + pV = U (T ) + nRT
H (T )

only
H

depends on T, no p dependence

= JT = 0 for an ideal gas

T

For a van der Waals gas:

a
b
RT
T
1.

If

a
<b
RT

JT

T
< 0

a
b = 0
RT
T >

so

then

when T =T inv=

a
Rb

a
=T
Rb inv

if

p < 0

then T > 0

( p2 < p1 )

gas heats up upon expansion.

2.

If

a
>b
RT

T
> 0
p H

then

T <
so

a
=T
Rb inv

if

p < 0

then T < 0

gas cools upon expansion.

Tinv >> 300K

for most real gases.

Use J-T expansion to liquefy gases

5.60 Spring 2008

Lecture #4

Proof that C p = CV + R

page 4

for an ideal gas

H
,
T p

T V

Cp =

CV =
H = U + pV ,
 

pV = RT





H
V
U

+p
T p T p
T p



R
U V
C p = CV +
+ p

V T T p
p
=0 for ideal gas

C p = CV + R