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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #4

page 1

Enthalpy

H(T,p)

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. gas (p, T1, V1)
reversible const . p

gas (p, T2, V2)

U1
U = q + w = qp p V U + p V = qp U + ( pV ) = qp

U2

define as H (U + pV ) = qp for a reversible constant p process

H H dp dT + T p p T

H U + pV
Choose

H (T , p )

H = q p

dH =

H H What are ? and T p p T

H T p

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

H and dH = dT T p H dT T p but

dH = q p

q p =

q p = C p dT

also

H = Cp T p

5.60 Spring 2008

Lecture #4

page 2

H p T

Joule-Thomson expansion

adiabatic, q = 0 porous partition (throttle)

gas (p, T1)

gas (p, T2)

w = pV V2 1 1 p2

U = q + w = pV V2 = ( pV 1 1 p2 U + ( pV ) = 0 H = 0

) (U + pV ) = 0

Joule-Thomson is a constant Enthalpy process.

dH = C p dT +
H dp p T

C p dT =

H dpH
p T
T p H

H T = C p p T p H

can measure this

Define

T T = lim JT Joule-Thomson Coefficient p

0 p H p H
= C p JT T

H p

and

dH = C p dT C p JT dp

5.60 Spring 2008

Lecture #4

page 3

For an ideal gas:

U(T),

pV=nRT

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

only H p depends on T, no p dependence = JT = 0 for an ideal gas T

For a van der Waals gas:

H p

a b RT T 1. If

JT

a b = 0 RT
T > a =T Rb inv

when T = T inv=

a Rb

a <b RT

then

T <0 p H

so

if

p < 0

then T > 0

( p2 < p1 )

gas heats up upon expansion. 2. If

a >b RT

T <
so

a =T Rb inv
p < 0

then

T >0 p H

if

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

page 4

Proof that C p = CV + R
Cp =
H , T p

for an ideal gas

CV = H = U + pV ,
  

U T V

pV = RT

     H V U = +p T p T p T p     R U V C p = CV + + p p V T T p = 0 for ideal gas

C p = CV + R