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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.

reversible
gas (p, T1, V1) =
const . p
gas (p, T2, V2)

U1 U2

∆U = q + w = qp − p ∆V
∆U + p ∆V = qp define as H
∆U + ∆ ( pV ) = qp ⇒ ∆ (U + pV ) = qp

H ≡ U + pV ⇒ ∆H = q p for a reversible constant p process

⎛ ∂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 = đq p and dH = ⎜ ⎟ dT
⎝ ∂T ⎠ p
∂H ⎞
⇒ đq p = ⎛⎜ ⎟ dT but đq p = C p dT also
⎝ ∂T ⎠ p

⎛ ∂H ⎞
∴ ⎜ ⎟ = Cp
⎝ ∂T ⎠ p
5.60 Spring 2008 Lecture #4 page 2

⎛ ∂H ⎞
• ⎜ ⎟ ⇒ Joule-Thomson expansion
⎝ ∂p ⎠T

adiabatic, q = 0
porous partition (throttle)

gas (p, T1) = gas (p, T2)

w = pV
1 1 − p2V2 ⇒ 1 1 − p2V2 = −∆ ( pV
∆U = q + w = pV )
∴ ∆U + ∆ ( pV ) = 0 ⇒ ∆ (U + pV ) = 0
∴ ∆H = 0

Joule-Thomson is a constant Enthalpy process.

⎛ ∂H ⎞ ⎛ ∂H ⎞
dH = C p dT + ⎜ ⎟ dp ⇒ C p dT = − ⎜ ⎟ dpH

⎝ ∂p ⎠T ⎝ ∂p ⎠T

⎛ ∂H ⎞ ⎛ ∂T ⎞ ⎛ ∆T ⎞
⇒ ⎜ ⎟ = −C p ⎜ ⎟ ← can measure this ⎜ ⎟
⎝ ∂p ⎠T ⎝ ∂p ⎠H ⎝ ∆p ⎠ H

⎛ ∆T ⎞ ⎛ ∂T ⎞
Define lim ⎜ ⎟ =⎜ ⎟ ≡ µJT ← Joule-Thomson Coefficient
∆p
→0
⎝ ∆p ⎠H ⎝ ∂p ⎠H

⎛ ∂H ⎞
∴ ⎜⎜ ⎟⎟ = −C p µJT and dH = C p dT − C p µJT dp
⎝ ∂p ⎠T
5.60 Spring 2008 Lecture #4 page 3

For an ideal gas: U(T), pV=nRT

H ≡ U (T ) + pV = U (T ) + nRT
only depends on T, no p dependence
⎛ ∂H ⎞
H (T ) ⇒ ⎜ ⎟ = µJT = 0 for an ideal gas
⎝ ∂p ⎠T

For a van der Waals gas:

⎛ ∂H ⎞ a a a
⎜⎜ ⎟⎟ ≈ b − ⇒ µJT ≈ −b = 0 when T =T inv=
⎝ ∂p ⎠T RT RT Rb

a a
1. If <b ⇒ T > =T
RT Rb inv

⎛ ∆T ⎞ so if ∆p < 0 ( p2 < p1 )
then ⎜⎜ ⎟⎟ < 0
⎝ ∆p ⎠H then ∆T > 0
gas heats up upon expansion.

a a
2. If >b ⇒ T < =T
RT Rb inv

⎛ ∆T ⎞ so if ∆p < 0
then ⎜⎜ ⎟⎟ > 0
⎝ ∆p ⎠H 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 for an ideal gas

⎛ ∂H ⎞ ⎛ ∂U ⎞
Cp = ⎜ ⎟ , CV = ⎜ ⎟
⎝ ∂T ⎠ p ⎝ ∂T ⎠V
H = U + pV , pV = RT
 

 
↑


⎛ ∂H ⎞ ⎛ ∂U ⎞ ⎛ ∂V ⎞
⎜ ⎟ =⎜ ⎟ +p⎜ ⎟
⎝ ∂T ⎠ p ⎝ ∂T ⎠ p ⎝ ∂T ⎠ p
↑

⎛ ∂U ⎞ ⎛ ∂V ⎞ ⎛R ⎞
C p = CV + ⎜ ⎟ ⎜ ⎟ + p ⎜⎜ ⎟⎟
⎝ ∂V ⎠T ⎝ ∂T ⎠ p ⎝ p ⎠
=0 for ideal gas

∴ C p = CV + R