This action might not be possible to undo. Are you sure you want to continue?

BooksAudiobooksComicsSheet Music### Categories

### Categories

### Categories

Editors' Picks Books

Hand-picked favorites from

our editors

our editors

Editors' Picks Audiobooks

Hand-picked favorites from

our editors

our editors

Editors' Picks Comics

Hand-picked favorites from

our editors

our editors

Editors' Picks Sheet Music

Hand-picked favorites from

our editors

our editors

Top Books

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Audiobooks

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Comics

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Sheet Music

What's trending, bestsellers,

award-winners & more

award-winners & more

Welcome to Scribd! Start your free trial and access books, documents and more.Find out more

edu

5.60 Thermodynamics & Kinetics

Spring 2008

For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.

p = gas (p. 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 .5. V1) reversible const .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. gas (p. Enthalpy turns out to be an especially useful function of state under those conditions. T2. T1. 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 = đq p ⇒ đq p = ⎛ ⎜ đq p = C p dT also ∴ ⎛ ∂H ⎞ ⎜ ⎟ = Cp ⎝ ∂T ⎠ p .

q = 0 porous partition (throttle) gas (p.60 Spring 2008 Lecture #4 page 2 • ⎛ ∂H ⎞ ⎜ ⎟ ⎝ ∂p ⎠T ⇒ Joule-Thomson expansion adiabatic. T1) = gas (p. 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 ⎜ ⎟ ⎟ ≡ µJT ← Joule-Thomson Coefficient ∆p → 0 ⎝ ∆p ⎠H ⎝ ∂p ⎠H ⎞ = −C p µJT ⎟ ⎟ ⎠T ∴ ⎛ ∂H ⎜ ⎜ ∂p ⎝ and dH = C p dT − C p µJT dp .5. 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.

no p dependence ⎞ ⎟ = µJT = 0 for an ideal gas ⎠T For a van der Waals gas: ⎛ ∂H ⎜ ⎜ ∂p ⎝ ⎞ a ⎟ b ≈ − ⎟ RT ⎠T 1. ⇒ Use J-T expansion to liquefy gases .5. Tinv >> 300K for most real gases. 2. pV=nRT H ≡ U (T ) + pV = U (T ) + nRT H (T ) ⇒ only ⎛ ∂H ⎜ ⎝ ∂p depends on T. 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.60 Spring 2008 Lecture #4 page 3 For an ideal gas: U(T). If ⇒ µJT ≈ 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.

⎝ ∂T ⎠ p for an ideal gas CV = ⎜ H = U + pV .5. ↓ ⎛ ∂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 .60 Spring 2008 Lecture #4 page 4 Proof that C p = CV + R Cp = ⎜ ⎛ ∂H ⎞ ⎟ .

therm

therm

Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

We've moved you to where you read on your other device.

Get the full title to continue

Get the full title to continue listening from where you left off, or restart the preview.

scribd