20.110J / 2.772J / 5.

601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005 Lecture #3 page 1

EXPANSIONS, ENERGY, ENTHALPY

Isothermal Gas Expansion ( ∆T = 0)

gas (p1, V1, T) = gas (p2, V2, T)

Irreversibly (many ways possible)

(1) Set pext = 0

p= 0

T p= 0 T
p 2,V2
p 1,V1
v2
w(1) = − ∫ pext dV = 0
V1

(2) Set pext = p2

p2

p2
T T
p 2,V2
p 1,V1
v2
w(2) = −∫ p2dV = −p2 (V2 −V1 )
V1

p
p1

p2

V1 V2
-w(2)
Note, work is negative: system expands against surroundings
20.110J / 2.772J / 5.601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005 Lecture #3 page 2

(3) Carry out change in two steps

gas (p1, V1, T) = gas (p3, V3, T) = gas (p2, V2, T) p1 > p3 > p2

p2
p3
T p3 T T
p 2,V2
p 3,V3
p 1,V1

v3 v2
w(3) = − ∫ p3dV − ∫ p2dV = − p3 (V3 −V1 ) −p2 (V2 −V3 )
V1 V3

p
p1
p3 More work delivered to
p2 surroundings in this case.

V1 V3 V2
-w(3)

(4) Reversible change p = pext throughout

p V
wrev = − ∫ 2 pdV
p1 V1

p2 Maximum work delivered to

surroundings for isothermal gas
V1 V2 expansion is obtained using a
- rev reversible path

For ideal gas:

V nRT V p
wrev = − ∫ 2 dV = −nRT ln 2 = nRT ln 2
V1 V V1 p1
20.110J / 2.772J / 5.601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005 Lecture #3 page 3

The Internal Energy U

dU = d-q + d-w (First Law)

dU = C pathdT − pext dV

⎛ ∂U ⎞ ⎛ ∂U ⎞
And U (T ,V ) ⇒ dU = ⎜ ⎟ dT + ⎜ ⎟ dV
⎝ ∂T ⎠V ⎝ ∂V ⎠T

Some frequent constraints:

• Reversible ⇒ dU = d-qrev + d-wrev = d-qrev – pdV

(p = pext )

• Isolated ⇒ d-q = d-w = 0

reversible
• Adiabatic ⇒ d-q = 0 ⇒ dU = d-w = -pdV

• Constant V ⇒ w = 0 ⇒ dU = d-qV
Constant V
∂U ⎞ ⎛ ∂U ⎞
dU = ⎛⎜ ⎟ dT + ⎜ ⎟ dV
⎝ ∂T ⎠V ⎝ ∂V ⎠T
⎛ ∂U ⎞
⇒ d- qV = ⎜ ⎟ dT
⎝ ∂T ⎠V
But also
⎛ ∂U ⎞
d-qV = CV dT ⇒ ⎜ ⎟ = CV very important result!!
⎝ ∂T ⎠V

⎛ ∂U ⎞
So dU = CV dT + ⎜ ⎟ dV
⎝ ∂V ⎠T
what is this?
20.110J / 2.772J / 5.601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005 Lecture #3 page 4

⎛ ∂U ⎞
Joule Free Expansion of a Gas (to get ⎜ ⎟ )
⎝ ∂V ⎠T

Adiabatic q=0
gas vac
Expansion into Vac. w=0
(pext=0)
gas (p1, T1, V1) = gas (p2, T2, V2)

Since q = w = 0 ⇒ dU or ∆U = 0 Constant U

⎛ ∂U ⎞
Recall dU = CV dT + ⎜ ⎟ dV = 0
⎝ ∂V ⎠T
⎛ ∂U ⎞
⎜ ⎟ dVU = −CV dTU
⎝ ∂V ⎠T
⎛ ∂U ⎞ ⎛ ∂T ⎞ ⎛ ∆T ⎞
⎜ ⎟ = −CV ⎜ ⎟ measure in Joule exp't! ⎜ ⎟
⎝ ∂V ⎠T ⎝ ∂V ⎠U ⎝ ∆V ⎠U

⎛ ∆T ⎞ ⎛ ∂T ⎞
Joule did this. lim ⎜ ⎟ =⎜ ⎟ ≡ ηJ ∴ dU = CV dT − CV ηJ dV
∆V → 0
⎝ ∆V ⎠U ⎝ ∂V ⎠U
Joule coefficient

• For Ideal gas ⇒ ηJ = 0 exactly

dU = CV dT Always for ideal gas
U(T) only depends on T

The internal energy of an ideal gas depends only on temperature

Consequences ⇒ ∆U = 0 For all isothermal expansions or

compressions of ideal gases

⇒ ∆U = ∫ CV dT For any ideal gas change in state

20.110J / 2.772J / 5.601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005 Lecture #3 page 5

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 đqp = C p dT also
⎝ ∂T ⎠ p

⎛ ∂H ⎞
∴ ⎜ ⎟ = Cp
⎝ ∂T ⎠ p
20.110J / 2.772J / 5.601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005 Lecture #3 page 6

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

adiabatic, q = 0
porous partition (throttle)

gas (p1, T1) = gas (p2, T2)

w = pV
1 1 − pV
2 2 ⇒ ∆U = q + w = pV 2 2 = −∆ ( pV
1 1 − 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
20.110J / 2.772J / 5.601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005 Lecture #3 page 7

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 an ideal gas C p = CV + R

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

  
↑

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

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

∴ C p = CV + R