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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008 Lecture #3 page 1

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
5.60 Spring 2008 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
5.60 Spring 2008 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
but also
⎛ ∂U ⎞
⇒ d-qV = ⎜ ⎟ dT
⎝ ∂T ⎠V

⎛ ∂U ⎞
d-qV = CV dT ⇒ ⎜ ⎟ = CV very important result!!
⎝ ∂T ⎠V

⎛ ∂U ⎞
So dU = CV dT + ⎜ ⎟ dV
⎝ ∂V ⎠T
what is this?
5.60 Spring 2008 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