MIT OpenCourseWare

http://ocw.mit.edu

5.60 Thermodynamics & Kinetics

Spring 2008

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

5.60 Spring 2008

Lecture #3

Isothermal Gas Expansion

page 1

(T = 0)

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

Irreversibly (many ways possible)
(1)

Set pext = 0
p= 0
T

p= 0
p 1,V1

p 2,V2

v2

w (1) = pext dV = 0
V1

(2)

Set pext = p2
p2
T

p2

T
p 2,V2

p 1,V1

v2

w (2) = p2dV = p2 (V2 V1 )

V1

p
p1

p2
V1

-w(2)

V2

Note, work is negative: system expands against surroundings

5.60 Spring 2008

(3)

Lecture #3

page 2

Carry out change in two steps

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

p1 > p3 > p2
p2

p3

p3

T
p 2,V2

p 3,V3

p 1,V1
v3

v2

V1

V3

w (3) = p3dV p2dV = p3 (V3 V1 ) p2 (V2 V3 )

p
p1

More work delivered to

surroundings in this case.

p3
p2
V1 V3

V2

-w(3)
(4)

Reversible change

p = pext throughout
V

wrev = 2 pdV
V1

p1

p2
V1

V2
rev

For ideal gas:

V

wrev = 2
V1

Maximum work delivered to

surroundings for isothermal gas
expansion is obtained using a
reversible path

V
p
nRT
dV = nRT ln 2 = nRT ln 2
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
And U (T ,V

U
U
dU =
dT +
dV

Some frequent constraints:

dU = d-qrev + d-wrev = d-qrev pdV

Reversible

Isolated

d-q = d-w = 0

Adiabatic

d-q = 0

Constant V

(p = pext )

reversible
dU = d-w =
-pdV

w = 0 dU = d-qV
Constant V

U
U
dU =
dT +
dV
T V
V T
but also
U

d-qV =
dT
T V

d-qV = CV dT

So

= CV
T V

very important result!!

V T

dU = CV dT +

dV
what is this?

5.60 Spring 2008

Lecture #3

U
)
V T

Joule Free Expansion of a Gas

gas

(to get

vac

gas (p1, T1, V1) = gas (p2, T2, V2)

Since q = w = 0
Recall

Adiabatic

q=0

Expansion into Vac.

(pext=0)

w=0

dU or U = 0

Constant U

U
dV = 0
V T

dU = CV dT +
U

V T

dVU = CV dTU

= CV
V T

Joule did this.

page 4

V U

measure in Joule exp't!

V U

T
T
dU = CV dT CV J dV
=
J
V U V U
Joule coefficient

lim
V 0

For Ideal gas

J = 0

dU = CV dT

U(T)

exactly
Always for ideal gas
only depends on T

The internal energy of an ideal gas depends only on temperature

Consequences

U = 0

U = CV dT

For all isothermal expansions or

compressions of ideal gases

For any ideal gas change in state