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Maxwell Relations: by Becky Rameden Physical Chemistry I

James Clerk Maxwell was a 19th century Scottish physicist known for his work in electromagnetism and field theory. He also made contributions to thermodynamics, introducing the Maxwell Relations. The Maxwell Relations provide a way to relate variables in thermodynamics that are difficult to directly measure experimentally, such as entropy. They can be derived by taking the total derivative of equations of state with respect to natural variables and applying rules of partial differentiation. The Maxwell Relations allow working equations to be derived and experimental data to be analyzed when some variables cannot be directly measured.

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53 views11 pages

Maxwell Relations: by Becky Rameden Physical Chemistry I

James Clerk Maxwell was a 19th century Scottish physicist known for his work in electromagnetism and field theory. He also made contributions to thermodynamics, introducing the Maxwell Relations. The Maxwell Relations provide a way to relate variables in thermodynamics that are difficult to directly measure experimentally, such as entropy. They can be derived by taking the total derivative of equations of state with respect to natural variables and applying rules of partial differentiation. The Maxwell Relations allow working equations to be derived and experimental data to be analyzed when some variables cannot be directly measured.

Uploaded by

Ayush Agarwal
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Maxwell Relations

By
Becky Rameden
Physical Chemistry I
James Clerk Maxwell (1831-1879)
Born in Edinburgh,
Scotland
Physicist well-known
for his work in
electromagnetism and
field theory
Also known for his
work in
thermodynamics and
kinetic theory of gases
http://en.wikipedia.org/wiki/James_Clerk
_Maxwell
Theory of Heat
Written by Maxwell and
published first in 1870
Describes his views of the
limitations of the Second
Law of Thermodynamics
Maxwell Relations were
first introduced in this
book

http://store.doverpublications.com/04
86417352.html
Why Use Maxwell Relations?
Certain variables in
thermodynamics are
hard to measure
experimentally such
as entropy
Maxwell relations
provide a way to
exchange variables
What are some examples of Maxwell
Relations?
V S
S
P
V
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
V T
T
P
V
S
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
P S
S
V
P
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
P T
T
V
P
S
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
Deriving Maxwell Relations
First, start with a known equation of
state such as that of internal energy
Next, take the total derivative of
with respect to the natural
variables. For example, the
natural of internal energy are
entropy and volume.
dV
V
U
dS
S
U
dU
S V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
Deriving Maxwell Relations Continued
T
S
U
V
=
|
.
|

\
|
c
c
P
V
U
S
=
|
.
|

\
|
c
c
Now that we have the total derivative with
respect to its natural variables, we can refer
back to the original equation of state and
define, in this example, T and P.
dV
V
U
dS
S
U
dU
S V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
Deriving Maxwell Relations Continued
We must now take into account a
rule in partial derivatives
When taking the partial derivative
again, we can set both sides equal
and thus, we have derived a
Maxwell Relation
Mnemonic Device for Obtaining Maxwell
Relations
The partial derivative of two neighboring properties (e.g. V and T)
correspond to the partial derivative of the two properties on the
opposite side of the square (e.g. S and P). The arrows denote the
negative sign; if both are pointed the same way, then the sign is
negative.
Using Maxwell Relations
Maxwell Relations can be derived from basic equations
of state, and by using Maxwell Relations, working
equations can be derived and used when dealing with
experimental data.
References
Darin J. Ulness: Course Notes, Chemistry
351 Fall 2004
Physical Chemistry, Laidler, Meiser
Sanctuary, 2003.
http://en.wikipedia.org/wiki/James_Cle
rk_Maxwell
http://store.doverpublications.com/048
6417352.html

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