Relationships between partial derivatives

Reminder to the chain rule

composite function: F( u, v, ....)

u(x, y,...), v(x, y,...) ,...

F( x, y,...)  F(u ( x, y,...), v( x, y,...),...)

You have to introduce a new symbol for this function, also the physical
meaning can be the same

Example: Internal energy of an ideal gas U(T)  n u 0  n c V T

PV PV
U(P, V)  n u 0  c V T(P, V) 
R nR
 F( x, y,...)  F(u ( x, y,...), v( x, y,...),...)
F( x, y,...)
Let’s calculate with the help of the chain rule
x

F(x, y,...) F(u, v,...) u(x, y,...) F(u, v,...) v(x, y,...)
   ...
x u x v x

Example: F(x, y,...)  x  y  2


2 3/ 2
sin xy

explicit:
F(x, y,...) 3 2
x

2
x  y 2 2x sin xy  x 2  y 2  
3/ 2
y cos xy

Now let us build a composite function with: u ( x, y)  x 2  y 2 and v(x, y)  xy

F(u, v) 3 1 / 2 u ( x , y)
F(u, v)  u 3/ 2
sin v  u sin v  2x
u 2 x
F(u, v) v( x , y)
 u 3 / 2 cos v y
v x
 F(x, y) F(u, v) u(x, y) F(u, v) v(x, y)
 
x u x v x

F(u , v) 3
F(x, y) 3 2
 u sin
x v
 u ( xx, y)  y 2x sinxy
2 x
2
2 x
2
 u

F(u, vx)  3y/ 2
2
3/ 2
cos
y cos
v v( xxy
, y)
yy
u 2 v x

Composite functions are important in thermodynamics

-Advantage of thermodynamic notation:
Example: F(X, Z)  F(X, Y(X, Z))

If you don’t care about new Symbol for F(X,Y(X,Z))

F F F Y F Y
wrong conclusion from   0
X X Y X Y X
can be well distinguished

 F   F   F   Y 
-Thermodynamic notation:        
 X  Z  X  Y  Y  X  X  Z
Apart from phase transitions thermodynamic functions are analytic

  F( x, y)    F( x, y) 
    2 F( x, y)  2 F( x, y)

y  x  x  y 

yx xy
See later consequences for physics
(Maxwell’s relations, e.g.)

Inverse functions and their derivatives

Reminder: function y( x ) inverse function x ( y) defined according to

y( x ( y))  y
1
Example: function y( x )  ( x  1) y  1 xy  y  1 1  y  xy
x 1
1  y y( x ( y))  1

1

y
y
x ( y) 
y x ( y)  1  1  y  (1  y)  y
   1
 y 
 10

8
X

6
Y

0
0 2 4 6 8 10
Y
X
What to do in case of functions of two independent variables y(x,z)
keep one variable fixed (z, for instance)

Let’s apply the chain rule to y(x( y, z), z)  y

dy( x ( y), z) dx
1
dx dy

y x
Result from intuitive relation: 1
x y

Thermodynamic notation:

 Y   X 
    1
 X  Z  Y  Z
y=y(x,z=const.)

y( x, z) is inverse to x ( y, z) if y(x( y, z), z)  y

 10 6

8 Numerical example
4
6

dY/dX
Y

4
2
2

0 0 3
0 2 4 6 8 10 0 2 4 6 8

dY/dX*dX/dY
X X 2

 1

10 6 0
0 1 2 3
8 X
4
6
dX/dY
x

4
2
2

0 0
0 2 4 6 8 10 0 2 4 6 8

Y Y
  Y   X 
Application of the new relation     1
 X Z  Y Z

1  V 
Definition of isothermal compressibility  T    
V  P  T

Remember the
 P 
Definition of the bulk modulus BT  V 
 V T

 V   P   BT 
With     1  V T    1
 P T  V T  V 

 T BT  1 or  T  1 / BT
  2 F( x, y)  2 F( x, y)
Application of 
yx xy

1  V   V 
Isothermal compressibility: T        V  T
V  P  T  P T

1  V   V 
Volume coefficient of thermal expansion:  V       V V
V  T  P  T  P

  ( V
V T )   2V  2 V  (VVV) 
         
T  TP   TP PT  P PT PT
 T P P T
 V    T   V    V 
  T  V  =   V   V 
 T P  T P  P  T  P  T
  T    
 V V  T  V  =  V T  V  V V 
 T P  P T

     
 T    V 
 T  P  P  T
 We learn: Useful results can be derived from general mathematical relations

Are there more such mathematical relations

Consider the equation of state: P  P(V, T) or V  V(P, T)

P  P(V(P, T), T)

For P  const. P(V(P, T), T)  const. (before we calculated derivative with respect to P @ T=const.
now derivative with respect to T @constant P)

Total derivative with respect to temperature

 P   V   P   T 
       0  
 V  T  T  P  T  V  P  V

 P   V   T   P   T   P   V   T 
           0        1
 V  T  T  P  P  V  T  V  P  V  V  T  T  P  P  V
1
 Is a physical counterpart of the general mathematical relation:
 P   V   T 
       1  X   Y   Z 
 V  T  T  P  P  V        1
 Y  Z  Z  X  X  Y

Let’s verify this relation with the help of an example

Z X=0 plane y=0 plane z=0 plane

z z y

y x x
Y
x 2  y2  z2  R 2 Surface of a sphere

X
  x  y y
x  R y z
2 2 2    
 y  z R 2  y2  z2 x

 y  z z
x y z  R
2 2 2 2
y  R x z
2 2 2    
 z  x R 2  x 2  z2 y
for x,y,z 
1st quadrant  z  x x
z  R x y
2 2 2    
X  x  y R 2  x 2  y2 z
cyclic permutation

 x   y   z   y z  x
        1
 y  z  z  x  x  y x y z
Y Z

Physical application: Change in pressure caused by a change in temperature

 P   V   T   P   V  1  P 
       1        
 V  T  T  P  P  V  V  T  T  P  T   T  V
 
 P  V

 P   P  1  V 
   V     BT  V
 T  V  V  T V  T  P