Mayer’s relation

Masatsugu Sei Suzuki

Department of Physics, SUNY at Binghamton
(Date: September 06, 2017)

Julius Robert Mayer (November 25, 1814 – March 20, 1878) was a German physician, chemist
and physicist and one of the founders of thermodynamics. He is best known for enunciating in
1841 one of the original statements of the conservation of energy or what is now known as one
of the first versions of the first law of thermodynamics, namely that "energy can be neither
created nor destroyed". In 1842, Mayer described the vital chemical process now referred to as
oxidation as the primary source of energy for any living creature. His achievements were
overlooked and priority for the discovery of the mechanical equivalent of heat was attributed to
James Joule in the following year. He also proposed that plants convert light into chemical
energy.

https://en.wikipedia.org/wiki/Julius_von_Mayer

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The Mayer’s relation is described by

CP  CV  R
for an ideal gas where the Boyle’s law is valid, where

 Q   Q 
CP    , CV   
 T  P  T V

Here we present several proofs (including the general case).

(a) Method -1 (Landau)

This proof can be found in the famous textbook by Landau and Lifshitz.

The thermodynamics first law:

dU  TdS  PdV

 Q   S 
CP     T 
 T  P  T  P

 S  ( S , P)
  
 T  P  (T , P)
( S , P)
 (T ,V )

 (T , P)
 (T ,V )
 S   S 
   
1  T V  V T

 P   P   P 
     
 V T  T V  V T
1  S   P   S   P 
 [        ]
 P   T V  V T  V T  T V
 
 V T
 S   P 
   
 S   V T  T V
  
 T V  P 
 
 V T

Here we use the Maxwell’s relation,

  S   P 
   
 V T  T V

Thus we get

 P  2
 
 S   S   T V
T   T  T
 T  P  T V  P 
 
 V T

or

 P  2
 
 T V
CP  CV  T (general case)
 P 
 
 V T

For an ideal gas; we have the Boyle’s relation

PV  RT

 P  RT  P  R
   2 ,   
 V T V  T V V

Then we have

2
R
 
CP  CV  T    R
V
(Mayer’s relation)
 RT 
 2 
 V 

(b) Method-2 (Kardar)

  Q 
CP   
 T  P
 dU  dW 
 
 dT P
(general case)
 dU  PdV 
 
 dT P
 U   V 
   P 
 T  P  T  P

For an ideal gas, U is independent of P and V , but is dependent only on T .

 U   T 
   CV    CV
 T  P  T  P

 V 
P  R
 T  P

leading to the Mayer’s relation.

(c) Proof given in general physics textbook (such as Halliday)

(i) Method-1
We derive a formula for the difference of CP and CV. If we warm a gas (n = 1 mole) slightly
at constant P, we have

dQ  CP dT
dW   PdV   RdT
dU  CV dT

or

dU  dQ  dW  CP dT  RdT  (CP  R )dT

 CV dT

Then we have

CP  CV  R (Mayer’s relation)
 Vf

Fig. Change of volume for gas at constant P0. W    PdV   P0 V   RT .

Vi

U  CV T . Q  C P T

(ii) Method-2
Using the Mayer’s cycle, we show the Mayer’s relation,

1: (P1, V1, T1), P1V1 = RT1

2: (P2, V2, T2), P2V2 = RT2 (T2 = T1).
3: (P2, V1, T3) P2V1 = RT3
(1) The process 1→2 (adiabatic free expansion, irreversible process)

Q12  0 , W12 = 0.

So we have

U12 = 0 (T1 = T2).

(2) The process 2→3 (pressure constant)

Q23  CP (T3  T2 )
V1

W23    P2 dV   P2 (V1  V2 )   R(T3  T1 )

V2

U 23  Q23  W23  CP (T3  T2 )  R(T3  T1 )

(3) The process 3→1 (volume constant)

Q31  CV (T1  T3 )
W31  0
U 31  Q31  W31  CV (T1  T3 )

Then we have

U  U12  U 23  U 31  CP (T3  T2 )  R (T3  T1 )  CV (T3  T1 )  0

From this we have the Mayer’s relation; CP  CV  R .

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REFERENCES
L.D. Landau and E.M. Lifshitz, Statistical Physics Part I, Third edition, revised and enlarged
(Pergamon Press, 1993).
M. Kardar, Statistical Physics of Particles (Cambridge, 2007).
D. Halliday, R. Resnick, and J. Walker, Fundamentals of Physics, 10-th edition (Wiley, 2014).