The Thermodynamic Definition of

Temperature

John W Daily
 Thermal Equilibrium

A B

An isolated system, composed of two subsystems

initially at different equilibrium states. Heat transfer
is then allowed across the barrier. What are the final
states?
What do we do with the Postulates?
• Maximize entropy
• Differentiate and set to zero

∂S " ∂S " ∂S "

dS = $
∂U # V , Ni
dU + $
∂V # U , Ni
dV + ∑ ∂N $# dN j
j j U ,V , N i ≠ j

• What are the partial derivatives?

 Thermal Equilibrium
Calculate total entropy

S = S A + SB

Differentiate
dS = dS A + dS B
dS # dS #
dS = ! dU A + ! dU B
dU " A dU " B

(V’s and Ni’s constant)

 Thermal Equilibrium
Note that total energy is conserved (1st Law)

U = U A + U B = Constant

So that
dU = 0 = dU A + dU B

and
dU B = −dU A
 Thermal Equilibrium
Eliminate dUB and set to zero

& dS ) dS ) #
dS = % ' − ' "dU A = 0
$ dU ( A dU ( B !

Since UA is an independent variable, we must have?

 Thermal Equilibrium

dS # dS #
! = !
dU " A dU " B

What does this mean?

What property do we know that has equal values
in two subsystems in equilibrium?
Thermal Equilibrium

Yes ........ T!

∂S #
But is T= ! ?
∂U "V , N i

Let’s try it
 dS = {TA − TB } dU A = 0

If TA > TB then {TA − TB } > 0

But if heat transfer is from high to low temperature we must have
dU A < 0 making dS < 0

NOT ALLOWED!

A B
 Thermal Equilibrium
So no, we must have:

1 ∂U #
T≡ = !
∂S # ∂S "V , N i
!
∂U "V , N i
and
TA = TB

Now you know what temperature is!