What is Temperature ?

There are five laws of Thermodynamics.

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Laws of Thermodynamics

0, 1, 2, 3, and ?

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Experimentally observed Zeroth law of Thermodynamics.

Diathermal walls:
Consider two systems (A,B) in
Heat
may
flow, boundary may move.
thermal contact.
If A and a third system C are
brought into thermal equilibrium,
A B
A C
B C
and this results in no change in the
values of the state variables of A.
then it is observed that B and C, if
put in thermal contact are also in
thermal equilibrium with each other.

This observation is the Zeroth Law of Thermodynamics:

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Zeroth Law of Thermodynamics

Zeroth Law: If each of two systems is in thermal equilibrium with a

third system they are in thermal equilibrium with each other.
The argument can be repeated for fourth, fifth, ... systems (D, E, ...).
If each is in thermal equilibrium with all the others, they must have the
same value of some property that has a common value.
This property is called thermodynamic temperature T.
The temperature of a system is a property that determines whether or
not that system would be in thermal equilibrium with other systems.

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What is Temperature?
Notice that the DEFINITION by equivalence does not mean there is a
numerical scale from high to low. We will have to prove this later.


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?
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Complete Thermodynamic Equilibrium

Two systems to be in complete thermodynamic equilibrium, must have

a common temperature
show no exchange of material (no diffusion through wall of contact),
show no chemical reactions (chemical equilibrium)
be subject to no unbalanced force (mechanical equilibrium).
All of these are associated with equal values of a state function:
temperature, pressure (stress), chemical potential etc.

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Temperature scales

Many possible practical temperature scales and thermometers. all depend

on a thermometric property of a material. Is there a unique scale?
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Ideal Gas Temperature Scale

Instead of a real material, use an idealised one.

We choose: T = TIG = PV /nR.

TIG has a value stated in kelvin, denoted by the symbol K.
This choice connects temperature to microscopic kinetic energy.
mv2 /2 = (3/2)kB T
introducing Boltzmanns Constant kB = R/NA
For a fixed amount of ideal gas in a fixed volume, the thermometric
property is the pressure.
Problem: theres no such thing as an ideal gas to build a thermometer.

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How to measure temperature.

For a fixed amount of ideal gas in a fixed volume, the thermometric

property is the pressure.
Other systems have their own thermometric properties,
the pressure of a real gas
XR , the electrical resistance of a sample
of (a carefully chosen) metal;
X` , the length by which a liquid
expands, when heated, into a
narrow-bore tube (mercury-in-glass
thermometer).
X , the density of a given material .

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How to measure temperature.

For a fixed amount of ideal gas in a fixed volume, the thermometric

property is the pressure.
Other systems have their own thermometric properties,

Good thermometric properties

Monotonic function of T
Linear variation with TIG
Can be easily and precisely measured

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Two point calibration - Celsius and centigrade scale

Practical thermometers must be
calibrated.
For a liquid-in-glass thermometer, suppose
the lengths of liquid are `, `steam and `ice , at
the unknown temperature ` , the
temperature of the boiling and freezing
points of water.
Centigrade temperature ` , defined by:


Anders Celsius, dead with TB at
` `ice
` = 100
42, suggested a two-point
`steam `ice
calibration with water freezing
at 100 and boiling at 0 .
Linnaeus, inventor of binomial
species nomenclature, reversed
the scale.
Graeme Ackland ()

Any nonlinearity ofthermometic property (in

Tig ), means different thermometers
calibrated at the same fixed points will not
agree at other temperatures.
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One point calibration - historical hangovers - matching

Kelvin and Celsius scales
with absolute zero as a calibration
point, need only one other.
Kelvin scale is defined by the
triple point of water: 273.16K.
Celsius was defined by T(C
=T(K)-273.15 to get the
freezing point of water at
atmospheric pressure:
0 C=273.15K.
Recent measurements say water boils at 99.98 C and Ice melts
at -0.001 C!

BUT...whats special about water?

An alternative is to define Boltzmanns constant equating kelvins to Joules

kB = 1.38065051023J/K
(people are still arguing about this one...)
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Triple point of water

It is easy to find the triple point of water.

Too cold: water freezes, releasing latent heat
Too hot: ice melts, absorbing latent heat
High pressure: gas condenses, reducing density
Low pressure: water boils, increasing gas
density

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Practicalities Definition of T

Water triple point defines TIG , 273.16K .

TIG of freezing and boiling at 1 atm. are approximately 273.15 K and
373.12 K.
Celsius scale, t, is specified by: ice point temperature is 0 C,
t( C) = T (K) 273.15
On Mount Everest, at 29,029 ft, the pressure is about 34 kPa and the boiling
point of water is 71 C.

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International temperature scale ITS-90

Approved thermometers
0.65-3K 3 He vapour pressure
1.25-5K 4 He vapour pressure
3K-24.5K He gas pressure
24.5-1235K Pt resistance
1235K+ Blackbody radiation

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Proving the Existence of a Temperature Scale

Equal Temperature is defined by the concept of equilibrium.
We want to prove two things: If TA = TB and TC = TB then TA = TC
NOT logically required: e.g. If zebras are stripy animals, and tigers are stripy
animals, but zebras arent tigers ...

If TA > TB and TB > TC then TA > TC

NOT logically required: e.g. stone beat scissors, scissors beat paper, but stone
doesnt beat paper

Specifically we show that there exist functions 1 (P1 , V1 ) and 2 (P2 , V2 )

such that if 1 (PA , VA ) = 2 (PB , VB ) ...
then states (PA , VA ) of system 1 and (PB , VB ) of system 2 are in thermal
equilibrium ...
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Zeroth law requires the existence of Temperature

Consider systems A, B, C fully specified by two mechanical variables P, V
For A & C to be in thermal equilibrium, some relationship between the
different state variables must be satisfied.
F1 (PA , VA , PC , VC ) = 0
Solving for PC = f1 (PA , VA , VC ) with f1 some other function.
Similarly for B,C to be in thermal equilibrium PC = f2 (PB , VB , VC )
For A and B to be separately in mechanical equilibrium with C
f1 (PA , VA , VC ) = f2 (PB , VB , VC );

f1 (PA , VA , VC )f2 (PB , VB , VC ) = 0;

The zeroth law asserts that A and B are in thermal equilibrium. Therefore
there must exist,
F3 (PA , VA , PB , VB ) = 0
For f1 f2 and F3 , to be equivalent VC must cancel
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Recall
f1 (PA , VA , VC ) f2 (PB , VB , VC ) = 0;
F3 (PA , VA , PB , VB ) = 0
For f1 f2 and F3 , to be equivalent VC must cancel
f1 (PA , VA , VC ) = 1 (PA , VA )(VC ) + (VC )
f2 (PB , VB , VC ) = 2 (PB , VB )(VC ) + (VC )
Therefore, there exist functions 1 (PA , VA ) and 2 (PB , VB ) that describe
each system, and 1 (PA , VA ) = 2 (PB , VB ) when A and B are in thermal
equilibrium.
We call these equilibrium-defining functions Temperature.
n.b. If the system requires more than two independent variables to define
it, the above argument still works.
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Zeroth law requires the existence of Temperature

To recap, the Zeroth Law asserted that there exists a concept of thermal
equilibrium,
...so...
it follows that some state function must relate to thermal equilibrium.
...and...
This function is then called Temperature

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Example

If only two state variables are required to specify the state, then T must
be a function of P and V : T = f (P, V ).
f depends on the material (different f for Ar, O2 , air, Ideal gas, etc.). We
use T (P, V ) to denote the function f (P, V ).
Equivalently we can also write P = P(V , T ) or V = V (P, T )
The material-dependent relationship between P, V and T is the equation
of state.
e.g. for an ideal gas PV=nRT; T(P,V)= PV/nR; P(T,V)=nRT/V;
V(P,T)=nRT/P

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Isotherms

Many equilibrium states correspond to the

same temperature T
The line through them is called an isotherm.
Isotherms can be drawn on a PV diagram for
each value of the temperature.
These states are in thermal equilibrium with
each other, but not mechanical equilibrium
No two different points on the PV diagram
can be in thermal and mechanical
Ideal gas isotherms do not
equilibrium.
cross one another,
But water isotherms do.

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A beardy equation

For each degree of freedom

Boltzmanns * Kelvins = Joules

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UK leads the way in race for new temperature definition

Speed of sound in ideal gas is
s

P
c0 =
s
s
P
=

r
NA kB T
=
M
July 2013, NPL measured
kB = 1.38065156(98) 1023 J/K
Using speed of sound in argon, by resonance of
copper sphere whose diameter is known to
11.7nm (500 atoms)
More accurate than the measurement of the critical temperature of water.
http://iopscience.iop.org/0026-1394/50/4/354, Michael de Podesta et al 2013 Metrologia 50 354
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