Zeroth Law of Thermodynamics

Zeroth Law
Definition of Temperature
Temperature scales
Thermometry
 Thermal Equilibrium
• Thermal equilibrium exists if there is no
spontaneous change in the coordinates of the
system in mechanical and chemical
equilibrium when it is separated from its
surroundings by diathermic walls.
• There is no exchange of heat between the
system and its surroundings.
Two systems in thermal
equilibrium with a third are in
thermal equilibrium with
each other
 Statement
Two systems in thermal equilibrium with a third are in thermal equilibrium with each other.
 Temperature
When two systems are in thermal
equilibrium with each other, they must
possess a property which assumes equal
value in both. This property is called
temperature.
Thus temperature of a system is a property
that determines whether or not a system is
in thermal equilibrium with other systems.
 Significance
The zeroth law establishes the basis for:
➢ the definition of temperature –
equality of temperature
➢ the use of thermometers to measure
temperature
To determine whether two systems A and B are in
thermal equilibrium, a third system C can be brought
in thermal equilibrium with system A and then
brought in contact with system B. Then, if there is no
change in system C we can say that systems A and B
are in thermal equilibrium as per the zeroth law. Thus
system C can be a thermometer to measure the
temperature of systems A and B.
 Thermometry
• Thermometers – temperature measurement
devices
• Substance used in thermometer –
thermometric substance
• Measurable property of substance that varies
with temperature – thermometric property
Thermometer Thermometric Thermometric
substance property
Bimetal thermometer Iron-copper Differential
expansion
Mercury-in-glass Mercury Length of
thermometer mercury column
Constant volume gas Helium Pressure of gas
thermometer
Platinum resistance Platinum Electrical
thermometer resistance of wire
Thermocouple Copper- Thermal emf at
Constantin wire joint
Radiation pyrometer Black body Radiant exitance
thermopile
 Temperature Scale
A temperature scale is a set of rules for assigning
values to different temperatures.
To develop an empirical temperature scale a
relationship between temperature and the
thermometric property is established.
The relationship expresses the temperature as a
function of the property - Ө(X).
This function is called the thermometric
function.
 Thermometric Function
• The thermometric function Ө(X) where ‘X’ is
the thermometric property, determines the
empirical temperature scale. This function can
be expressed in different mathematical forms:
• Directly proportional Ө(X) = aX
• Linear Ө(X) = aX+b
• Quadratic Ө(X) = aX2+bX+c
• Polynomial Ө(X) = a+bX+cX2+·····
 Fixed Point
In the thermodynamic function chosen, a
number of constants are to be determined. This
is done by placing the thermometer in contact
with an arbitrarily chosen standard system in a
reproducible state.
Such a state of the system is called a fixed point,
that is, a fixed temperature.
The fixed temperature provides a reference
temperature for the determination of
temperature scales.
 Celsius temperature scale
• Before 1954 the international temperature scale was
the Celsius temperature scale which was based on two
fixed points:
• The ice point – the equilibrium temperature of ice with
air saturated water at standard atmospheric pressure,
which is assigned a value of 0o C.
• The steam point – the equilibrium temperature of pure
water with its own vapour at standard atmospheric
pressure, which is assigned a value of 100o C
• Due to the problems in accurate determination of the
steam point, in 1954, a single fixed point is chosen for
the Celsius temperature scale – the triple point of
water and is assigned a value of 0.01o C.
 Kelvin temperature scale
In 1967 the Kelvin temperature scale was chosen as
the new international temperature scale which has
the triple point of water as the single fixed point.
The thermometric function arbitrarily chosen for
the empirical scale is Ө(X) = aX.
Since the fixed temperature point is 273.16 K,
aXTP = 273.16 K
Or a = 273.16 K/XTP, where the subscript TP
identifies the thermometric property value XTP
explicitly with the triple point temperature. Hence
the general equation for the Kelvin temperature
scale can be written as
Ө(X) = 273.16 K X/XTP.
 Ideal gas temperature scale
In the empirical temperature scale it is difficult
to separate the effect of the working substance.
It is important that a temperature scale is
devised which is independent of the nature of
the thermometric substance.
Hence a temperature scale based on the ideal
gas equation of state is developed. This scale is
known as the ideal gas temperature scale.
(Scales are exaggerated)
T
Oxygen

Nitrogen
Helium
373.124 K

Ideal gas temperature at steam point measured

using a constant volume gas thermometer
 Ideal gas temperature scale
Since it is known that at zero pressure all gases behave
ideally, the temperature corresponding to zero pressure
is defined as the ideal gas temperature of that fixed
point.
This can be written mathematically as
Өig = 273.16 K P/PTP as P tends to zero, v = constant.
If Өig is denoted as T, this becomes T = 273.16 K P/PTP as
P tends to zero, v = constant.
Using this equation the values of T at different fixed
points can be measured. The empirical scale thus
developed based on the constant volume gas
thermometer is known as the ideal gas temperature
scale.
 Absolute temperature scale
• The temperature scale that is independent of
any thermometric substance is called an
absolute temperature scale.
• The absolute scale of temperature is
developed based on the second law of
thermodynamics and is called the
thermodynamic temperature scale.
International practical temperature scale
The International Temperature Scale – ITS 90
is developed due to the difficulties in using
the gas thermometer for routine calibrations.
• Based on a number of fixed and easily
reproducible points.
• These points are assigned definite
numerical values and measured with
specified thermometers.
• Set of rules for interpolation between fixed
points using ordinary thermometers.
 Assignment
Briefly describe the working of the following
thermometers giving neat sketches and listing
their advantages, disadvantages, and
application:
1. Constant volume gas thermometer
2. Resistance Thermometer
3. Thermocouple
4. Radiation pyrometer