Methods & Means for Property Measurement &

Need For A Law

P M V Subbarao
Professor
Mechanical Engineering Department
I I T Delhi

Be Cautious, while Numerically Describing a

Macroscopic Property… …
 Temperature Scales
Significance of Temperature
Fahrenheit Celsius Kelvin

 
Black body temperature of visible surface
9,944.45°F 5,506.92°C 
5,780.07 K  of Sun
3774.69 2096
C .33 C
6,169.76°F 3,409.87°C 3,683.02 K Freezing point of tungsten
3,034.26°F 1,667.92°C 1,941.07 K Freezing point of titanium
1,984.32°F 1,084.62°C 1,357.77 K Standard freezing point of copper
1,947.53°F 1,064.18°C 1,337.33 K Standard freezing point of gold
1,763.20°F 961.78°C 1,234.93 K Standard freezing point of silver
1,220.58°F 660.32°C 933.47 K Standard freezing point of aluminum
787.15°F 419.53°C 692.68 K Standard freezing point of zinc
449.47°F 231.93°C 505.08 K Standard freezing point of tin
313.88°F 156.60°C 429.75 K Standard freezing point of indium
212°F.00 100°C.00 373.15 K Standard boiling point of water
136°F.00 57.78°C 330.93 K World record high air temperature
Multiple Options :Temperature Measuring Devices

Liquid in glass
Bimetallic
Thermocouple
Resistance Temperature Detectors
Radiation and optical pyrometers
Gas thermometers
Liquid in Glass Thermometer

V final  Vinitial1    T final  Tinitial 

V final  Vinitial V
l   l final  linitial  2
d capillary
2
d capillary
4 4
 Vinitial  T final  Tinitial 
l final  linitial 
d capillary
2

Material Coefficient of Volumetric

Thermal Expansion  in 10-6 /K
Mercury 180
Ethyl Alcohol 1120
petrol 950
Water 0 to 695 (4 to 90 0C)
Glass 9.9
 Bimetallic Expansion Thermometer
At Reference Temperature

Free End
A Measure of
Temperature
At Higher Temperature

Material a in 10-6 /K
Chromium 4.9

Copper 16.5
lead 28.9
Zinc 30.2
 The Problem of Quantification of Temperature

• Numerical description of temperature demands a zero

temperature point.
• Each temperature scale identified one such zero
temperature point.
• Most popular zero was freezing point of water.
• Knowing the true zero was felt to be a scientific challenge.
 Ideal Gas Temperature Scale

• This is the most important empirical scale.

• An ideal gas is defined to be one which obeys Boyle’s
Law.
• Boyle’s Law: At constant temperature, the volume of a
gas varies inversely with pressure.
• Mathematically:
1
p   pv  Constant
v

C  f T 
T is the empirical temperature, a (primitive) property….
Gas Thermometers
Further Experiments on Gas Thermometers

p  p0  CT

P, kPa

T (0C)
Further Experiments on Gas Thermometers : Unit
mass of Gas at a fixed volume

Gas B

Gas A

p, kPa
Gas C

T (0C)
Absolute Zero!
Further Experiments on Gas Thermometers : Unit
mole of gas

Gas A

Gas C Gas B
p, kPa

T (0C)
Absolute Zero!
Further Experiments on Gas Thermometers : Unit
mole of gas

~
p  RT

p, kPa

T (0C)
Absolute Zero!
98.60°F 37°C.00 310.15 K Human body temperature reference
85.58°F 29.76°C 302.91 K Standard melting point of gallium
68°F.00 20°C.00 293.15 K Room temperature reference
39.15°F 3.97°C 277.12 K Temperature of maximum water density
32.02°F 0.01°C 273.16 K Triple point of water
32°F.00 0°C.00 273.15 K Standard freezing point of water
0°F.00 -17.78°C 255.37 K Fahrenheit's zero
-37.90°F -38.83°C 234.32 K Triple point of mercury
-128.56°F -89.20°C 183.95 K World record low air temperature
-308.82°F -189.34°C 83.81 K Triple point of argon
-361.82°F -218.79°C 54.36 K Triple point of molecular oxygen
-415.47°F -248.59°C 24.56 K Triple point of neon
-434.82°F -259.35°C 13.80 K Triple point of molecular hydrogen
-459.67°F -273.15°C 0 K.00 Thermodynamic absolute zero
 Thermodynamic Temperature

• There is a naturally-defined zero on this scale.

• It is the point at which the pressure of an ideal gas is zero,
by making the temperature also zero
• Thermodynamic temperature is the fundamental empirical
temperature;
its unit is the Kelvin which is defined as the fraction
1/273.16 of the thermodynamic temperature of the triple
point of water.

How to use these quantified macroscopic

properties to identify a Thermodynamic
System ?
 State of A Thermodynamic System
• The collection of all properties for a thermodynamic
system at a certain condition is defined as the state of the
system.
• These properties are not independent.
• It was observed that any of them can be expressed as a
function of some of the others.
• The first three as internal properties of state.
• While the others as called state-functions.
• Internal and external properties of state are generically
mentioned as variables of state.
• If the variables of state can take arbitrary values, they are
defined as independent variables; in the opposite case,
they are called dependent variables.
 What is the beginning of Happening ……
What is the culmination of Happening ……
 Scottish physicist Joseph Black
• On returning to Glasgow as professor in 1756, Black met up
with James Watt ("mathematical instrument maker to the
University").
• This meeting stimulated the next phase of his work involving
the concept of latent heat, and the first steps in calorimetry.
• Here again, it was the quantitative aspects of his work which
led to his discoveries, particularly in the careful measurement
of heat.
• "He waited with impatience for the winter" in Glasgow so that
he could do experiments on the freezing and melting of water
and water/alcohol mixtures that led to the concept of latent heat
of fusion.
 Scottish physicist Joseph Black in his (1786)
Lectures on Chemistry, as such:
• “[There exists] a tendency of heat to diffuse itself from any
hotter body to the cooler around,
• until it be distributed among them, in such a manner that
none of them are disposed to take any more heat from the
rest.
• The heat is thus brought into a state of equilibrium.
• This equilibrium is somewhat curious.
• We find that when all mutual action is ended, a
thermometer, applied to any one of the bodies, acquires the
same degree of expansion:
• therefore the temperature of them all is the same, and the
equilibrium is universal.”
 Equilibrium
• Frequently we will refer not only to the properties of a
substance but to the properties of a system.
• It is necessarily imply that the value of the property has
significance for the entire system.
• This implies equilibrium.
• Every system in this universe spontaneously move towards
equilibrium.
 Thermal Equilibrium

• It is observed that a higher temperature object which is in

contact with a lower temperature object will spontaneously
transfer heat to the lower temperature object.
• The objects will approach the same temperature, and in the
absence of loss to other objects, they will then maintain a
equal temperature.
• They are then said to be in thermal equilibrium.
• Thermal equilibrium refers to equality of temperatures.
• Thermal equilibrium is the subject of the Temperature
measurement.
 Zeroth Law of Thermodynamics

An Universal Law for Measurement …

 Zeroth Law of Thermodynamics

• The "zeroth law" states that two

thermodynamic systems in
thermal equilibrium with the same
environment are in thermal
equilibrium with each other.
• If A and C are in thermal
equilibrium with B, then A is in
thermal equilibrium with C.
Maxwell [1872]
• Practically this means that all
three are at the same temperature.
• A basis for comparison of effect
of temperatures.
 Demonstration of Zeroth Law

If the substance that composes the system is in thermal

equilibrium, the temperature will be the same throughout the
entire system, and we may speak ofWhen Two bodiesashave
the temperature a
property of the system equality of
temperature with a
third body, they in
turn have equality of
temperature with each
BRASS other.
Copper