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TEMPERATURE
THERMAL EQUILIBRIUM
Two bodies are in thermal equilibrium (i.e at the same temperature) when there is no net
transfer (exchange) of heat between them.
Zeroth Law of thermodynamics states that if bodies A and B are each separately in thermal
equilibrium with body C, then A and B are in thermal equilibrium with each other.
If body C is a thermometer and gives the same reading when in contact with bodies A and B
separately, then A and B are in thermal equilibrium with each other. So, temperature of a
body is that property which determines whether it is in thermal equilibrium with
another body.
TEMPERATURE SCALE
1 THE EMPIRICAL SCALE
A thermometric property is a physical property which either increases only with
increasing temperature or decreases only with increasing temperature.
The empirical temperature scale is a scale based on experimental results using a
thermometric property. It is established using a thermometric physical property X of a
substance and two fixed points. X can be volume or length of column of a liquid (liquid-inglass thermometer), resistance of a metal (resistance thermometer), e.m.f (thermocouple) and
pressure of a fixed mass of gas at constant volume (constant-volume gas thermometer)
The two fixed points are ice point and steam points which are fixed temperatures at standard
atmospheric pressure and are also easily reproducible. An example of the empirical scale is
the centigrade scale where X between the two fixed points is divided into 100 equal parts (or
degrees).
(a) Linear Scales:

Assuming that the thermometric property P varies


linearly with temperature,

Hence,

, where

Xi = value of thermometric property at ice point


Xs = value of thermometric property at steam point
X = value of thermometric property at unknown
temperature

Linear
variation

Xs
X
Xi

100

calibration graph

/C
C

Junction at room
temprature

mV
,
where = temperature
difference between the two
junctions.
The cold junction is known
as the reference junction and
is usually kept at 0 C. The
hot junction is known as the
hot junction or measuring
junction.

mV
copper

iron

copper

iron

cold
junction

hot
junction

Measuring junction

(b) Non-Linear Scales:

R/

e.m.f /V

graph of thermocouple e.m.f against temperature

/C

/C

graph of resistance of a thernistor against temperature

Between 1 and 2 variation of e.m.f with temperature is not single value and so cannot be
used to measure temperatures.
Over a small temperature range, there is a rapid change in resistance and the variation is more
or less linear. This makes the thermistor a sensitive thermometer over this temperature range
and so can be used to detect small changes in temperature.
Limitations of the empirical (centigrade) scale
Different types of thermometer measuring the same temperature show different readings on
the centigrade scale. Reasons: (i) the thermometric property may not vary linearly with
temperature, (ii) different thermometric substances do not respond in the same way to
changes in temperature, except at the two fixed points or points of calibration. Also, it is not
obvious whether one particular thermometric property P is better than another.
2 THE IDEAL GAS TEMPERATURE (or ABSOLUTE THERMODYNAMIC) SCALE
An absolute (thermodynamic or ideal gas temperature) scale overcomes the limitations of the
empirical scale because it does not depend on the thermometric property of any substance.
It is defined by the Ideal Gas Equation pV=nRT.

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The two fixed points on the thermodynamic scale are:
1. absolute zero (0 K): temperature at which particles have no k.e.
2. triple point of water (Ttr = 273.16 K) : temperature at which ice, pure water and water
vapour all coexist in equilibrium.
Ttr is fixed at 273.16 K to make temperature difference between ice point and steam point
exactly 100 K on the thermodynamic scale.
The unit of thermodynamic scale is the Kelvin (K). One Kelvin is defined as

of the

thermodynamic temperature of the triple point of water (Ttr):


The Ideal Gas Equation:

pV

or

So,
(pV)tr
An ideal gas is only theoretical. In practice real gases
behave closely to the ideal gases at very low pressures.
So for a real gas,

real gas
0

But at low temperatures and high pressures


intermolecular forces cannot be neglected, a real gas
deviates from its ideal.

pV

The constantvolume gas thermometer can be used to


determine the thermodynamic temperature scale using
approximation
.
In
this
thermometer, the pressure of a fixed volume of gas is
used as the thermometric property (p T). The scale is
close to the thermodynamic scale when the gas pressure
in the thermometer bulb is reduced to very low values.
This is why for accurate calibration the constant-volume
gas thermometer is used as a standard.

Ttr

real gas and ideal gas at


a given temperature T

real gas (e.g air)


(pV)T

ideal gas

Graph shows how pV varies with p for a fixed


mass of gas at temperature T

Experimental procedure to determine


the
thermodynamic temperature
of a body using the constant-volume gas (He or H)
thermometer
The bulb of the gas thermometer is placed in thermal equilibrium with a triple point cell and
its pressure
is measured (
). It is then placed in the bath of unknown temperature
and its pressure pT of the gas in the thermometer is measured when thermal equilibrium is
reached (
). The value of
is calculated. Some gas in the thermometer is
removed so that to reduce its pressure. The new pressures
and
are measured again and
the new value of
is calculated. The procedure is repeated a number of times for
smaller and smaller amount (as far as possible) of gas in the bulb.

T/K

...........
...........
...........

/cmHg
/cmHg
/K

The unknown temperature of the bath (T1 T 2


T3.) are different at different values of

real gas
ideal gas

because real gases behave differently (


)
from ideal gases at moderate and high
pressures. This is why at high pressures different gas thermometers give different temperature
readings for the same temperature. All real gases behave like ideal gases in the limit
.
i.e all real gases give the same value of
at
(or
), implying different gas
thermometers would give the same thermodynamic temperature at the limit of
(or
). A graph of
against
(or ) is plotted. The graph is then extrapolated
to

(or

) to obtain the value of

the bath is then calculated using

. The thermodynamic temperature

of

THE CELSIUS SCALE


The Celsius scale is derived from absolute thermodynamic scale with the same fixed points as
the thermodynamic scale to make it coincide with the centigrade scale. The defining equation
for the Celsius Scale is
, giving
. E.g
Temperature of triple point of water is 273.16K or 0.01 C. Ice point is 273.15 K or 0 C and
steam point is 373.15 K or 100 C. temperature difference between ice point and steam point
is 100 C or 100 K. For most calculations involving conversion, 273 is sufficiently accurate.
PRACTICAL THERMOMETERS

Advantages

Disadvantages

Thermocouple
Self-powered
cheap, robust
Wide temperature range
short response time
Non-linear scale
Low voltage across junctions
Reference point required

Thermistor Thermometer
allows remote measurement
cheap, robust, short response time, very
sensitive ( 200C-1)
Poor accuracy, non-linear scale
Current source required
Self heating,
narrow temperature range

Note: (1) Sensitivity: change in length/volume per degree Celsius


(2) Range: lowest to highest (measured) temperatures
(3) Linear scale: same distance between all degrees intervals.
(4) Empirical scale is a scale based on experimental results by using a thermometric property.
(5) A thermometer with a small heat capacity is very responsive and has negligible effect on
temperature it is measuring.
(6) A thermometer based on electricity can be linked to other circuits/computer which allows
remote temperature measurement.

Thermometer

Range/C

Mercury-inglass

-39 to 357
(limited)

n.t.c Thermistor

-50 to 200
(limited)

Thermocouple

-250 to
1500
(wide)

Accuracy

Poor

Poor

Average

Sensitivity

Response
time

Scale

Average

Medium

Linear

High

Short
(small heat
capacity)

Nonlinear

Average

Short
(small heat
capacity)

Nonlinear

Uses
Measuring
temperature of
cooling or heating
water
Room temperature
measurement,
electronic
thermometers,
measuring varying
and remote
temperatures
Measuring
temperature that
varies rapidly at a
point or a remote
place