TEMPERATURE AND THE ZEROTH LAW OF

THERMODYNAMICS
WILDAN HIDAYAT (E1Q014051)
EDUCATION PHYSIC | Jl.Majapahit 62 Mataram

THERMODYNAMIC SUMMARY OF CHAPTER 1

1.1 MACROSCOPIC POINT OF VIEW

The study of any special branch of natural science starts with a separation of a restricted
region of space or a finite portion of matter from its surroundings by means of a closed surface
called the boundary. The region within the arbitrary boundary and on which the attention is
focused is called the system, and everything outside the system that has a direct bearing on the
system's
behavior is known as the surroundings, which could be another system. If no matter crosses the
boundary, then the system is closed; but if there is an exchange of matter between system and
surroundings, then the system is open.
There are, in general, two points of view that may be adopted: the macroscopic point of
view and the microscopic point of view. The macroscopic point of view considers variables or
characteristics of a system at approximately the human scale, or larger; whereas the microscopic
point of view considers variables or characteristics of a system at approximately the
molecular scale, or smaller.
For example, the contents in a cylinder of an automobile engine. A chemical analysis
would show a mixture of hydrocarbons and air in cylinder. The contents can be describe by
specifying the quantities of mass, composition, volume, pressure, and temperature. These
quantities refer to the large-scale characteristics, or aggregate properties, of the system and
provide a macroscopic description. The quantities are, therefore, called macroscopic
coordinates. The macroscopic coordinates, in general, have the following properties in common:
1. They involve no special assumptions concerning the structure of matter, fields, or radiation.
2. They are few in number needed to describe the system.
3. They are fundamental, as suggested more or less directly by our sensory perceptions.
4. They can, in general, be directly measured.

1.2 MICROSCOPIC POINT OF VIEW

The microscopic point of view is the result of the tremendous progress of molecular,
atomic, and nuclear science during the past hundred years. From this point of view, a system is

considered to consist of an enormous number N of particles. The particles are assumed to interact
with one another by means of collisions or by forces caused by fields.
Number of particles in each of the microscopic energy states (known as the populations
of the states) when equilibrium is reached. A microscopic description of a system involves the
following properties:
1. Assumptions are made concerning the structure of matter, fields, or radiation.
2. Many quantities must be specified to describe the system.
3. These quantities specified are not usually suggested by our sensory perceptions, but rather
by our mathematical models.
4. They cannot be directly measured, but must be calculated.

1.3 MACROSCOPIC VS. MICROSCOPIC POINTS OF VIEW

Both points of view, applied to the same system, must lead to the same conclusion. The
few measurable macroscopic properties are as sure as our senses. They will remain unchanged as
long as our senses remain the same and are not deceived. The microscopic point of view,
however, goes much further than our senses and many direct experiments. It assumes the
structure of microscopic particles, their motion, their energy states, their interactions, etc., and
then calculates measurable quantities. The microscopic point of view has changed several times,
and we can never be sure that the assumptions are justified until we have compared some
deduction made on the basis of these assumptions with a similar deduction based on the
experimentally proven macroscopic point of view.

1.4 SCOPE OF THERMODYNAMICS

In dealing with the mechanics of a rigid body, we adopt the macroscopic point of view in
that only the external aspects of the rigid body are considered. The position of its center of mass
is specified with reference to coordinate axes at a particular time. Position and time and a
combination of both, such as velocity, constitute some of the macroscopic quantities used in
classical mechanics and are called mechanical coordinates.

A macroscopic point of view is adopted, and emphasis is placed on those

macroscopic

quantities which have a bearing on the internal state of a system. Macroscopic quantities,
including temperature, having a bearing on the internal state of a system are called
thermodynamic coordinates. Such coordinates serve to determine the internal energy of a
system.
A system that may be described in terms of thermodynamic coordinates is called a
thermodynamic system.

1.5 THERMAL EQUILIBRIUM AND THE ZEROTH LAW

Some thermodynamic systems composed of a number of homogeneous parts require the
specification of two independent coordinates for each homogeneous part. In referring to any
unspecified system, we shall use the symbols X and Y for the pair of independent coordinates,
where the symbol X refers to a generalized force (for instance, the pressure of a gas) and Y refers
to a generalized displacement (for instance, the volume of a gas).
A state of a system in which the coordinates X and Y have definite values that remain
constant so long as the external conditions are unchanged is called an equilibrium state.
Experiment shows that the existence of an equilibrium state in one system depends on the
proximity of other systems and on the nature of the boundary or wall separating the different
systems. Walls are said to be either adiabatic or diathermic in ideal cases. If a wall is adiabatic
[see Fig. 1-l(a)], an equilibrium state for system A may coexist with any equilibrium state of
system B for all attainable values of the four quantities, X, Y

and

'

X ,

'

- provided

only that the wall is able to withstand the stress associated with the difference between the two
sets of coordinates
If the two systems are separated by a diathermic wall [see Fig. 1-l (b)], the values of X, Y
and

X' , Y '

will change spontaneously until an equilibrium state of the combined system is

attained. The two systems are then said to be in thermal equilibrium with each other. Thermal
equilibrium is the state achieved by two (or more) systems, characterized by restricted values of

the coordinates of the

systems, after they have
been in communication
with each other through
a diathermic wall.

Imagine two systems A and B, separated from each other by an adiabatic wall but each in
contact simultaneously with a third system C through diathermic walls, the whole assembly
being surrounded by an adiabatic wall as shown in Fig. l-2(a). Experiment shows that the two
systems will come to thermal equilibrium with the third system. No further change will occur if
the
adiabatic wall separating A and B is then replaced by a diathermic wall, as well as if the
diathermic wall separating C from both A and B is also replaced by an adiabatic wall [Fig. 12(b)].
These experimental facts may then be stated concisely in the following transitive relation:
Two systems in thermal equilibrium with a third are in thermal equilibrium with each other. As
suggested by Ralph Fowler, this postulate of transitive thermal equilibrium has been numbered

the zeroth law of thermodynamics, which establishes the basis for the concept of temperature
and for the use of thermometers.

1.6 CONCEPT OF TEMPERATURE

A scientific understanding of the concept of temperature builds upon thermal equilibrium,
X1 ,

established in the zeroth law of thermodynamics. Consider a system A in the state

Y1

in thermal equilibrium with

another system B in the
X '1 , Y '1 .

state

If

system A is removed and its

state

changed,

there will be found a

X2 ,

second state
that

X1 ,

in

thermal

X '1 , Y '1 of system B. Experiment shows that there exists

equilibrium with the original state

a whole set of states -

is

Y2

Y1 ;

thermal equilibrium with this same state

X2 ,
'

X1 ,

Y2 ;
'

Y1

X3 ,

Y 3 - any one of which is in

of system B, and all of which, by the

zeroth law, are in thermal equilibrium with one another. We shall suppose that all such states,
when plotted on an X-Y diagram, lie on a curve such as I in Fig. 1-3, which we shall call an
isotherm. An isotherm is the locus of all points representing states in which a system is in
thermal equilibrium with one state of another system.
Similarly, with regard to system B, we find a set of states -

X '1 ,

Y '1 ; X '2 ,

Y '2 ;

'
'
X 3 , Y 3 - all of which are in thermal equilibrium with one state ( X 1 , Y 1 ) of system A,

and, therefore, in thermal equilibrium with one another. These states are plotted on the
Y '1
states

X '1 ,

diagram of Fig. 1-3 and lie on the isotherm I'. From the zeroth law, it follows that all the
on

isotherm

of

system

are

in thermal equilibrium with all the states on isotherm

and

'

'

of system B. We shall call curves I

corresponding isotherms of the two systems.

To determine whether or not two beakers of water are in equilibrium, it is not necessary

to bring them into contact by means of a diathermic wall and see if their properties change with
time. Rather, an unmarked glass capillary tube filled with mercury (system A) is inserted into the
first beaker (system B) and, shortly, some property of this device, such as the height of the
mercury
column, comes to rest. Such a device is a thermoscope, which indicates only equality of
temperature for the corresponding isotherms of the systems.
1.7 THERMOMETERS AND MEASUREMENT OF TEMPERATURE
To establish an empirical
temperature scale, we select
some

system

with

coordinates X and Y as a
standard, which we call a
thermometer. The simplest
procedure is to choose any
convenient path in the X - Y
plane,

such

as

that

shown in Fig. 1-4 by the

dashed line Y =

Y1 ,

which intersects the isotherms at points each of which has the same Y-coordinate but a different
X-coordinate. The temperature associated with each isotherm is then taken to be a convenient
function of the X at this intersection point. The coordinate X is called the thermometric property,
and the form of the thermometric function (X) determines the empirical temperature scale.

Let X stand for any one of the thermometric properties listed in Table 1.1, and let us
decide arbitrarily to define the temperature scale so that the empirical temperature is directly
proportional to X. Thus, the temperature common to the thermometer and to all systems in
thermal equilibrium with it can be given by the thermometric function,
(X)

= ax

(constant )

(1. 1)

where a is an arbitrary constant. Notice that as the coordinate X approaches zero, the temperature
also approaches zero,
When the thermometer is placed in contact with an arbitrarily chosen standard system in
a reproducible state; such a state of an arbitrarily chosen standard system is called a fixed point,
that is, fixed temperature. The fixed point

provides

reference

temperature

for

the

determination of temperature scales.

Before 1954, the international metric temperature scale was the Celsius scale, which was
based on the temperature interval between two fixed points: (1) the temperature at which pure
ice coexisted in equilibrium with air-saturated water at standard atmospheric pressure (the ice
point); and (2) the temperature of equilibrium between pure water and pure steam at standard
atmospheric pressure (the steam point). The temperature interval between these two fixed points
was assigned 100 "degrees" (of hotness), abbreviated as 100C.
In 1954, a single fixed point was chosen as the basis for a new international temperature
scale, the Kelvin scale. The state in which ice, liquid water, and water vapor coexist in
equilibrium, a state known as the triple point of water, provides the standard reference

temperature. The temperature of the triple point of water, which can be very accurately and
reproducibly measured, was assigned the value 273.16 kelvin, corresponding to 0.01 C, in order
to maintain the magnitude of a unit of temperature. We can now solve Eq. (1.1) for the
coefficient a:
a=

273.16 K
X TP

Where the subscript TP identifies the property value

(1.2)
X TP

explicitly with the triple-point

temperature. The temperature of the triple point of water is the standard fixed point of
thermometry. To achieve the triple point, one distills water of the highest purity and of
substantially the same isotopic composition of ocean water into a vessel depicted schematically
in Fig. 1-5. When all air has been removed, the vessel is sealed off. With the aid of a freezing
mixture in the inner well, a layer of ice is formed around the well. When the freezing mixture
is replaced by a thermometer bulb, a thin layer of ice is melted nearby. So long as the solid,
liquid, and vapor phases coexist in equilibrium, the system is at the triple point.

1.8 COMPARISON OF THERMOMETERS

Applying the principles outlined in the preceding paragraphs to the first three thermometers
listed in Table 1.1, we have three different ways of measuring temperature. Thus, for a gas at
constant volume,
(P) = 273.l6K

P
PTP

(constant V);

(1.3)

for a platinum wire resistor,

'

'

( R ) = 273.l6K

R
R 'TP ;

and for a thermocouple,

() = 273.l6K

TP ;

Such a comparison is shown in Table 1.2, where the constant-volume gas thermometer is used at
high pressure and low pressure. The letters NBP stand for the normal boiling point, by which the
word normal specifies that the temperature at which a liquid boils occurs at standard atmospheric
2
pressure (101,325 Pa or 14.7 lb/i n ), Similarly, the letters NMP stand for the normal melting

point,

NSP for the normal sublimation point, and TP for the triple point, the temperature at which the
solid, liquid, and vapor coexist in thermal equilibrium. The numerical values are not meant to be
exact, and 273.16 has been written simply 273.

1.9 GAS THERMOMETER

A simplified schematic diagram of a constant-volume gas thermometer is shown in Fig. 1-6. The
gas is contained in the glass bulb B, which communicates with the mercury column M through a
capillary

.
The volume of the gas is kept constant by adjusting the height of the mercury column M
until the mercury level just touches the tip of a small pointer (indicial point) in the space above
M, known as the dead space or nuisance volume. The mercury column M is adjusted by raising
or lowering the reservoir. The pressure in the system equals atmospheric pressure plus the
difference in height h between them two mercury columns M and

'

and is measured twice:

when the bulb is surrounded by the system whose temperature is to be measured, and when it is
surrounded by water at the triple point. The various values of the pressure must be corrected to
take account of many sources of error, such as:

1. The gas present in the dead space (and in any other nuisance volumes) is at a temperature
different from that in the bulb.
2. The gas in the capillary connecting the bulb with the manometer has a temperature gradient;
that is, it is not at a uniform temperature.
3. The bulb, capillary, and nuisance volumes undergo changes of volume when the temperature
and pressure change.
4. A pressure gradient exists in the capillary when the diameter of the capillary is comparable
to the mean free path of the gas particles.
5. Some gas is adsorbed on the walls of the bulb and capillary; the lower the temperature, the
greater the adsorption.
6. There are effects due to temperature and compressibility of the mercury in
the manometer.
Improvements and alternative ways of measuring pressure have been incorporated into the
design of gas thermometers, so these errors can be estimated and eliminated from the data. As a
result, the behavior of real gases approaches the behavior of the ideal gas in limiting conditions.

1.10 IDEAL-GAS TEMPERATURE

The theoretical basis for gas thermometry became the well-understood relationship between
pressure, volume, and temperature embodied in the ideal-gas law, namely,

PV = nRT,

(1.4)

where P is the pressure of the system of gas, V is the volume of gas, n is the number of moles of
gas, and R is the molar gas constant. The temperature T is the theoretical thermodynamic
temperature. In this section, we show the experiment that yields reproducible and accurate
empirical temperatures B. The ideal-gas temperature is found using a constant-volume gas
thermometer. Applying Eq. (1.4) initially to the gas at the assigned temperature of 273.16 K and
then to the gas at the unknown empirical temperature, one obtains the proportion
P

=
,
PTP 273.16 K

or

= 273.16 K

P
PTP

(constant V).
(1.5)

Consider measuring the ideal-gas temperature at the normal boiling point (NBP) of water
(the steam point). An amount of gas is introduced into the bulb of a constant-volume gas
PTP

thermometer, and one measures

when the bulb of the constant-volume thermometer is

inserted in the triple-point cell shown in Fig. 1-5. Suppose that

Keeping

PTP

is equal to 120 kPa.

the

volume

V constant, carry out the following procedures:

1. Surround the bulb with steam at standard atmospheric pressure, measure the gas pressure
PNBP

and calculate the empirical temperature using Eq. (1.6),

P NBP
( PNBP ) = 273.16 K 120

2. Remove some of the gas so that

the new value of

PNBP

PTP

has a smaller measured value, say, 60 kPa. Measure

and calculate a new value,

( PNBP ) = 273.16 K

P NBP
60

3. Continue reducing the amount of gas in the bulb so that

and smaller values,

PTP

PTP

and

PNBP

have smaller

having values of, say, 40 kPa, 20 kPa, etc. At each value of

PTP , calculate the corresponding ( PNBP )

4. Plot ( PNBP ) against PTP and extrapolate the resulting curve to the axis where

PTP

= 0. Read from the graph,

lim ( P NBP )

PTP 0

The results of a series of tests of this sort are plotted in Fig. 1-7 for three different gases
in order to measure (P) for the normal boiling point of water. The graph conveys the
information that, although the readings of a constant volume gas thermometer depend upon the

nature of the gas at ordinary values of

PNBP , all gases indicate the same temperature as

PTP is lowered and made to approach zero.

Therefore, we define the ideal-gas temperature T by the equation
T

= 273.16K

lim

PTP 0

P
PTP

(constant V).

(1.6)

1.11 CELSIUS TEMPERATURE SCALE

The Celsius temperature scale, named after the Swedish astronomer Anders Celsius, was the
international temperature scale prior to the introduction of the Kelvin scale in 1954. The Kelvin
temperature scale is based upon a degree of the same magnitude as that of the Celsius scale; the
fixed point was shifted from the ice point of water (273.15 K) to the triple point of water, which
was defined to be 0.01 C above the ice point of water, that is 273.16 K. The relationship
between the Celsius scale and the Kelvin scale is simply

(C) = T (K) - 273.15.

(1.7)

For example, the Celsius temperature NBP at which water boils at standard

atmospheric

pressure is
NBP

T NBP

273.15,

and reading T NBP from Fig. 1-7,

NBP373.124273.1599.974 C

1.12 PLATINUM RESISTANCE THERMOMETRY

The platinum resistance thermometer may be used for very accurate work within the
range 13.8033 to 1234.93 K (-259.3467 to 961.78C). The calibration of the instrument involves
the measurement of

R' (T) at various known defining temperatures and the representation of

the results by an empirical formula. In a restricted range, the following quadratic equation is
often used:
'
2
R' (T) R TP ( 1+ aT +b T ) ,

where R'(T) is the resistance of the platinum wire at the temperature T,

(1.8)
R' TP

is the

resistance of the platinum wire when it is surrounded by water at the triple point, and a
and b are constants. In order to avoid the need for precise absolute measurements of
'
resistance, the calibration of thermometers is always in terms of the ratio R'(T)/ R TP ,

known as W (T).

1.13 RADIATION THERMOMETR

Optical pyrometry, radiation pyrometry, infrared pyrometry, and spectral or total-radiation

pyrometry are some of the methods of thermometry based on the measurement of thermal
radiation, or so-called blackbody radiation.
Radiation thermometers called pyrometers were developed for measuring high
temperatures (greater than approximately 1100 C), and they have the advantage that they are
noncontact thermometers. Optical pyrometers measure temperatures of objects by comparing the
visible radiation from the hot objects over a narrow wavelength band with the radiation from a
standard, preferably using a photoelectric detector for measurements rather than the human eye.

1.14 VAPOR PRESSURE THERMOMETR

Saturation vapor pressure thermometry is commonly used for the measurement of temperature in
the range between 0.3 and 5.2 K, because of the sensitivity and convenience of this type
of measurement. The thermometric substance is the vapor in equilibrium with the liquid of either
of the two

isotopes of helium:

He

or

He . Helium vapor pressure is the

thermometric
parameter, because it depends only on a physical property of a pure element and can be
reproduced at any time, it requires no interpolation device, and it is relatively easy to measure
with sufficient precision over much of the temperature range.

1.15 THERMOCOUPLE
A schematic diagram of a thermocouple is shown in Fig. 1-8, where the temperature to be
measured is located at the test junction. The thermal electromotive force (emf) is generated at the
point where wire A and wire B are joined. The two thermocouple wires are connected to copper
wires located at the reference junction, which is maintained at the temperature of melting ice.

A thermocouple is
calibrated by measuring the
thermal emf at the test
junction at various known
temperatures, the reference
junction being kept at 0 C.
The

results

of

such

measurements

on

most

thermocouples can usually

be represented by a cubic
equation, as follows:
2

c0 c 1 0c 2 0 c 3 0

where is the thermal emf, and the constants c 0 , c 1 , c 2 . and c 3 are different for each
thermocouple. Within a restricted range of temperature, a quadratic equation is often sufficient.
The temperature range of a thermocouple depends upon the materials of which it is composed.
The type K thermocouple, made of a chromel wire (90% Ni and 10% Cr) and an alumel wire
(95%

Ni,

2%

Al,

2% Mn, and 1 % Si) has a temperature range of -270 to 1372C.

1.16 INTERNATIONAL TEMPERATURE SCALE OF 1990 (ITS-90)

The International Committee of Weights and Measures is concerned with two temperature scales:
the first is the theoretical thermodynamic scale; the second is, at any given time, the current
practical temperature scale.

The International Temperature Scale of 1990 (ITS-90) consists of a set of defining fixed
points measured with the primary gas thermometer, and a set of procedures for interpolation
between the fixed points using secondary thermometers.
The lower temperature limit of ITS-90 is 0.65 K. Below this temperature, the scale is
undefined in terms of a standardized thermometer, but research continues in order to select a
reference thermometer from competing instruments. Various intervals of temperature on ITS-90
and secondary thermometers are established, as follows:
1. From 0.65 to 5.0 K. Between 0.65 and 3.2 K, the ITS-90 is defined by the vapor pressuretemperature relations of

He , and between 1.25 and 2.1768 K (the -point) and between

2.1768 and 5.0 K by the vapor pressure-temperature relations of

He .

2. From 3.0 to 24.5561 K. Between 3.0 and 24.5561 K, the ITS-90 is defined by the
4

He

or

He constant-volume gas thermometer.

3. From 13.8033 to 1234.93 K. Between 13.8033 and 1234.93 K (-259.3467 to 961.78C), the
ITS-90 is defined by resistance ratios W(T) of platinum resistance thermometers using the

specified fixed points given in Table 1.3 and by reference functions and deviation functions
of resistance ratios between the fixed points. Eleven subranges have been established to
accommodate a variety of necessary measurements.
4. Above 1234.93 K. At temperatures above 1234.93 K (961.78C), ITS-90 is defined by an
optical pyrometer using the ratio of spectral concentrations of the radiance of a blackbody as
calculated using Planck's radiation law. Only one reference temperature is required for the
pyrometer: the freezing point of gold, the freezing point of silver, or the freezing point of
copper.

1.17 RANKINE AND FAHRENHEIT TEMPERATURE SCALES

The Rankine scale, named after the English engineer, is an absolute scale and is based solely on
the temperature of the triple point of water. The Rankine scale, which does not use the word
"degree," is related to the Kelvin temperature scale by the equation
9

T(R) = 5

T (K).

(1.9)

The Fahrenheit scale, named after the German instrument maker, is defined in relation to the
Rankine scale by the equation

(F) = T(R) - 459.67.

(1.10)

Thus, at the ice point, where the Kelvin temperature is 273.15, the Rankine temperature is (9/5)
(273.15) = 491.67 R. Hence, the Fahrenheit temperature is

(F) = 491.67 - 459.67 = 32.00F.

The Fahrenheit temperature is related to the Celsius temperature by the equation
(F) =

9
5

(C)

32.

(1.11)