ME2121/E Thermodynamics

Chapter 2 Definitions and Basic

Concepts, and Temperature Scales
by
Professor KC Ng (EA-07-22)
Email: mpengkc@nus.edu.sg
(August 2014)
As in all subjects of mechanical engineering,
classical thermodynamics is defined by sets of
terminologies that engineers and scientists used
to describe the behaviours of matters, processes,
reactions and energy interactions. As students
taking thermodynamics for the first time, one of
the most common questions asked is:

What is a thermodynamic system?

It is simply a study of behaviour of matter
(gases, liquids or solids) in an enclosed space
which an engineer or scientist would like to
investigate. Matters (such as gases, liquid or
solids) are contained within a physical or
imaginary boundary of a closed or open system.
The energy generated or consumed by the
matters may be transferred in and out from the
boundary of system. Outside the system
boundary is called the surroundings, as shown
schematically in Figures 2.1.

aircraft carrier that ejects a jet-plane taking off

from the deck of an aircraft carrier.
(http://science.howstuffworks.com/aircraftcarrier3.htm).
One
of
the
terminologies
used
in
thermodynamics is called property. It is a
variable is used to describe the behaviours or
characteristics of a system. The changes in the
states of matter are measured by variables such
as temperature (T), pressure (P), volume (V),
enthalpy (h), entropy (s), etc. They are measured
by using suitable sensors, calorimeters, etc.,
where their changes are monitored by
quantifiable readings of sensors.
One common example of a system is the pistoncylinder assembly, as shown in Fig. 2.2. For
example, the matter contained inside the
cylinder is air (a mixture of N2 and O2). They
have direct relationships between its volume (V)
and the temperature (T) as well as the pressure
(P) that one can measure or monitor. These
measurable variables are termed the properties
or characteristics of a system.
Gas matter, as
measured by P, V &
T

Fig. 2.1 Boundary and surroundings of a

thermodynamic system

air

Boundary
Boundary
system

Work
transfe
r (W)

Heat transfer
(Q)

Fig. 2.2 An example of the piston-cylinder

assembly
Matter, e.g., gases, liquids or solids
A close system has no mass leaving its
boundary (dm = 0). An example to demonstrate
this concept is the piston-cylinder assembly,
commonly found in engineering devices such as
the shock absorber of a car or the catapult on an

Similarly, there are other variables of a

thermodynamic system that we will come across
in the coming lectures; For example, mass (m),
energy of matters in system or internal energy
(U), enthalpy (H=U+PV), specific heats (Cp),
entropy (dS=dQ/T), etc.

Thus, a thermodynamic system is described by

the following key points:

It can be characterize by variables called

properties,
a property measures the state of
matter(s) without causing changes to it,
a property is used to describe the path of
an event or process: from a starting
point (1) to an ending point (2). Eg., we
define the specific heat of a matter as;

Cv

example, 1 kmol of Carbon (C12) contains the

number of carbon molecules (basic structure of
matter) equal to a mass of 12 kg. For gases at
the standard temperature and pressure (STP),
this number of molecules (volumetric basis) per
kmol is termed the Avogadros number, i.e.,

No = 6.023 1026 [molecules/kmol].

Hence, the mass of 1 kmol of any substance is
also called the molar mass (M), i.e.,
m [kg] = nM [mol x kg/mol]
or

1 2 U

m 1 T v

where the subscripts 1 denotes the

starting point, 2 the ending point of a
process. The subscript v is a variable
(outside the bracket) being held at
constant during the integration along the
process.
a property can be defined in terms of
other established properties, e.g., the
enthalpy (H=U+PV) and it is given by
(in the extensive form function of
mass)

H U PV
or in the intensive (per kg) form as

H U
V
p
or h u Pv .
m m
m
where the lower case variables represent
mass independent or intensive variables.
Note that P is not dependent on the mass
in the control volume.

Quantity of matters
In SI units, the basic amount of substance is
given by mass in kilogram (kg). It is also
common for an engineer to refer to the amount
of matter as mols, and 1000 mols or 1 kmol. For

m/M = n, also equal to its volume fractions

where n is the number of moles. This implies
that the mass fraction is given by volume
fractions since mols are related to the volume
via the Avogadros number (No) .
Example: Air is a mixture and its mass fractions
in the atmosphere can be computed via the mol
fractions)
Constituents

Volume
Fraction
(n/n)

Mole-cular
mass
[kg/kmol]

mi=
ni xMi
[ kg]

By mass
Fraction
(m/m)

Nitrogen
(N2)
Oxygen
(O2)

0.79
(79%)
0.21
(21%)
1.0
100%

28

=0.79x28
=22.12
=0.21x32
6.72
=28.82

22.12/28.82
=0.767
=6.72/28.82
=.233
1.0

32

State of a thermodynamic system:

The state of a system is defined by the
thermodynamic properties and at least two
independent properties are needed to locate a
state, e.g., the (P & T) or (P & v). When two
points on a thermodynamic diagram have the
same numerical values, it is termed as identical
states.

Process(es):
A process is the path between two given
states where there may be interactions of heat
2

(Q) and work (W) transfer in or out of a control

volume. The Q or W are deemed as a useful
effect arising from the process.
The area under a process path is of
interest to an engineer because it represents a
variable e.g., Q or W, which is a non-property as
it is path dependent. Fig. 2.3 shows that when
two processes are connected in such a manner
that at the end of the processes, and should the
path returns to its initial state point, 1 this is
termed a cycle.
Fig. 2.3 A cycle is demonstrated by two process
paths between 2 state points: 12 is an
outgoing process path whilst the dotted line --- is the return path of a cycle.

Path A

1
(P1, v1)

cycle

2
(P2, v2)

As the initial (1) and final (2) states are

defined by thermodynamic properties, say
(pi). The net change of a variable undergoing a
cyclic process would be zero (naught), i.e.,

A requirement of a property is that the variable

of the states (numerically) must sum to zero
when the process path returns to the same
starting point.

Y=P

B (2,4)

C (4,4)

A (2,2)

D (4,2)
X= V

That is: 0 where

can be P, T or V

P (4 2) (4 4) (2 4) (2 2) 0

Path
B

cycle

A cycle, as shown below, is described by two

thermodynamic variables, say X and Y. If their
states are defined numerically by the values
indicated (in bracket), demonstrate from these
states that the principle of a property is valid.

(1)

because is the property of a system, such as P

or v or T or any variable of the system. A
property of a thermodynamic system must
satisfy the definition of a continuous function,
that is, it not an abrupt or discontinued function.

The numerical numbers at every state point in

the cycle represent the respective properties of
the matter. You can repeat with any other
thermodynamic variable, say V, and it would
sum to zero when taken over a cycle. This
proves the point that a property in a
thermodynamic system always adds to zero
when it is returned to its original state.

Mathematical Test of a Property

We start with a temperature (T) relation for air
in a piston-cylinder assembly (see Fig. 2.2),
expressed mathematically as a function of two
other variables of the system (such as P and v),
namely;
T = T (P,v).

(2)

Thermodynamic property relation for

a cycle

However, from experiments conducted on a

piston-cylinder assembly, one obtains a relation
for the gas behavior that is given by;
Pv = RT or T=Pv /R - an experimental fact (3)

where R is a gas constant (= Ro /M), Ro is the

universal gas constant (= 8314 J/kmol.K), M is
the molecular mass of the gas (kg/kmol).
(1) For T to be a property of the
thermodynamic system, its change must
satisfy the
continuous
function
requirement. From mathematics, the
total differential of a variable T in terms
of independent variables P and v, that is
T = T(P,v)) :
Partial differential

dT

P v

change in P

dP

(2) Another point to note is that a property is

independent of path. The change from
points A to B (see fig below) can be
obtained by a partial integration of any
path to obtain the total change on a
surface (eg., path C or the sum of
dotted paths).
T

From mathematics, a continuous function of the

form z = z(x,y), the order of partials of z with
respect to x and y would be immaterial, i.e.,
z

z .

x y
y x
y x
x y

Thus, extending this mathematical principle to a

thermodynamic system, we demonstrate that the
continuous function of the property as given by
T = T (P,v), would be

Partial differntial

Change in v

T
dv

v P
(4)
where the subscripts P and v indicate that they
are held constant that follows the partial
gradients of T vs. P and T vs. v, respectively.
Total
differential

From equation (3)- the experimental fact, the

gradients of T to P and T to v are
v
P
T
T
and
(5)

,

P v R
v P R

A continuous
surface

p
Path along
constant P

Path C

Partial differntial

v P

Path along
constant V

Partial differential

P v

2T 2T

v. P P. v

(6)

Differentiating the gas relation again to obtain

the second order differentials, we have
2T T 1 and

v.P v P R

2T T 1 ,

P.v P v R

(7)
Note: we have the same result in Left Hand Side
term = Right Hand Side term in equation (7): Proven the requirement of continuous function.
Hence, we conclude that the equation (3) is a
property of a thermodynamic system because it
satisfies the requirements of a continuous
function.
Furthermore, a property can be expressed in
terms of other thermodynamic properties. This
relation is also known as the equation of state
(EOS) i.e., P v = R T.

Independency Test or Cyclic relation

Independency is also a necessary condition for
being a property in a thermodynamic system. To
4

demonstrate independency of variables in an

equation of state (EOS), we need to use two
mathematical relations in addition to the
thermodynamic relations.

term is a constant (-1). The individual partials

on the RHS can have any value (independent of
each other) as long as their product is summed
to unity,

The first is the chain rule:

z z y

x a y a x a
and the second is the derivative inversion: i.e.,
1
x

z y z

x y
Invoking Equation (4) on the total differential
on the change in temperature (T= T(p,v) ):

An alternate proof of independency with

thermodynamic variables is demonstrated
below by assuming the variables P,v, T of a
thermodynamic system. Let us choose arbitrary
the relations for P and T as P = P (T,v). From
mathematics, the total differential is

T
T
dT
dP
dv
P v
v P

P
P
dP
dT dv
T v
v T

Should we arbitrary select T = T(P,v) as the

variable of interest, then the total differential is
given by

If we now take the partial derivative of each

term with respect to P but at constant T;
=0
=1
dT
T P T v

dP

T P v P T v P P T

Since T is held constant, the only possible

solution for the left hand side term is
dT

0
dP T
and noting that
P
1
P T
Applying the above results and invoking the
derivative inversion rule on the partial
derivative, gives
T
T v
0
1

P v v P P T
or
P T v
1


T v v P P T

This proves the independency requirement of

the variables (P, v, T) in the system as the LHS

T
T
dT
dP
dv
v P
P v

Now, substitute dT of the second equation into

the first equation, and re-arrange, we get
1
0

P T
P T P
1 dP dv
T v P v
T v v P v T

We note that
(i)

dP can have any value, i.e.,

independent of the others if the
product of bracketed terms is equal
P

T
to unity, ie., 1 - this
T v P v
is obviously a trivial solution.

Similarly,
On the right-hand side, dv can have
(ii)
any value, i.e., independent of the
others if

P T P
0

T v v P v T
5

From the second condition of independency,

and re-arranging, we can easily show that
P T v
1


T v v P P T

Hence, we prove again the independency

requirement for P,v and T in a thermodynamic
system. It is a necessary requirement for being a
property of a thermodynamic system.

Example 2.1
Consider the relationship between V, T and P of
a gas contained in a vessel (closed system). If
the experimental relationship between the
expansion and compression coefficients of the
gas are inversely proportional to T and P,
respectively, then from mathematics, derive
from 1st principles the ideal gas law, PV / T =
constant (mR).
Note the definitions of the expansion ( ) and
compression ( ) coefficients for real gases are
respectively given by

1 V
1 V
1
1

and
.
V T P T
V P T P

(note that these approximations are found from

experiments).
Solution:
The general expression for the variables can be
given by
V= V (P,T)

From mathematics, the total differential of V is

given by
V
V
dV
dT
dP
T P
P T

Using the definitions and the experimental

relation of the gas, the above can be re-written
as
dV VdT VdP
dT
dP
V
V
P
T
or
dV dT dP

0
V
T
P
Integrating, we have,
ln(V) - ln(T) + ln(P) = ln (constant),
i.e., taking the anti-log, we arrived at the
equation of state (EOS) of an ideal gas:
PV

cons tan t
cons tan t (= mR)
e

Example 2.2
Estimate the change in the specific volume of
air (assuming ideal gas) if the temperature and
pressure changes are from T1 = 25oC and P1
=122 kPa to T2 =65o C and P2 =102 kPa,
respectively. Compare the changes as calculated
directly from the ideal gas law (as derived in
example 2.1).
Solution:
The relationship for the specific volume is given
by
v
v
dv
dT dP
T P
P T
RT
R
dT 2 dP
P T
P
Here, R= Ro /M = 8314.5 (kJ/kmol.K) / 28.98
(kg/kmol) = 0.287 kJ/kg.K,
Tmean= ((65+25)/2+273.15) = 318.15 K,
Pmean= (122+102)/2 =112 kPa,

 0.287 x103
0.287x103 x318.15

dv
(
40
)

(20x103 )
3
3 2
(112x10 )

112 x10
3
0.1025 0.1457 0.248 m / kg

state of thermal equilibrium. This implies that

A & B are in the same state, 30 oC.
Thermometer :A

Using the ideal gas equation, (Pv=RT), the

specific volume, v = V/m, can also be estimated
by using a finite differencing approach, i.e.,

Thermometer B

Equilibrium with each other

dv v 2 v1
RT RT
2 1
P2 P1
0.287 x338 0.287 x 298

102
122

0.9510 0.7010 0.2499 m 3 / kg.

Obviously, the partial differential approach

provides a more accurate answer than the finite
difference method. The latter employs the
equation of state across the initial and final
states whilst the former tracks the changes of
fluid properties along the paths of processes.

2.1

Zero Law of Thermodynamics

When two bodies are said to be in equilibrium

with each other, they are said to have the same
property (eg., temperature, T). Although we
termed this statement (below) as a law, it can
not be proven mathematically but it is merely a
statement of truth: - that is, an axiom.
The Zero Law states that when two systems,
are each in mutual equilibrium with a third
system, they are also in equilibrium with each
other in the same manner
Let us illustrate this statement graphically. Say,
a master thermometer, such as a mercury-inbulb type, has an accuracy of 30 0.05o C. Now
one brings but separately the thermometer A
to be in equilibrium with C and thermometer
B to be with C. According to the Zero Law,
if B & C are said to be in thermal
equilibrium, then A&C are also in the same

Master thermometer C
However, many students/researchers tend to
extrapolate the results to imply that
thermometers A & C would have the same
accuracy of 0.05o C. Accuracy of instrument
does not follow in such calibration techniques as
the latter is dependent only on the properties of
instrument.

2.2

Units

Before proceeding further, it is timely to

examine the units that are likely to come across
in this course and they are tabulated below:
Quantity
Length
Mass
Time
Electric current
Temperature
Amount
of
substance
Solid angle
Plane angle
Energy
Pressure
Atm pressure
Specific internal
energy
Specific enthalpy
Specific entropy

Units
meter
kilogram
seconds
Ampere
Kelvin
mole

SI symbols
m
kg
s
A
K
mol.

Steradian
Radian
Joule
Pascal;
Bar
J/kg

sr
rad
J
Pa
105 Pa
u

J/kg
J/kg.K

h
s

2.3 Empirical and Thermodynamic

Temperature scales
Have you ever wondered how a
numerical number of a temperature scale at ice
point of water takes a value of 273.15 K or
491.67 R ? Why not any other numerical
numbers?
One employs an instrument to read the
temperature of a body. This implies that the
sensor device has a thermometric property, X,
(measurable changes) that responds to the
changes in the temperature of a body. Some of
the commonly used devices are as follows:

a
liquid-in-bulb
device,
called
thermometer (X= expansion of liquid)
resistance change of an inert wire,
called resistance-temperature device or
RTD, - (X= change in resistance)
the electro-motive force generated across
a pair of wires of different materials,
called the thermocouples, (X= change in
electro-motive force or emf.).
the constant-volume bulb with pressure
changes (indicated by mercury), called
constant-volume bulb thermometer,
(X=change in gas pressures and hence
the liquid column).

For any of the above-mentioned devices, if X

denotes the thermometric property, the ratio of
thermometric
properties
across
two
temperatures (easily reproducible) is described
by a linear empirical law,
X2
2

1 X 1 or reference

(8)

The below figure shows a schematic of a

constant-volume bulb thermometer. It comprises
a bulb of finite volume, a connecting tubing
with a marked point, a U-tube with one end
open to atmosphere and a bottom connection to
a flexible tubing where the other end is attached
to a reservoir containing a fluid, say mercury.
The volume in the gas bulb is always held
constant by adjusting the height of the reservoir
in the flexible arm. When a temperature change
of the surroundings of the bulb changes, it
causes the pressure in the bulb to vary.
From equation (8), the empirical temperature is
height of columns

h2
P
2 X 2
given by

2 , (9)
1 X 1
h1
P1

Gas bulb
containing
gas
molecules

where the variable X is dependent on the type of

instrument used.

Constant-Volume
Gas
Thermometer (CVGB)

Bulb

The state 1 of equation (9) refers to a

reference temperature (3), taken to be the
triple-point of water, 3 (a state where three
8

phases of water co-exist). In general, the

empirical equation becomes

X
P

.
3 X 3
P3

(10)

Based on experiments reported in the literature,

the thermometric properties of three types of
temperature sensors are compared, using the
common physically reproducible states such as
the boiling point (NBP), melting point (NMP),
triple point (TP), etc. For example,

Thermocouples (X = electro-motive
force or emf)
RTDs (X = Resistance in Ohms)
CVGB (X= Pressure of gas)

The table below compares the thermometric

variables for six types of natural phenomena
(such as Normal Boiling Point (NBP), Normal
Sublimation Point (NSP), Normal Melting Point
(NMP), Triple Point (TP), etc.) of Nitrogen,
Oxygen, water (H2O), Tin (Sn) etc.:
Thermo RTD CVGB
Natural
points of couples sensor
pure
P
R
substances
3
P3
R3
N2 (NBP) 0.12
0.20
0.27
O2 (NBP) 0.15
0.25
0.31
CO2
0.56
0.68
0.71
(NSP)
H2O (TP) 1.0
1.0
1.0
H2O
1.51
1.30
1.37
(NBP)
Sn (NMP) 2.79
1.89
1.97
NBP= normal boiling point; NSP=
sublimation point; TP= triple-phase
NMP= normal melting point.

CVGB

P
P3

numbers

of

an

The answer lies in the celebrated experiments of

Lord Kelvin where he employed the CVGB
thermometer (the gas inside the bulb follows
thermodynamic behavior), filled (i) with
different types of gases such as O2, N2, H2, and
air and (ii) at assorted gas-bulb pressures
(partial vacuum) when measuring the triple
point and boiling states of water, that is
.
The CVGB thermometer is first filled

with one of the mentioned gases at 1000

Torr (1 Torr = 1mm Hg or 101.325/741=
0.136 kPa). Experiments were carried
out for two points, namely the triple
point of water (where 3-phases of water
could be formed when Psat = 0.006112
bar) and the boiling point of water at
ambient pressure (boiling could be
observed) and record the values of
thermometric readings, Ps/P3.
Evacuate
the gas bulb slightly, say to

750 Torr, and repeat the experiments to

obtain various readings of Ps/P3
Repeat the steps with a lower gas

pressure in the CVGB thermometer,

until near vacuum.

0.29
0.33
0.72

Ps
P3

1.0
1.37

1.3680

The extrapolated values of

Ps/P3 when pressure in bulb
approaches zero.
1.3661

O2
N2

1.3670
1.85
normal
point;

Let us now re-visit the question posed at the

beginning of section 2.3. How are the

numerical

temperature scale (K or R) for the

freezing or boiling point of water
assigned?

absolute

Air

1.3660

H2

1.3650
250

500

750

1000

P3 (Torr),

A plot of Ps/P3 versus the gas pressure in the

bulb is then plotted, as shown above. There are
two important facts needed to formulate the
numerical values, namely;

The arbitrary number of divisions (A)

assigned between the steam to ice point
(nearly at Triple Point),i.e.,

s i A,
where

set no of divisions

(11)
A 100 or 180,

The experimental value of the

thermometric property at steam point to
the triple point, Ps/P3, see the
experiments, i.e.,

100
100

273.15
Ps
0.3661
1
Pi

273.16

NBP of H2O

373.15

100

671.67

212

100
divisions

180
divisions

273.15

491.67

32

NBP of O2

90

-183

162

-297

Absolute
Zero

-273.15

-459.67

(13)

Example 2.3

This is called the Kelvin scale (or K). Since, the

triple point is found to be 0.01 K higher than the
ice point, the thermometric formulae for the
CVGB thermometer is written with triple point
as the reference point;

T B

(12)

From equations (11) and (12), for an arbitrary

number of A, say 100 divisions on a selected
temperature scale, one obtains

Equivalent between
empirical and ther mod ynamic
temperatures ,

In the International Temperature and Pressure

Systems (ITPS) meeting (some 6 decades ago),
all scientists/engineers from many countries
agreed to employ only two temperature scales in
honour of Celsius (100 divisions) and Rankine
(180 divisions). In principle, you could select
say 50 or any number of divisions but it will be
unlikely to have anyone using the new scale.

NFP of H2O

s s PS

1.3661
3 i P3

B=1). Should the number of divisions used in

equations (11) or (13) is set to 180 (as in
Fahrenheit scale), then the freezing point of
water is 491.67, or known as the Rankine scale.

P
P3

(14)

where the empirical temperature () is now

equivalent to absolute temperatures (T). This is
because the gases (molecules) in a constantvolume gas bulb thermometer () obeys the
Laws of Thermodynamics (hence. the constant

This exercise relates to the expansion or

contraction coefficients when a liquid
experiences a change in temperature.
The volume of mercury contained in a bulb type
thermometer is Vb,o (m3) at ice point. If the
capillary of thermometer has a cross sectional
area As,o (m2) and the linear expansion
coefficients of glass and mercury are
G (1 / K ) and m (1 / K ) respectively, determine
the change in height of mercury column for a
small change in temperature, t (K)?
Solution:

10

The incremental increase in the volume of

mercury (that fills the bulb and stem) due to its
properties being sensitive to a t change is
given by;
effect of t

V1 Vb ,o Vb ,o m t Vb ,o (1 m t )

where subscript 1 refers to the state after there

is a small change in the temperature. Similarly,
the effect of temperature change on the crosssectional area of capillary tube (stem) is given
by
effect of temperature , t

As ,1 ( rs , o

rs , o G t

small 0

2
rs , o (1 2 G t ( G t ) 2 )

(Vb ,o Vs ,o )(1 m t ) V b ,o(1 3 G t )

hAs ,o (1 2 G t )

After re-arranging, that is

Vb ,o m 3 G

t
As ,o 1 2 G t

where h is the height of mercury in the stem in

meter. Note that t = (t - to). Note that this
exercise is for a simple case where hs,o=0.
This expression is important when making of a
master thermometer. The typical values of
G 1 / K and m 1 / K are 910-9 [1/K] and
210-4 [1/K] for the glass and mercury,
respectively.

A s , o (1 2 G t )
A picture of the process is shown below:
Similarly, the effect of a temperature change on
the volume of glass bulb is

4
Vb ,1 ( rb ,o
3

As1h

effect of t on radius rbo

rb ,o G t

)3

0
small
terms

bycomparison

4 3
2
rb ,o (1 3 G t 3( G t ) ( G t )3 )
3
V b ,o(1 3 G t )

Simultaneously, the mercury (liquid), also

expands due to a temperature change, would
have to fill the cavity left behind by expanded
glass tube and the expanded bulb, i.e.,
exp ended mercury

V1

new bulb volume

Vb ,1

new capillary volume

As ,1h

Note that Vs ,o =0 (the stem initially is hs,o=0)

hso=0

h
V1=Vb,1 +
As1h

Vbo
to =T C

Vb,1
t= T+t

If the initial height in the tube is hs,o( 0), show

that the change in height is given by
A h

m 3 G so so (2 G m )
Vbo
V t

hs1 hso o

Aso
1 2 G t

If t = 0, then h equals to zero (naught). Also,

11

if hso is zero (the mercury is just at the brim of

bulb), then the expression reverts back to the
earlier case shown in example 2.3.
Home Assignment #1
(Please submit to your tutor (during tutorial
session) two weeks after the lecture of Chapter 2.
It carries 2.5 marks out of 10 marks).

Question:
Experiments were conducted using a constant
volume gas bulb (CVGB) thermometer to
measure the triple-point of water (where 3
phases of water co-exist). Four types of gas
were used in the CVGB thermometer to
measure this condition.

(a) Write down the empirical temperature

scale for the gases at any temperature, .
(b) If the numerical number for the triple
point of water is adopted internationally
as * = T* = 273.16 K, then, write down
the absolutely temperature scale T(K).
(c) From the figure, demonstrate that the gas
constant is 82.05 cm3.atm/mol.K or
8.314 J/mol.K. (Note: 1 atm = 1.01325
bar, 1 m3 = 106 cm3). Explain, briefly,
why this is a universal value?
(d) Explain why the product PV converges
to a single point in the experiments?

For each type of gas charged into the

thermometer, the product of pressure and
volume of gas of sensor, i.e., (PV), is calculated.
By varying the gas pressure charged into the
thermometer, say from 250 Torr to 1000 Torr, a
range of PV readings of the CVGB are taken
and recorded against the charged pressures.

Q1. The behaviour of an ideal gas in a

thermodynamic system can be expressed by
three variables in an explicit form:

These experiments are repeated for H2, N2, Air

and O2. As the charged pressure of gas in the
CVGB thermometer reduces to zero (P 0), as
shown in the figure below, the product (PV)* at
the triple point of water converges to a single
value of 22414 cm3.atm/g.mol.

RT

v
where R is a gas constant [J/kg.K]; P, T and v
are the pressure (Pa), temperature in Kelvin [K]
and specific volume of the gas [m3/kg],
respectively. Using mathematics, show that

Tutorial #1 (Chapter 2 ME2121/2121E)

(i)
*

T = Ttriple point, of water=273.16 K

(PV)

H2
N2
Air
O2

(PV)*P0 = 22414
cm3.atm/g.mol
0

250

500

750

1000

P (Torr)

(ii)

the variable, P, is a property of

the thermodynamic system,
the remaining variables, T and v,
as specified in the given relation,
are independent of each other.

(Hint: Read up the requirements of exact

differentials and the test for independency of an
exact function.)
Q2. A mass of gas is trapped in a cylinder fitted
with a leak-proof piston. The initial temperature
and pressure of the gas are 30C and 3 bar. The
pressure of the gas in the cylinder is then

12

reduced to 2.5 bar and its temperature is

increased to 60C.
Describe qualitatively, how you would conduct
the above-mentioned process in a quasi-static
manner. You may make suitable assumption(s)
about the boundary and the surroundings.
Would friction between the wall and piston
affect your answer?
(There is no exact answer for this question. You
should read up on the basic definitions and the
concept of heat and work interactions for a
simple system).
Q3. Write down the thermometric property of a
mercury-in-glass thermometer. The length of a
mercury column in a mercury-in-glass
thermometer is 5 cm when it is in contact with
water at triple point. Calculate
(a) the empirical temperature when the
mercury length is at 6 cm,
(b) the length of mercury column when
it is at steam point,
(c) If the thermometric property X of
the sensor can be read with a precision of 0.1
mm (height of the mercury column of CVGB),
what is the error uncertainty of a measurement
of temperature difference, i.e., dT = (T1 T2)?

Note: From mathematics, the uncertainty of a

variable (f) is given by =

e xi .

i 1 xi

i k

You may wish to read about experimental

uncertainty in a paper by RJ Moffat, entitled,
Describing the Uncertainties in Experimental
Results, Robert J. Moffat, Experimental
Thermal and Fluid Science 1988; 1:3-17.

experimental value of vapour pressures between

the ratio of the boiling to the ice point of water
is found to be
Ps
1.3661
Pi
where the subscripts s and i refer to the steam
and ice points, respectively (See attached figure).
If an engineer decides to have an absolute
temperature scale that divides equally in 50
divisions between the boiling (steam) and ice
points of water (i), show from first principles
that the numerical numbers for such an absolute
temperature scale (called the S Scale for
convenience) at these states of water are 136.57
S and 186.57 S, respectively.

P (torr)

Ps = pressure at steam (boiling) point of

water,
P3 = triple-point of water, which is 0.01 K
higher than ice point of water (i).
1 Torr = pressure at 1 mm of mercury (1 atm
= 746 mm Hg)
The Y-axis is (Ps / P3) which is the ratio of the
gas pressure in Constant-Volume Gas Bulb
(CVGB) thermometer when the bulb is dipped
separately in steam point and triple point of
water.
-- End of Tutorial #1 --

Ans: (a) 327.8 K, (b) 6.83 cm, (c) 0.77 K.

Q4. Write down the thermometric property of a
constant-volume gas thermometer. The best

13