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ME2121/ TM1121- Thermodynamics

Chapter 2 1/ 19

Definitions and Basic Concepts

What is a thermodynamic system?
A close system is one
where no mass leaves
or enters the boundary.
System boundary

Work transfer,
dW

Energy content of
matter, dE = dU

Heat transfer
dQ

Matter
Eg. Gases, liquids,
solids

An open system is one

where mass enters and leaves
the boundary.

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ME2121/ TM1121- Thermodynamics

Chapter 2 2/ 19

System characterizes by properties (P,T, V, U, H, S etc.),

Property measures the state of matter(s), it describes
two states to form a process,
property can be defined by other established properties,
e.g., enthalpy (H) is given by (in extensive form)
U = U (P,T) or U = U (P,V)
and H =H (P,T) = H (P,V)= U + PV
Piston-cylinder

Measured by P, T, V
work

Gas, dU
dW

dQ

V
H U
p
m
m m
h u Pv

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ME2121/ TM1121- Thermodynamics

Chapter 2 3/ 19

Quantity of matters
Use SI units (kg, m, mol, s, J, radians, etc)
Mol. Is a basic measure of matter, eg. kmol of
Carbon (C12) has a mass of 12 kg.
For gases at STP, 1 kmol has 6.023 x 1026
gaseous molecules
Conversion between gravimetric (mass) analysis
to volumetric (molar) analysis is via the molecular
mass (M),
Eg.,

ni = mi / Mi

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ME2121/ TM1121- Thermodynamics

Chapter 2 4/ 19

Cycle and property

A cycle requires two or more processes to complete
The summation of a thermodynamic variable for a
cycle leads to
Y=P

2
(P2, v2)

Equation of state (EoS),

eg., PV = mRT
Or PV = nRo T

Path A

Path B
1
(P1, v1)

x= v

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ME2121/ TM1121- Thermodynamics

Chapter 2 5/ 19

Mathematical tests of a property

A property satisfies continuum requirement and from maths,
Total
Partial differntial
Partial differential

differenti
al
change
in
y
Change
in x

z
z

dx
dz
dy

x y
x

and if continuous, then it satisfy the following identity

(exactness requirement):
z z

Order of differentiation is
y x x y
immaterial.
y x
x y

Letting z= T, x = P, y= v, and writing for the total change in dT,

the function is T = T(P,v)
T
T
dT
dP
dv
P v
v P

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Chapter 2 6/ 19

Invoking exactness,
2T 2T

v.P P.v

For ideal gas, the equation of state is Pv=RT,

differentiating twice
T 1
T P
and

P v R
v R

T 1

v.P R
2

and

2T 1

P.v R

The other requirement of a property is

independency.

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ME2121/ TM1121- Thermodynamics

Chapter 2 7/ 19

Test for independency (Tutorial#1, Q1)

P = P(T,v); and T=T(P,v)

Writing for total differentials

T
T
P
P
dT
dP

dP
dv

dT dv and
v P
P v
v T
T v
Step 1

Step 2

To show that the mathematical requirement for

independency (by inter-substituting)

Re-arranging
P and V can take any value when
the bracketed terms are zero.

P T v
1

T v v P P T
Step 3
PV= (R)T ,
Equation of state

Worked example 2.1

Consider an ideal gas in a system where
the gas has its expansivity ( ) and
compressibilty
( ) expressed as

Using the definitions and the experimental

relation of the gas, the above can be rewritten as

By experiments

1 V
1

V T P T

dV VdT VdP

1 V
1

V P T P

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

V
V
dV
dT
dP
T P
P T

Replace &

dT
dP
V
T
P

or
dV dT dP

0
V
T
P
And taking log, we have,
ln V- ln T + ln P =ln (constant),
That is, the equation of state
(EoS)

PV

cons tan t
T

and the cons tan t is (mR )

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ME2121/ TM1121- Thermodynamics

Chapter 2 10/ 19

Zero Law of Thermodynamics

Thermometer A

Equilibrium with each other

Thermometer B

Thermodynamic
equilibrium

Thermodynamic
equilibrium

Master thermometer

Thermometric property of sensor,

2
X2

1 X 1 or reference

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ME2121/ TM1121- Thermodynamics

Chapter 2 11/ 19

Types of temperature measuring devices

a liquid-in-bulb device, called thermometer (X=
expansion of liquid represented by height of column)
resistance change of an inert wire, called resistancetemperature device or RTD, - (X=change in R (ohms))
the electro-motive force generated across a pair of wires
of different materials, called the thermocouples, (X=
change in e.m.f.(micro-volts).
the constant-volume bulb with pressure changes
(mercury in tube), (X= change in gas pressures (Pa)).
2 X 2 h2 P2

1 X 1 h1 P1

empirical temperature, X thermometric property

ME2121/ TM1121- Thermodynamics

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Chapter 2 12/ 19

Constant-volume bulb
thermometer ( 3 triple
point of water, s steam
point)

Gas
molecules
inside the
bulb

Ps/P3
O2

1.3661
1.3680

N2

1.3670

Air

1.3660

H2

1.3650

250

500

750
P3 (Torr)

1000

Temperature
to be
determined

P3 = is the pressure
at the triple point, 1 torr = 1/1000 mm hg

How do you calibrate?

Reading of mercury height is an indication
of the Pressure (P) of gas in the bulb,
Immerse the bulb into a reference
temperature (i.e., the triple point of water),
Then immerse the bulb into an environment
of steam (boiling water) at 1 atm.,
Evacuate some gas out of the bulb and
repeat the processes,
Plot the ratio, Ps /P3 to P3 using the
experimental data
Triple point of
water where all
3 phase of water
can co-exist.

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ME2121/ TM1121- Thermodynamics

Chapter 2 13/ 19

How are the numerical numbers of an

absolute temperature scale assigned?
Require two pieces of information,
(a) The number of divisions between freezing point and ice point,

s i 100 or 180 or a cons tan t " A",

(b) The thermometric property ratio of a thermometer (that follows
the thermodynamics law), eg., constant volume bulb thermometer.

s P

1.3661
i Pi
Solving,

100
100
i

273.15 K
Ps
1 0.3661
Pi

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ME2121/ TM1121- Thermodynamics

Chapter 2 14/ 19

Other absolute temperature scales

oC

oF

NBP of H2O

373.15

100

671.67

212

NFP of H2O

273.15

491.67

32

90

-183

162

-297

-273.15

NBP of O2
Absolute
Zero

-459.67

Tutorial #1, Q4

The thermometric property of a constant-volume bulb thermometer is

s Ps

3 P3

where subscript s refers to steam point, and 3 refers to the triple point of
water (0.01 C).
Needed two information to define a temperature scale: (i) the number of
divisions between ice point and boiling of water, (ii) the ratio of Psteam to Pice =
1.3661 (see lecture notes also).

s i 50,
and

s Ps
1.3661 (an experimental fact)
i Pi
solving these two equations, we have
i 136.57 deg and s 50 136.57 186.57 deg.

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ME2121/ TM1121- Thermodynamics

Chapter 2 16/ 19

Example 2.2
The volume of mercury contained in a bulb type
thermometer is Vo (m3) at ice point. If the capillary
of thermometer has a cross sectional area Ao (m2)
and the linear and volume expansion coefficients
of glass and mercury are
, respectively,

G and m

determine the change in height (m) of mercury

column for a small change in temperature, (K)?

ME2121/ TM1121- Thermodynamics

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Chapter 2 17/ 19

Graphical interpretation

K-1

effect of t

V2 V1 V1 m t Vb1 (1 m t )
increase in stem area
effect of t

A2 ( r1 r1 G t ) 2

small

2
r1 (1 2 G t ( G t ) 2 )
A1 (1 2 G t )

For a T, increase in mercury volume

stem

A 2h 2

h1

h2

V2=V,b2 + A2h2

bulb
V0=Vb1+A1h1

t=0oC

Vb2

t= 0+t (C)

Increase on bulb volume

effect of t

4
Vb 2 ( r1 r1 G t ) 3
3
4
r13 (1 3 G t )
3
V b1(1 3 G t )

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Mercury volume

ME2121/ TM1121- Thermodynamics

New bulb volume

Chapter 2 18/ 19

New stem volume

re-arranging, we obtained
Vo
h
Ao

m 3 G

t
1 2 G t

Should h1 0 , then initial volume of mercury in thermometer is V0 = Vb1 + A1h1.

(Vb1 +A1 h1)(1+m t) = (Vb1 )(1+3G t)+h A1 (1+2G t)

You can re-arrange the expression to find the new height, h?.

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ME2121/ TM1121- Thermodynamics

Chapter 2 19/ 19

Home exercise (the case when h1 is not

naught. May worth your while to derive!)
A1h1

(2 G m )
m 3 G
V1t
V1

h2 h1

A1
1 2 G t

and if h1 0, then equation revert to previous solution.

and Tutorial #1- (4 challenging questions.

Q1 & Q4 are past year exam questions)

Home assignment #1 (Chapter 2)

An experiment is conducted for four types of gases where the product,
pressure and volume, (PV), of each gas is monitored at a reproducible
temperature of water, namely the triple point of water. These experiments
are repeated consecutively with the gas pressure in the apparatus is
reduced, P0, as shown in the figure below.
Write down the empirical temperature scale for
the gases at any temperature, .
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).
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?

Example 2.1 (b) of Notes

v
dv

v
dv dp
P T

v
dv
dT
T P

Actual 3-D surface

of specific volume

T
Here, R= Ro/M = 0.287 kJ/kg.K,
Tmean= 318 K, Pmean= 112 kPa,
using total differential,

0.287 x10 3 x318

0.287 x10 3
(20 x10 3 )
(40)
dv
3
2

112 x10 3
112 x10

0.1025 0.1455 0.248 m 3 / kg

v
v
dv
dT dP
P T
T P
R
RT
dT 2 dP
P
P T
From the ideal gas equation, dv can
also be estimated, i.e.,
v2
v1

RT RT 0.287 x338
dv 2 1

102

P2 P1
0.287 x 298

122

0.9510 0.7010 0.2499 m 3 / kg.