Thermodynamics Part I (Student Version)

Dr.
Hong Nam Nguyen

General Education Department
nguyen-hong.nam@usth.edu.vn
Table of Contents
• Overview and basic concept of thermodynamics

• Temperature, Heat, and the First Law of Thermodynamics
• The kinetics theory of gases
• Second law of Thermodynamics and applications
2
Evaluation
• Attendance: 10% (final exam prohibited for those absent
>30%)
• Mid-term exam + participation in tutorial classes (30%)
• Final exam (60%)
• Bonus (10%)
3
I. Overview and basic concepts
Outcomes
• Remember the historical development of
thermodynamics as a branch of science
• Understand some terminologies in
thermodynamics
• Understand some basic concepts in
thermodynamics
4
Thermodynamics
• Heat (thermo) + movement (dynamics)
• A branch of science which deals with energy
transfer and its effects on properties (physical and
chemical) of the substance
• Lots of applications in daily life and industries
are engineered using the principles of
thermodynamics
5
6
7
Thermodynamics as a
scientific discipline
• 1650: Otto von Guericke (German scientist)
built and designed the first vacuum pump
• 1656: Robert Boyle (Anglo-Irish physicist and
chemist) in coordination with Robert Hooke
(English scientist) built an air pump.
• 1679: Denis Papin (French physicist and
Otto von Guericke (1602 – 1686) mathematician) built a steam digester
8
Thermodynamics as a
• 1697: Thomas Savery (English inventor and
engineer) built the first engine
• 1824: Sadi Carnot (French engineer) - "father
of thermodynamics", published Reflections on the
Motive Power of Fire, a discourse on heat, power,
energy and engine efficiency.
Nicolas Léonard Sadi Carnot
(1796 – 1832) 7
Thermodynamics as a
• 1873–76: Josiah Willard Gibbs (American
mathematical physicist) showed how thermodynamic
processes could be graphically analyzed
• Early 20th century: Gilbert N. Lewis, Merle
Randall, and E. A. Guggenheim (chemists) applied
the mathematical methods of Gibbs to the analysis of
chemical processes.
William Thomson
(1824 – 1907) 8
Basic concepts
• Open system: both energy interactions and mass
interactions take place
• Closed system: only energy interactions and no
mass interactions take place
• Isolated system: no energy interactions and no
mass interactions take place
11
Basic concepts
• Macroscopic system is concerned with the
effects of a certain number of matter, and these
effects can be perceived by human senses.
• Macroscopic properties: The properties
associated with a macroscopic system, i.e. pressure,
volume, temperature, density, composition,
viscosity, surface tension, refractive index, colour,
etc.
12
Basic concepts
• Microscopic system is concerned with the
effects of the action of many molecules, and these
effects cannot be perceived by human senses.
• Microscopic properties: The properties
associated with a microscopic system, i.e. molar
mass, velocity of atoms or molecules, momentum,
kinetic energy, etc.
13
Basic concepts
• Intensive (intrinsic)
properties: properties
that are independent of
the mass of the system
• Extensive (extrinsic)
properties: properties that
are dependent of the mass
of the system
14
Basic concepts
• State: defined by specifying values of a set of
measurable properties sufficient to determine all
other properties. Ex: The state of fluid systems
requires typical properties are (V, T, P).
• Process: any change of state of the system
• Process path: infinite states through which the
system passes while going from initial state to
final state
15
Basic concepts
•Reversible process: Ex:
uniform and slow
expansion or compression
of a fluid in a piston
• Irreversible process:
Ex: Heat transfer, Diffusion
Electricity flow through a
resistance
(In reality no process is really

“reversible”)
16
Thermal Equi.
Basic concepts
Mechanical • Thermodynamic equilibrium: there is no
Equi.
tendency for the state of a system to change
spontaneously.
Chemical • E.g.: the gas in a cylinder with a movable piston
Equi.
will be at equilibrium if T & P inside are uniform
and if the restraining force on the piston is just
sufficient to keep it from moving.
Phase
Equi.
17
II. Temperature, heat and
The First law of thermodynamics
Outcomes
• Understand the concept of temperature
• Understand the concept of heat
• Apply the first law of thermodynamics
18
Temperature Temperature
• The degree or intensity of
heat present in a substance
or object
• Express the “hotness” or
“coldness” of matter or
radiation.
• 1 of the 7 SI base unit
• What are they?
• Conversions of
temperature scales:
TK = TC + 273.15
TC = (5/9)(TF – 32)
19
Temperature Zeroth law
• “If bodies A and B are
each in thermal equilibrium
with a third body T, then A
and Bare in thermal
equilibrium with each other”
• In less formal language:
When two bodies are in
thermal equilibrium, their
temperatures are equal.
• Why it has the name of 0th
law?
• Came to light in the 1930s,
long after the 1st and 2nd laws
had been discovered and
numbered. 20
Zeroth law
• “If bodies A and B are
each in thermal
equilibrium with a third
body T, then A and Bare
in thermal equilibrium
with each other”
21
Temperature Thermal
Linear expansion: If temperature of a metal rod of length L is expansion
raised by an amount ΔT, its length is found to increase by: • The tendency of matter
to change its shape, area,
α: coefficient of linear expansion volume and density in
response to a change in
temperature
• Why is that possible?
• With the added energy,
the atoms can move a bit
Volume expansion: If the temperature of a solid or liquid farther from one another
whose volume is V is increased by an amount ΔT, the increase than usual, against the
in volume is: spring-like interatomic
β: coefficient of volume expansion forces that hold every
22
solid together
Temperature Thermal
expansion
• Why is thermal
expansion important?
• Thermal expansion of
materials with an increase
Truck buckling due to thermal expansion
in temperature must be
anticipated in many
common situations.
23
Heat Heat
The energy transferred from
one medium or object to
another because of a
temperature difference that
exists between them
Is heat an intrinsic
property of a system?
No! They have meaning

only as they describe the
transfer of energy into or
out of a system.
24
Heat Heat
Unit of heat?
Before 1948: Calorie/Btu

(Before scientists realized
that heat is transferred
energy, heat was measured in
terms of its ability to raise
temperature of water)
After 1948: Joule (Scientists

decided that heat (like work)
is transferred energy)
1cal = 3.968x 10-3 Btu

= 4.1868 J 25
Specific Heat Heat
If heat Q is absorbed by an object, the object’s temperature • C : heat capacity of
change Tf and Ti is related to Q by: an object (J/K)
• What is the meaning?
(the amount of heat
If the object has mass m : required to change the
temperature of a given
amount of matter by 1
unit of temperature).
• c : specific heat of a unit
mass of material of which
the object is made
(J/kg.K)
26
Specific heat
IMPORTANT: When using the specific heat of any substance,
we need to know the conditions under which energy is
transferred as heat.
For solids and liquids, we usually assume that the sample is:
- Under constant pressure (usually atmospheric) during the
transfer.
- Held at constant volume while the heat is absorbed.
→Cv and Cp differ usually by no more than a few percent.
For gases: quite different values for their specific heats under
constant-pressure conditions and under constant-volume
conditions.
27
Heat of transformation • L : heat of transformation (J/Kg)
• Lv : Heat of vaporization
Melting. To melt a solid means to change it from the solid Water at its normal boiling or
state to the liquid state condensation temperature:
Vaporizing. To vaporize a liquid means to change it from Lv = 539 cal/g = 40.7 kJ/mol
the liquid state to the vapor (gas) state. = 2256 kJ/kg
Amount of energy required to change the state - but not the • Lf : Heat of fusion
temperature - of a particular material of mass m: Water at its normal freezing or
melting temperature:
Lf = 79.5 cal/g = 6.01 kJ/mol
= 333 kJ/kg
28
Exercise
(a) How much heat must be absorbed by ice
of mass m =720 g at -10°C to take it to
the liquid state at 15°C?
(b) If we supply the ice with a total energy of
only 210 kJ (as heat), what are the final
state and temperature of the water?
Copyrights @ Hello Techie Vietnam

24
Copyrights @ Hello Techie Vietnam
The First law of Thermodynamics How energy can be
transferred as heat and work
between a system and its
• A formulation of the law of conservation of energy: the environment?
total energy of any isolated system, which cannot exchange energy
or matter, is constant. Energy can be transformed from one form
to another, but can be neither created nor destroyed.
• Adapted for thermodynamic processes.
• It distinguishes two forms of energy transfer: heat and

thermodynamic work for a system of a constant
amount of matter.
• It defines the internal energy of a system, an

extensive property for taking account of the balance of
31
energies in the system.
The First law of Thermodynamics
Let consider an isolated system: Question:
A gas confined to a cylinder with
a movable piston
How energy can be
The upward force on the piston
= the weight of lead shot between a system and its
environment?
The bottom rests on a reservoir
for thermal energy
The walls does not allow any

transfer of energy as heat
32
Question:
The system (the gas) starts from:
How energy can be
an initial state (Pi, Vi,,Ti) transferred as heat and work
to between a system and its
a final state (Pf, Vf,,Tf) environment?
Here, we perform
a thermodynamic
process
33
Question:
Energy as heat (Q) may be
transferred into the system from
How energy can be
the thermal reservoir (+ Q) or vice
versa (- Q).
Work (W) can be done by the between a system and its
system to raise the loaded piston environment?
(+ W) or lower it (- W).
Assume that all such changes
occur slowly -> the system is
always in (approximate) thermal
equilibrium
34
If a few lead shot is removed, the gas

Question:
pushes the piston upward through a
differential displacement with an How energy can be
upward force . transferred as heat and work
We can assume that is constant environment?
during this tiny displacement. Then:
=pA
p: pressure of the gas
A: the face area of the piston.
35
Question:
Differential work dW done by the gas
during displacement: How energy can be
environment?
dV: differential change in gas volume
due to piston’s movement
36
Question:
When enough shot is removed to allow
the gas to change from V i to Vf: How energy can be
environment?
To evaluate the work, weneed to know how pressure varies
with volume for the actual process by which the system changes
from state i to state f
37
PV diagram:
A pressure–volume diagram
(or PV diagram, or volume–
pressure loop) is used to
describe corresponding
changes in volume and
pressure in a system
38
PV diagram:
A pressure–volume diagram
(or PV diagram, or volume–
pressure loop) is used to
describe corresponding
changes in volume and
pressure in a system
39
To sump up:
• A system can be taken from a given initial state
to a given final state by an infinite number of
processes.
• Heat Q and work W are path-dependent quantities.
40
However…
• Q –W is the same for all processes!
• Must represent a change in some intrinsic
property of the system: Internal energy Eint
41
The internal energy Eint of a systemtends to

The first law of increase if energy is added as heat Q
and tends to decrease if energy is lost as work W
thermodynamics done by the system
ΔEint = Eint,f – Eint,i =Q - W
42
BE CARREFUL OF THE SIGN!!

The first law of
Q positive heat added to the system
thermodynamics Q negative: Heat lost from the system
W positive : work done by the system
W negative: work done on the system
ΔEint = Eint,f – Eint,i =Q - W
43
44
The First law of Thermodynamics: special cases
Constant-volume If the volume of a system is held

constant, that system can do no work:
process W=0
If heat is absorbed by a system (Q
>0), the internal energy increases
If heat is lost during the process
ΔEint = Q (Q <0), the internal energy decreases
45
1. Expulsion of heat in heat engines:

waste heat is expelled right after the
Constant-volume vehicle receives power from
combustion, but since the piston is not
process in real life? moving, the volume of the chamber is
unchanging and the pressure drops.
2. Boiling of water in a pressure cooker:
When heat is transferred to the
container, isovolumetric process is
done since temperature and pressure
increase is done at a constant volume.
46
A process that occurs so rapidly or
occurs in a system that is so well
Adiabatic process insulated that no transfer of energy as heat
occurs between the system and its
environment: Q = 0
If work is done by the system (W >0),
ΔEint = - W the internal energy decreases by the
amount of work.
If work is done on the system (W <0),
the internal energy increases by by the
amount of work.
47
1. Insulate the system: A vacuum
flask does a good job of retaining
Adiabatic process in heat - because of it’s insulation.
real life? 2. Do not insulate the system:

An expanding and contracting sound
wave (air compression and
decompression) is a good example. It
happens far too quickly for inflow or
outflow of heat.
48
After certain interchanges of heat and
work, the system is restored to its
Cyclical process initial state: ΔEint = 0
The net work done during the process
(Closed cycle) must exactly equal the net amount of
energy transferred as heat
The store of internal energy of the
system remains unchanged
Q= W
49
1. All the real cyclics behave as non-
cyclical process, but…
Cyclical process in real 2. A cyclic process is the underlying
life? principle for an engine.
50
Adiabatic processes in which no
transfer of heat occurs between the
system and its environment and no
Free expanssions work is done on or by the system:
Q= W = 0
ΔEint = 0
51
40
1. ΔEint =0 means that the process is isothermic. True or False?
a) True
b) False
2. Relation between the internal energy and heat supplied in the process 1 & 2?
a) ΔEin1 > ΔEin2, Q1 > Q2
b) ΔEin1 < U2, Q1 > Q2
c) ΔEin1 = ΔEin2, ΔEin1 = ΔEin2
d) ΔEin1 = ΔEin2, Q1 > Q2
40
3. True or False?
a) ΔEint = -W in an isothermal process
b) ΔEint = W in an isothermal process
c) ΔEint = -W in an adiabatic process
d) ΔEint = -W in an adiabatic process
4. A system is taken from state A to state B along two different paths, 1 and 2, then:
a) Q1 = Q2
b) W1 = W2
c) Q1 – W1 = Q2 – W2
d) Q1 + W1 = Q2 + W2
40
Exercise
◦ Let 1.00 kg of liquid water at 100°C be
converted to steam at 100°C by boiling at
standard atmospheric pressure.
◦ The volume of that water changes from an
initial value of 1.00 x 103 m3 as a liquid to
1.671 m3 as steam.
(a) How much work is done by the system
during this process?
(b) How much energy is transferred as heat
during the process?
(c) What is the change in the system’s internal
energy during the process?
41

Thermodynamics Part I (Student Version)

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Dr.

Hong Nam Nguyen

• Overview and basic concept of thermodynamics

(In reality no process is really

No! They have meaning

Before 1948: Calorie/Btu

After 1948: Joule (Scientists

1cal = 3.968x 10-3 Btu

Copyrights @ Hello Techie Vietnam

• Adapted for thermodynamic processes.

• It distinguishes two forms of energy transfer: heat and

• It defines the internal energy of a system, an

The walls does not allow any

If a few lead shot is removed, the gas

The internal energy Eint of a systemtends to

ΔEint = Eint,f – Eint,i =Q - W

BE CARREFUL OF THE SIGN!!

ΔEint = Eint,f – Eint,i =Q - W

Constant-volume If the volume of a system is held

1. Expulsion of heat in heat engines:

real life? 2. Do not insulate the system:

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