NATIONAL UNIVERSITY HO CHI MINH CITY

UNIVERSITY OF TECHNOLOGY

GENERAL PHYSICS 1
Dr. Pham Thi Hai Mien
Department of Applied Physics
Faculty of Applied Science
 CHAPTER 4. THERMODYNAMICS
1. THE IDEAL GAS LAW
2. THE KINETIC THEORY OF GASES
3. THE FIRST LAW OF THERMODYNAMICS
3.1. Heat
3.2. Work
3.3. Some special cases
4. THE SECOND LAW OF THERMODYNAMICS
4.1. Heat engines
4.2. Refrigerators or heat pumps
4.3. Entropy

2
 1. THE IDEAL GAS LAW
• The concept of an ideal gas implies that the gas molecules do not
interact except upon collision, and that the molecular volume is
negligible compared with the volume of the container.
• In reality, an ideal gas does not exist. However, all real gases
approach the ideal state at low enough densities (or low pressures) –
that is, their molecules are far enough apart that they do not interact
with one another.
• The ideal gas law is the equation of state of an ideal gas: pV  nRT
where: P – pressure (N/m2), 1 atm = 1.013x105 N/m2 = 760 mmHg
V – volume (m3)
T – absolute temperature (Kelvin temperature ), TC  T  273
n – number of moles;
R – universal gas constant,
R  8.31 J / mol.K  0.08214 L.atm / mol.K
3
 PV DIAGRAMS FOR BASIC THERMAL PROCESSES
• Isovolumetric process: V = const
p
 const
T
• Isobaric process: P = const
V
 const
T
• Isothermal process: T = const
pV  const A = isovolumetric process
B = adiabatic process
• Adiabatic processes: no transfer of C = isothermal process
energy as heat between the system and D = isobaric process
its environment (Q=0).
1
 1
pV  const; TV  const; Tp 
 const (γ - the ratio of specific heats)
4
 SAMPLE PROBLEM 1
Oxygen gas having a volume of 1000 cm3 at 40.0°C and 1.01x105 Pa
expands until its volume is 1500 cm3 and its pressure is 1.06x105 Pa.
Find the final temperature of the sample.

SOLUTION

p1V1 p 2 V2
The ideal gas law : n  
RT1 RT2
p 2 V2 T1 1.06 105 1500  (273  40)
 T2    493K
p1V1 1.0110 1000
5

5
 2. THE KINETIC THEORY OF GASES
• The kinetic theory of gases relates the motion of the atoms to the
volume, pressure, and temperature of the gas.
• The molecules in a gas move randomly.
• The molecules interact only by short-range forces during elastic
collisions.
• The pressure that a gas exerts on the walls of its container is a
consequence of the collisions of the gas molecules with the walls.
• The pressure of an ideal gas is proportional to the number of
molecules per unit volume and the average translational kinetic
energy per molecule:
2 N 1 2
p  ( ) m0v 
3 V 2 
where m0 is the molecular mass; N is the number of molecules; V is
the volume of the gas; v 2  v rms is the root-mean-square speed. 6
• The average translational kinetic energy per molecule in a gas is
proportional to the absolute temperature:
1 3 3 R
m 0 v  k BT 
2
T
2 2 2 NA
• The total translational kinetic energy of n moles of gas:
3
K tot  nRT
2
• The root-mean-square speed:
3RT 3k BT
v rms  v 
2

M m0

where M is the molar mass; kB=1.38x10-23 J/K is the Boltzmann

constant.
7
 THEOREM OF EQUIPARTITION OF ENERGY

• Translational motion has 3 degrees of freedom  The average

translational kinetic energy per molecule can be divided into 3
components:
1 1 1 1 3
m 0 v  m 0 v x  m 0 v y  m 0 v z  k BT
2 2 2 2

2 2 2 2 2
Each translational degree of freedom contributes an equal amount

 
of energy 1 k BT to the gas.
2
• Theorem of equipartition of energy: each degree of freedom
 
contributes 1 k BT to the energy of a system, where possible
2
degrees of freedom are those associated with translation, rotation
and vibration of molecules.

8
 DEGREES OF FREEDOM
• The degrees of freedom of a mechanical system is the number of
independent parameters that define its configuration or state.
i  i trans  i rot  i vib
itrans irot ivib i
Monoatomic gas 3 0 0 3
Diatomic gas 3 2 0 (at low temperature) 5
Polyatomic gas 3 3 0 (at low temperature) 6

9
 INTERNAL ENERGY
• The internal energy of a system is the sum of the kinetic and
potential energies of the particles that form the system.
• Because the particles in an ideal gas do not interact, this system has
no potential energy. The internal energy of an ideal gas is therefore
the sum of the kinetic energies of the particles in the gas:
E int  K trans  K rot  K vib

• The internal energy of an ideal gas is a function of the gas

temperature only, it does not depend on any other variables.
i
E int  nRT
2

10
 SAMPLE PROBLEM 2

Determine the internal energy of a container of oxygen if its

translational kinetic energy is 228.3 J.

SOLUTION

3 2 K trans
K trans  nRT  T 
2 3 nR
i i   2 K trans  i 5
E int  nRT   nR     K trans   228.3  378.9J
2 2   3 nR  3 3

11
 3. THE FIRST LAW OF THERMODYNAMICS
• The first law of thermodynamics is a statement of conservation of
energy: The change in the internal energy of a system equals the sum
of the energy transferred across the boundary by heat and the energy
transferred by work.
E int  Q  Won or E int  Q  Wby
where: Q – the energy transferred to the system by heat;
Won / Wby – the work done on / by the system;
ΔEint – the change in internal energy.
• The values of both Q and W depend on the path taken between the
initial and final states; ΔEint is path independent.
• In an isolated system, there is no exchange of energy or matter with
the surroundings: Q = W = 0  ΔEint= 0  The internal energy
remains constant.
• In a cyclic process that starts and ends at the same state: E2 = E1 
ΔEint= 0  The internal energy remains constant. 12
 3.1. HEAT
• The energy transferred to the system by heat:
T2 T2

Q   mcdT  mcT or Q   nCdT  nCT

T1 T1

• The specific heat c is the amount of heat required to raise the

temperature of one kg of a substance by one kelvin (J/kg.K).
• The molar specific heat C is amount of heat required to raise the
temperature of one mole of a substance by one kelvin (J/mol.K).
• The molar specific heat at constant pressure or constant volume:
iR i2 CP i  2
CV  , CP  R    (γ - the ratio of specific heats)
2 2 CV i
• If the heat is absorbed by the system: Q > 0.
• If the heat is lost by the system: Q < 0.
13
 3.2. WORK
V2

• The work done on the gas: Won    pdV

V1

V2

• The work done by the gas: Wby    pdV

V1

• The work done on a gas in a quasi-static process is the negative of

the area under the curve on a PV diagram.

Won  0 Won  0
14
 3.3. SOME SPECIAL CASES OF THE FIRST LAW

a) Isothermal processes

T  const  pV  const
i P1
Eint  nRT  0 (1)
2
(2) V2
nRT V2
Won    pdV    dV   nRT ln (2)
(1) V1
V V1 P2
V2 V1 V2
Eint  Q  Won  0  Q  Won  nRT ln
V1

15
b) Constant-volume processes
p
V  const   const
T
V2

Won    pdV  0
V1

i
Eint  Q  Won  Q  Eint  nRT  nCv T
2

16
c) Isobaric processes
V
p  const   const
T
i
Eint  nRT  nCV T
2
V2

Won    pdV   pV  nRT

V1

i i2
Q  Eint  Won  nRT  nRT  n RT  nC p T
2 2
d) Adiabatic processes
Q0
i p2V2  p1V1
Won  Eint  nRT 
2  1
17
SUMMARY

18
 SAMPLE PROBLEM 3
A thermodynamic system undergoes a process in which its internal
energy decreases by 500 J. Over the same time interval, 220 J of work
is done on the system. Find the energy transferred from it by heat.

SOLUTION

E int  500J
Won  220J
E int  Q  Won  Q  E int  Won  500  220  720J

720 J of energy is transferred from the system by heat.

+19
 4. THE SECOND LAW OF THERMODYNAMICS
• The first law of thermodynamics is a statement of conservation of
energy: a change in internal energy in a system can occur as a result
of energy transfer by heat or by work, or by both. But the law makes
no distinction between the results of heat and the results of work.
• In fact, there is an important distinction between heat and work that is
not evident from the first law. One manifestation of this distinction is
that it is impossible to design a device that, operating in a cyclic
fashion, takes in energy by heat and expels an equal amount of
energy by work.
• A cyclic device that takes in energy by heat and expels a fraction of
this energy by work is possible and is called a heat engine.
• The first law makes no distinction between processes that occur
spontaneously and those that do not, whereas the second law of
thermodynamics establishes which processes do and which do not
occur. 20
• In a reversible process, the system can be
returned to its initial conditions along the
same path on a PV diagram, and every point
along this path is an equilibrium state.
• Irreversible processes occur naturally in one
direction only.
• An example of irreversible processe:
 The gas is confined to the left half of an
insulated container by a closed stopcock.
 When the stopcock is opened, the gas
rushes to fill the entire container.
 The gas can not spontaneously collect itself
in the left half of the container.
• Although all real processes are irreversible, some are almost
reversible. If a real process occurs very slowly such that the system is
always very nearly in an equilibrium state, then the process can be
approximated as being reversible. 21
 4.1. HEAT ENGINES
• A heat engine is a device that takes in energy by heat and, operating
in a cyclic process, expels a fraction of that energy by means of work.
• A heat engine carries some working substance through a cyclic
process during which the working substance absorbs energy by heat
from a high-temperature (hot) reservoir, work is done by the
engine, and energy is expelled by heat to a lower-temperature (cold)
reservoir.
• Example: In an automobile engine
 The working substance is a gasoline–air mixture.
 The hot reservoir is the burning fuel.
 The cold reservoir is the environment to which the combustion
products are exhausted.
 Operating principle: The engine uses energy from a burning fuel in
the combustion chamber to perform work on pistons that results in
the motion of the automobile. 22
• The engine absorbs a quantity of energy Qh > 0
from the hot reservoir, does work Weng and
then gives up a quantity of energy Qc < 0 to the
cold reservoir.
• Because the working substance goes through a
cycle, its initial and final internal energies are
equal: E int  Q  Wby  0  Q  Weng  0
 Weng  Q  Q h  Qc  Q h  Qc
Convention: we will use absolute values to
make all energy transfers positive.
• The thermal efficiency e of a heat engine is defined as the ratio of
the net work done by the engine during one cycle to the energy input
at the higher temperature during the cycle:
what we want Weng Q h  Qc Qc
e  e   1
what we pay for Qh Qh Qh
23
• A heat engine has 100% efficiency (e = 1) only if Qc = 0. Because
some energy Qc must be rejected to the environment, efficiencies of
real engines are well below 100%.
Qc
e  1 1
Qh

• The Kelvin–Planck form of the second law of thermodynamic: It

is impossible to construct a heat engine that, operating in a cycle,
produces no effect other than the input of energy by heat from a
reservoir and the performance of an equal amount of work.

24
 CARNOT ENGINES
• In 1824 a French engineer named Sadi Carnot showed that a heat
engine operating in an ideal, reversible cycle called a Carnot cycle
between two energy reservoirs is the most efficient engine possible.
• All real engines are less efficient than the Carnot engine because they
do not operate through a reversible cycle.
• The Carnot cycle consists of two adiabatic
processes and two isothermal processes, all
reversible.
• The thermal efficiency of the Carnot engine:
Qc Tc
e  1  1  1
Qh Th

• The efficiency increases as Tc is lowered

and as Th is raised. The Carnot cycle
25
 THE CARNOT CYCLE
• Process A-B: The gas is placed in
thermal contact with a hot reservoir at
temperature Th, absorbs energy Qh from
the hot reservoir and does work WAB in
raising the piston.
• Process B-C: the gas expands
adiabatically QBC=0. The temperature of
the gas decreases from Th to Tc and the
gas does work WBC in raising the piston.
• Process C-D: the gas is placed in thermal
contact with a cold reservoir at
temperature Tc and is compressed
isothermally at temperature Tc. The gas
expels energy Qc to the cold reservoir,
and the work done by the piston on the
gas is WCD.
• Process D-A: the gas is compressed
adiabatically QDA=0. The temperature of
the gas increases to Th, and the work
done by the piston on the gas is WDA. 26
 SAMPLE PROBLEM 4
A Carnot engine whose low-temperature reservoir is at 17°C has an
efficiency of 40%. By how much should the temperature of the high-
temperature reservoir be increased to increase the efficiency to 50%.

SOLUTION

Tc Tc 290
e1  1   Th1    483K
Th1 1  e1 1  0.4
Tc Tc 290
e2  1   Th 2    580K
Th 2 1  e 2 1  0.5
Th 2  Th1  580  483  97K

+27
 SAMPLE PROBLEM 5
Could this heat engine be built?
A. Yes. B. No.
C. It’s impossible to tell without knowing
what kind of cycle it uses.
D. It’s impossible to tell without knowing
what kind of working substance it uses.
SOLUTION
• The thermal efficiency of a real engine is always less than that of a
Carnot engine: Qc Tc
e  1  1
Qh Th
• The thermal efficiency of the above mentioned engine:
Qc 40 TC 300
e  1  1  0.6  1   1  0.5
Qh 100 TH 600
 This engine can not exist  Answer B.
28
 4.2. REFRIGERATORS OR HEAT PUMPS
• A refrigerator or a heat pump is a device that
uses work to transfer energy from a low-
temperature reservoir to a high-temperature
reservoir.
• Heat pumps have long been used for cooling or
heating homes and buildings.
• A heat pump in cooling mode: absorbs energy
from the interior of the building (cold reservoir)
and releases it to the outside (hot reservoir).
• A heat pump in heating mode: absorbs energy
from the outside (cold reservoir) and releases it
to the interior of the building (hot reservoir).
• A household refrigerator is a heat pump in cooling mode. The work is
done by an electrical compressor to transfer energy from the food
storage compartment (cold reservoir) to the room (a hot reservoir). 29
• The effectiveness of a heat pump is described in terms of a number
called the coefficient of performance:
Qc Qc
COP(cooling mode)  
what we want W Qh  Qc
COP  
what we pay for Qh Qh
COP(heating mode)  
W Qh  Qc

• If it could be accomplished without doing any work (W=0), then the

heat pump would be perfect (COP = ∞). However, energy does not
transfer spontaneously by heat from a cold object to a hot object. This
direction of energy transfer requires an input of energy to a heat
pump, which is often supplied by means of electricity (W ≠ 0).
• The Clausius form of the second law of thermodynamic: It is
impossible to construct a cyclical machine whose sole effect is to
transfer energy continuously by heat from one object to another object
at a higher temperature without the input of energy by work. 30
 THE REVERSED CARNOT CYCLE FOR HEAT PUMPS

• The Carnot COP for a heat pump:

Qc Qc Tc
COP(cooling mode)   
W Q h  Qc Th  Tc
Qh Qh Th
COP(heating mode)   
W Q h  Qc Th  Tc

• As the difference between the

temperatures of the two reservoirs
approaches zero, the theoretical COP
approaches infinity. In practice, the
COP is below 10.

31
 4.3. ENTROPY
• Entropy is a state property of the system like pressure, volume,
temperature and energy.
• Entropy is a measure of disorder.
• The change in entropy of a system during a reversible process that
takes the system from an initial state to a final state:
2 2
dQ
S   dS   (J/K)
1 1
T
2
dQ
(for irreversible processes: S   )
1
T
• The change in entropy during a process depends only on the end
points and therefore is independent of the actual path followed.
• When energy is absorbed by the system, dQ > 0  ΔS increases.
When energy is expelled by the system, dQ < 0  ΔS decreases.
32
• One form of the second law of thermodynamics: If a process
occurs in an isolated system, the entropy of the system increases for
irreversible processes and remains constant for reversible processes.
It never decreases.
S  0 for reversible processes
In isolated systems : 
S  0 for irreversible processes
• In the real world almost all processes are irreversible, so the entropy
of isolated systems undergoing real processes always increases.
• The change in entropy of an ideal gas in reversible processes:
Isobaric processes Isovolumetric processes

SP  nCP ln  2  SV  nCV ln  2 

T T
 T1   T1 
Isothermal processes Adiabatic processes
S  0
ST  nR ln  2 
V
 V1  33
 SAMPLE PROBLEM 6
Suppose that 1.00 kg of water at 0.00°C is mixed with an equal mass of
water at 100°C. After equilibrium is reached, the mixture has a uniform
temperature of 50.0°C. What is the change in entropy of the system?

SOLUTION
m1  m 2 1 1.0 kg
c1  c 2  4186 J / kg.K
T1  273K, T2  373K, Tfinal  323K
Tfinal Tfinal
dQ dT Tfinal
S1  
T1
T
 
T1
m1c1
T
 m1c1 ln
T1
 704 J / K  0

Tfinal Tfinal
dQ dT Tfinal
S2  
T2
T
 
T2
m2c2
T
 m 2 c 2 ln
T2
 602 J / K  0

S  S1  S2  102 J / K  0  Irreversible process in an isolated system

34
 REFERENCES

1. R.A. Serway and J.W. Jewett, Physics for Scientists and

Engineers, 6th Ed., Thomson 2004.
2. Halliday, Resnick, Walker, Fundamental physics , 9th Ed., Wiley,
2011.

VIDEO LINK
Carnot Engine: https://www.youtube.com/watch?v=kJlmRT4E6R0