Chapter 4- laws of thermodynamics

• Zeroth law of thermodynamics.

• First law of thermodynamics.
• Mechanical equivalent of heat.
• Second law of thermodynamics.
• Equivalent of Clausius and Kelvin Plank’s
statements.
• Gibbs-Dalton’s law.
• Application of Second law to heat pump and
refrigerator.
• Simple related problems.
 First Law of Thermodynamics
• Energy conservation law
• Relates changes in internal energy to energy
transfers due to heat and work
• Applicable to all types of processes
• Provides a connection between microscopic
and macroscopic worlds
 More on First Law
• Energy transfers occur
– By doing work
• Requires a macroscopic displacement of an object
through the application of a force
– By heat
• Occurs through the random molecular collisions
• Both result in a change in the internal energy,
U, of the system
 First Law, Equation
• If a system undergoes a change from an initial
state to a final state, then U = U2 – U1 = Q - W
– Q is the energy transferred to the system by heat
– W is the work done by the system
– U is the change in internal energy
 First Law – Signs
• Signs conventions:
–Q
• Positive if energy is transferred to the system by heat
• Negative if energy is transferred out of the system by heat
–W
• Positive if work is done on the system
• Negative if work is done by the system
– U
• Positive if the temperature increases
• Negative if the temperature decreases
 Results of U
• Changes in the internal energy result in
changes in the measurable macroscopic
variables of the system
– These include
• Pressure
• Temperature
• Volume
 IMPORTANT
Notes About Work
• Positive work increases the internal energy of
the system
• Negative work decreases the internal energy
of the system
• This is consistent with the definition of
mechanical work
 Special Case 1:Isolated Systems
• An isolated system is one that does not interact with its
surroundings

• No energy transfer by heat takes place

• The work done on the system is zero

Q=W=0  Uint = 0 (Isolated System)

• The internal energy of an isolated system remains

constant
 Special Case 2: Cyclic Process
• A cyclic process is one that starts and ends in the same
state
– This process would not be isolated
– On a PV diagram, a cyclic process appears as a closed
curve
• The internal energy must be zero since it is a state
variable
Uint = 0  Q = ̶ W (Cyclic Process)
• In a cyclic process, the net work done on the system per
cycle equals the area enclosed by the path representing
the process on a PV diagram
 Some Applications of the 1st Law of
Thermodynamics
• An adiabatic process is one during which no energy
enters or leaves the system
Q = 0  Uint = Q - W  Uint = W
• This is achieved by:
– Thermally insulating the walls of the system
– Having the process proceed so quickly that no
heat can be exchanged
• If the gas is compressed adiabatically, W is positive
so Uint is positive and the temperature of the gas
increases
• If the gas expands adiabatically, the temperature of
the gas decreases
 Adiabatic Processes, Examples
• Some important examples of adiabatic processes related
to engineering are:

– The expansion of hot gases in an internal combustion

engine

– The liquefaction of gases in a cooling system

– The compression stroke in a diesel engine

 Adiabatic Free Expansion
• An example of adiabatic free expansion
– The process is adiabatic because it takes
place in an insulated container

• Because the gas expands into a vacuum, it

does not apply a force on a piston and W = 0

• Since Q = 0 and W = 0  Uint = 0 and the

initial and final states are the same

• No change in temperature is expected

 Isobaric Process
• An isobaric process is one that occurs at a constant
pressure

• The values of the heat and the work are generally both
nonzero

• The work done is

W = – P (Vf – Vi)
where P is the constant pressure
 Isovolumetric Process
• An isovolumetric (isochoric) process is one in which there is
no change in the volume

• Since the volume does not change: W = P V = 0

• From the first law:

Uint = Q - W  Uint = Q

• If energy is added by heat to a system kept at constant

volume, all of the transferred energy remains in the system
as an increase in its internal energy
 Isothermal Process
• An isothermal process is one that occurs at a
constant temperature
• Since there is no change in temperature:
Uint = 0  Q = ̶ W
• Any energy that enters the system by heat
must leave the system by work
• At right is a PV diagram of an isothermal
expansion of an Ideal Gas
• The curve is a hyperbola
• The curve is called an isotherm
• Diagram indicates: PV = constant
 Isothermal Expansion, Details

• Because it is an ideal gas and the process is quasi-static:

PV = nRT 

Vf Vf nRT V f dV  Vi 
W    PdV    dV  nRT   nRT ln  
Vf
 nRT lnV V(20.13)
Vi Vi V Vi V V 
 f 
i

• Numerically, the work equals the area under the PV curve

– The shaded area in the diagram
• If the gas expands, Vf > Vi and the work done on the gas is negative
• If the gas is compressed, Vf < Vi and the work done on the gas is
positive
 Special Process, Summary

• Adiabatic: No heat exchanged

Q = 0 and Eint = W

• Isobaric: Constant pressure

W = P (Vf – Vi) and Eint = Q + W

• Isothermal: Constant temperature

Eint = 0 and Q = ̶ W

• Isochoric: Constant volume

W = 0 andEint = Q
 Thermodynamics –
Historical Background
• Thermodynamics and mechanics were considered to be separate
branches
– Until about 1850
– Experiments by James Joule and others showed a connection
between them
• A connection was found between the transfer of energy by heat in
thermal processes and the transfer of energy by work in mechanical
processes
• The concept of energy was generalized to include internal energy
• The Law of Conservation of Energy emerged as a universal law of
nature
 Heat

• Heat is defined as the transfer of energy across the boundary of a

system due to a temperature difference between the system and
its surroundings

• The term heat will also be used to represent the amount of energy
transferred
 Changing Internal Energy

• Both heat and work can change the internal energy of a system

• The internal energy can be changed even when no energy is

transferred by heat, but just by work

• Example: compressing gas with a piston

– Energy is transferred by work
 Units of Heat

• Historically, the calorie was the unit used for heat

– One calorie is the amount of energy transfer necessary to raise
the temperature of 1 g of water from 14.5oC to 15.5oC
• The “Calorie” used for food is actually 1 kilocalorie!!

• In the US Customary system, the unit is a BTU (British Thermal

Unit)
– One BTU is the amount of energy transfer necessary to raise the
temperature of 1 lb of water from 63oF to 64oF

• The SI units for heat is: Joules

 Mechanical Equivalent of Heat
• Joule established the equivalence between mechanical
energy and internal energy
• The loss in potential energy associated with the blocks
equals the work done by the paddle wheel on the water
• Joule found that it took approximately 4.18 J of
mechanical energy to raise the water 1oC
• Later, more precise, measurements determined the
amount of mechanical energy needed to raise the
temperature of water from 14.5oC to 15.5oC
1 cal = 4.186 J
• This is known as: The mechanical equivalent of heat!!!
 Specific Heat
• The heat capacity, C, of a particular sample is defined as the
amount of energy (Q) needed to raise the temperature of that
sample by 1oC
• If energy Q produces a change of temperature of T, then
Q = C T
C = Q/T
• Specific heat, c, is the heat capacity per unit mass
• If energy Q transfers to a sample of a substance of mass m and the
temperature changes by T, then the specific heat is: c = C/m 

Q
c
m T
 Specific Heat, cont

• The specific heat is essentially a measure of how insensitive a

substance is to the addition of energy

• The greater the substance’s specific heat, the more energy that
must be added to cause a particular temperature change

• The equation is often written in terms of Q :

Q = mc T
Some Specific Heat Values
 Second Law of
Thermodynamics
 Introducing the second law
• A process should satisfy the first law in order
to occur.
• However, satisfying first law alone does not
guarantee that the process will take place.
Examples of impossible processes that
do not violate first law

A cup of coffee does not get hotter

in a cooler room by absorbing
heat from environment.

Transferring heat to a resistance will not generate

electrical energy

Transferring heat to this paddle-wheel device

Heat will not cause the paddle-wheel to rotate and
raise the mass through the pulley.
 It is clear from the previous
examples that..
• Processes proceed in certain direction and not
in the reverse direction.

• The first law places no restriction on the

direction of a process.

• Therefore we need another law (the second

law of thermodynamics) to determine the
direction of a process.
29
• The second law of thermodynamics states
that processes occur in a certain direction, not
in just any direction. Physical processes in
nature can proceed toward equilibrium
spontaneously:

• Water flows from higher to lower elevation.

• Gases expand from a high pressure to a low
pressure.
• Heat flows from a high temperature to a low
temperature.
 Some Definitions
To express the second law in a workable form, we need the
following definitions.
Thermal (Heat) Reservoir
A heat reservoir is a sufficiently large system in stable
equilibrium to which and from which finite amounts of heat
can be transferred without any change in its temperature.

• If it supplies heat then it is

called a source.

• If it absorbs heat then it

is called a sink.
• Work reservoir
A work reservoir is a sufficiently large system in
stable equilibrium to which and from which finite
amounts of work can be transferred adiabatically
without any change in its pressure.
• Thermodynamic cycle
A system has completed a thermodynamic cycle
when the system undergoes a series of processes
and then returns to its original state, so that the
properties of the system at the end of the cycle are
the same as at its beginning. Thus, for whole
numbers of cycles
• Heat Engine
- A heat engine is a thermodynamic system
operating in a thermodynamic cycle to which
net heat is transferred and from which net
work is delivered.
- The system, or working fluid, undergoes a
series of processes that constitute the heat
engine cycle.
- The following figure illustrates a steam power
plant as a heat engine operating in a
thermodynamic cycle.
 Generally, there are two ways to state the second
law of thermodynamics:

(1) Kelvin-Planck: It is impossible to build a cyclic engine that

will have a thermal efficiency of 100%
* All work can be converted to heat, but all heat CANNOT
be converted into work
* Maximum possible thermal efficiency for a heat engines
is the Carnot cycle efficiency

(2) Clausius Statement: It is impossible to devise a cycle

such that its only effect is the transfer of heat from a
low-temperature body to a high-temperature body
* An input of work is always required for refrigeration cycles
 Kevin-Planck Statement
• It is impossible for any device that operates on a cycle to receive heat from a
single reservoir and produces a net amount of work.
• This is a statement without proof, but has not been disproved yet.
•It is not possible to built a heat engine that is 100%.

• A heat engine has to reject some

energy into a lower temperature sink
in order to complete the cycle.
TH • TH>TL in order to operate the engine.
Therefore, the higher the
QH temperature, the higher the quality of
the energy source since it can
produce useable work to more lower-
Heat engine temperature energy sinks.
Wnet
 Clausius Statement
• It is impossible to construct a device that operates in a cycle and produces no
effect other than the transfer of heat from a lower-temperature body to a higher-
temperature body.
• Also can not be proved, rather depends on experimental observations.
• Heat can not transfer from low temperature to higher temperature unless
external work is added.

• Therefore, it is not possible to built a heat

TH pump without external work input.
QH

Heat pump

QL
TL
 Equivalence of the Two Statements
• It can be shown that the violation of the one statement means the violation of the
other statement. They are equivalent.

100% heat engine: against K-P Statement

TH
QL
TH
QH QH+QL Heat pump

Heat engine Heat pump

QL
TL
Wnet
=QH QL
Heat transfer from low-temp body to
high-temp body without work- violation of
TL
the C-statement
 Heat Engine
• A heat engine takes in energy by heat and
partially converts it to other forms
• In general, a heat engine carries some working
substance through a cyclic process
 Heat Engine
• Energy is transferred
from a source at a high
temperature (Qh)
• Work is done by the
engine (Weng)
• Energy is expelled to a
source at a lower
temperature (Qc)
• Since it is a cyclic process,
ΔU = 0
– Its initial and final internal
energies are the same
• Therefore, Qnet = Weng
• The work done by the
engine equals the net
energy absorbed by the
engine
• The work is equal to the
area enclosed by the
curve of the PV diagram
Thermal Efficiency of a Heat Engine
• Thermal efficiency is defined as the ratio of
the work done by the engine to the energy
absorbed at the higher temperature

W en g Qh  Qc Qc
e   1
Qh Qh Qh

• e = 1 (100% efficiency) only if Qc = 0

– No energy expelled to cold reservoir
Work was completely converted into
heat in Joule’s experiment
Q=W
An engineer attempts to convert heat
to work
 Heat Pumps and Refrigerators

• Heat engines can run in reverse

– Energy is injected
– Energy is extracted from the cold reservoir
– Energy is transferred to the hot reservoir
• This process means the heat engine is running as
a heat pump
– A refrigerator is a common type of heat pump
– An air conditioner is another example of a heat pump
 Heat Pump Abstraction
• The work is what you pay
for
• The Qc is the desired
benefit
• The coefficient of
performance (COP)
measures the
performance of the heat
pump running in cooling
mode
 Heat Pump, COP
• In cooling mode,

• The higher the number, the better

• A good refrigerator or air conditioner typically
has a COP of 5 or 6
 Heat Pump, COP
• In heating mode,

• The heat pump warms the inside of the house

by extracting heat from the colder outside air
• Typical values are greater than one
 Refrigeration Cycles
• In refrigeration cycles, heat is transferred from a
low-temperature area (i.e. inside the refrigerator) to
a high-temperature area (e.g., in the kitchen)
• Since heat spontaneously flows only from high to low
temperature areas, work is required to force heat transfer
• Opposite of heat engines
• Systems:
• Refrigerator: Heat is removed from air inside
• Air conditioner: Heat is removed from air in an occupied
space
• Heat Pump: Heat is supplied to air in an occupied space
• Chiller: Heat is removed from water
 Refrigeration Cycles: Performance
• In refrigeration cycles, the coefficient of performance
(COP) is used in place of thermal efficiency to
measure performance
• The COP is always the ratio of useful energy transfer
to the work input

heat transfer from low-

QL
COPrefrigerator, AC  temperature reservoir

W work input

QH
COPheat pump  heat transfer from high-
W temperature reservoir
Structure of A Domestic Refrigerator

1: Evaporator/Freezer
4: Condenser
7: Compressor
8 : Temperature control
9 : Throttling Device
Thermodynamic Cycle of A Refrigerator
                                                                                                                                           
Simplified Diagram of A Refrigerator

Throttling Valve
Condenser : Transient
Constant Pressure Cooling.

Compressor : Transient
Adiabatic Compression

Throttling Device:
Homogeneous and Transient
Isoenthalpic process.

Evaporator: Transient Constant

Pressure Cooling.
Compressor
Engines and Refrigerators
HEAT ENGINE REFRIGERATOR

TH TH

QH QH
system

W W
QC QC

TC TC

11
 Problem 1
Given: A Carnot engine receives 100 kJ of heat from a hot reservoir at 370 oC and
rejects 37 kJ of heat. Determine the temperature of the cold reservoir.

Analysis:
Q net Q H  Q L 100 kJ  37 kJ
 th    TH
Q in QH 100 kJ
th  0.63 or 63% QH
W
TH  TL T
th,Carnot   1 L
 TH TH
QL
TL  TH  TH th,Carnot
TL  (370  273)   370  273 0.63
TL

 TL = 237.91 K = -35.09 oC
 Problem 2
Given: What is the maximum thermal efficiency possible for a power cycle operating
between 600 oC and 110 oC?

Analysis:
Carnot yields maximum possible efficiency
TL
th,Carnot  1
TH

th,Carnot  1
110  273K
600  273K

th,Carnot  0.561 or 56.1%



 Problem 3
Given: A heat pump takes heat from groundwater at 7 oC and maintains a room at
21oC. What is the maximum coefficient of performance possible for this heat
pump?
upper limit of heat pump is set
Analysis: by a Carnot heat pump cycle

QH QH TH
COPheat pump   
W Q H  Q L TH  TL
TH

QH COPheat pump 
 21  273 K
W
 21  273 K   7  273 K
COPheat pump  21
QL

TL How does a refrigerator COP differ?

A steam power plant produces 50 MW of net work while
burning fuel to produce 150 MW of heat energy at the high
temperature. Determine the cycle thermal efficiency and the
heat rejected by the cycle to the surroundings.
Wnet , out
 th 
QH
50 MW
  0.333 or 33.3%
150 MW

Wnet , out  QH  QL
QL  QH  Wnet , out
 150 MW  50 MW
 100 MW
 Dalton’s Law
Dalton’s Law states that the pressure
exerted by a mixture of gases equal the
sum of the partial pressures of the gases in
the mixture.

Ptotal = P1 + P2 + P3 + . . .
 Dalton’s Law
The pressure of each component is
called the partial pressure of that
component.
 Dalton’s Law
For example: If we have a flask
containing nitrogen gas, whose partial
pressure is .78 atm and oxygen gas,
whose partial pressure is .20 atm, the
total pressure in the flask is
Ptotal = PN2 + PO2
Ptotal = .78 + .20 = .98 atm
 Dalton’s Law
Another way to think about this is
through the use of the mole fraction.
The mole fraction is rather like
calculating the percent of each
component.
 Dalton’s Law
The mole fraction is written as follows

aN2 = moles N2
total moles

This is basically the percent (by number) of

some element.
 Dalton’s Law
We can rearrange Dalton’s Law to use
the mole fraction as follows:
Px = ax (Ptotal)

Or specifically:
PN2 = aN2 (Ptotal)
 Dalton’s Law
For example: ordinary air contains
78.084% nitrogen. We might be
interested in knowing what the
partial pressure of nitrogen is in the
atmosphere.
 Dalton’s Law
The mole fraction of N2 must be .
78084, so

PN2 = .78084(Ptotal)
If the atmospheric pressure is 640 torr,
PN2 = .78084(640) = 500 torr
 Composition of Air
78.084% Nitrogen
20.948% Oxygen
.934% Argon
.0315% Carbon dioxide
.001818% Neon
.000524% Helium
.000114% Krypton
.0000087% Xenon