laws thermodynamics
TRANSCRIPT
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What is Thermodynamics?
Thermodynamics is the branch of science
which deals with energy transfer and its
effect on the state or condition of a system.Essentially, thermodynamics pertains to the
study of :
Interaction of system and surroundings; it
relates the changes which the system
undergoes to the influences to which it is
put.
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Energy and its transformation; energyintercon!ersions in the form of heat and
wor". #ames a #oule has pro!ed with his
well"nown e$periments with churnerthat mechanical wor" can be con!erted
into heat energy.
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%elationship between heat, wor", and
physical properties such as pressure,
!olume and temperature of the wor"ingsubstance employed to obtain energy
con!ersion
&easibility of a process and concept ofe'uilibrium processes.
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Thermodynamics the study of heat and related 'uantities
system is some part of the world in which we are
interested and plan to describethermodynamically.E$. a piece of matter, a reaction !essel and its contents,or an engine.
surroundings is the rest of the world outside the system.
state of the system is determined when we specify!aluesfor the minimum number of intensi!e !ariables
( temperature, pressure, etc. ) so that all other properties(dependent !ariables ) are fi$ed.
state function - a physical property that has a specific
!alue once the state is defined; including the !olume *(T,+), whose relationship to T and + was gi!en by thee'uation of state
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&orms of Energy
Energy comes in a !ariety of forms
+otential
-echanical hemical Electrical
Internal /inetic
0eat
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Thermodynamics is based on a few statements
called laws that ha!e broad applications to physical
and chemical systems. Three such statements thatwe will e!entually discuss are the first, second, and
third laws of thermodynamics (profound
discussions on the last two laws will be discussed
in the sub1ect Thermodynamics).
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The 2eroth 3aw of Thermodynamics
4 more fundamental idea that is usually
assumed but rarely stated because it is too
ob!ious. 5ccasionally, this idea is referred
to as thezeroth law of thermodynamics.
Thermal e'uilibrium is the sub1ect of the
2eroth 3aw of Thermodynamics. The
67eroth law6 states that if two systems are at
the same time in thermal e'uilibrium with athird system, they are in thermal e'uilibrium
with each other.
http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/thereq.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/thermo/thereq.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/thermo/thereq.htmlhttp://hyperphysics.phy-astr.gsu.edu/hbase/thermo/thereq.html -
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If 4 and are in thermal e'uilibrium with 8,then 4 is in thermal e'uilibrium with .
+ractically this means that all three are at the
same temperature, and it forms the basis for
comparison of temperatures. 9 2eroth law is
so named because it logically precedes the
&irst and econd 3aws of Thermodynamics.
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Energy onser!ation
The First Law of Thermodynamicsstates that total energy is conser!ed for any
thermodynamic system < energy can not be created nor destroyed< energy can only change from one form to another
constant)( =EEnergy
constantelectricalchemicalheat
mechanicalpotentialkineticinternal
=++
++++
EEE
EEEE
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The First Law of Thermodynamics
The first law of thermodynamics is a statement of
the conservation of energy.
If a systems volume is constant, and heat is
added, its internal energy increases.
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The First Law of Thermodynamics
If a system does work on the external world, and
no heat is added, its internal energy decreases.
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The First Law of Thermodynamics
Comining these gives the first law of
thermodynamics. The change in a systems
internal energy is related to the heat Qand the
work Was follows!
It is vital to kee" track of the signs of Qand W.
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The First Law of Thermodynamics
The internal energy of the system de"ends only
on its tem"erature. The work done and the heatadded, however, de"end on the details of the
"rocess involved.
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The oncept of Wor"
#orkis a $echanicalform of %nergy!
DistanceForceWork =
xFdW =
ForceForce
&istance&istancexx
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The oncept of Wor"
#orkis a $echanicalform of %nergy!
%ecall the definition of pressure:
We can thus define wor" as:
DistanceForceWork =xFdW =
( ) 2Area
Forcep
x
F
==
pdVdW=
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The oncept of Wor"
Changes in 'olume Cause #ork!
Wor" is performed when air e$pands
Wor" of E$pansion:
5ccurs when a system performs wor"
(or e$erts a force) on its en!ironment
Is positi!e:
%ising air parcels (or balloons) undergo e$pansion wor"ince the en!ironmental pressure decreases with height,
with height a rising parcel must e$pand
to maintain an e'ui!alent pressure
0dW>
F
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The oncept of Wor"
Changes in 'olume Cause #ork!
imilar to a piston in a car engine
FF
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The oncept of Wor"
Changes in 'olume Cause #ork!
Wor" is performed when air contracts
Wor" of ontraction:
5ccurs when an en!ironment performs wor"
(or e$erts a force) on a system
Is negati!e:
in"ing air parcels (or balloons) undergo contraction wor"ince the en!ironmental pressure decreases with height,
with height a sin"ing parcel must contract
to maintain an e'ui!alent pressure
0dW+otential Energy
(of the molecules in the system)epends onlyon the current system state (p,*,T)oes notdepend on past statesoes notdepend on how state changes occur
hanges are the result of e$ternal forcing on the system (in the form of workor heat)
&irst 3aw of Thermodynamics
tenvironmentenvironmeninternal HeatWorkE +=
dQdWdU +=
dQpdVdU +=
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+ressure*olume (+*) iagrams
(nother #ay of &e"icting Thermodynamic )rocesses!
onsider the transformation: i f
"
''f'i
"i
"f
i
f
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(nother #ay of &e"icting #ork!
onsider the transformation: i f
"
'
pdVdW=
= f
ipdVW
'f'i
"i
"f
i
f The wor" done is the areaunder the i < f cur!e
(or gray area)
+ressure*olume (+*) iagrams
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#oules 3aw
'alve
Closed
(ir(ir'acuum'acuum
Thermally Insulated ystem
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Thermodynamics
#oules 3aw
Thermally Insulated ystem
'alve
*"en
(ir(ir(ir(ir
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Thermodynamics
#oules 3aw
dQpdVdU +=
'alve
*"en
(ir(ir(ir(ir
(ir ex"anded to fill the container
hange in !olumehange in pressure
+o external work was done4ir e$panded into a !acuum
within the system
+o heat was added or sutractThermally insulated system
+o change in internal energy+o change in tem"erature
#hat does this mean
0dU=
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Thermodynamics
#oules 3aw
dQpdVdU +=
'alve
*"en
(ir(ir(ir(ir
(ir ex"anded to fill the container
hange in !olumehange in pressure
+o external work was done4ir e$panded into a !acuum
within the system
+o heat was added or sutractThermally insulated system
+o change in internal energy+o change in tem"erature
Internal %nergy is only a function oftem"erature
0dU=U()U=
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Thermodynamics
Thermal apacities (pecific 0eats)
(ssume! 4 small 'uantity of heat (d@) is gi!en to a parcel
The parcel responds by e$periencing a small temperature increase (dT)
"ecific eat /c0!
Two Ty"es of "ecific eats!
epends on how the material changes as it recei!es the heat
Constant 'olume!
Constant )ressure!
vol!meconstant
vd
dQc
= +arcel e$periences no
change in !olume
+arcel e$periences no
change in pressure
press!reconstant
pd
dQc
=
dT
dQ=c
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Thermodynamics
Thermal apacities (pecific 0eats)
"ecific eat at Constant 'olume!
tarting with:
If the !olume is constant (d* = A), we can rewrite the first law as:
4nd substitute this into our specific heat e'uation as
vol!meconstant
vd
dQc
=
dQpdVdU += dQdU=1
=d
dUcv or dcdU v=
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Thermal apacities (pecific 0eats)
"ecific eat at Constant 'olume!
ince the internal energy is a state !ariable and does not depend on past states or how state changes occur, we can define changes in internal energy as:
4lso, if we substitute our specific heat e'uation into the first law:
We can obtain an alternative formof the First Law of Thermodynamics:
=2
"
dcU vT
T
pdVdcdQ v =
dQpdVdU +=1dcdU v=
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Thermodynamics
Thermal apacities (pecific 0eats)
"ecific eat at Constant )ressure!
tarting with
and recogni7ing that,
we can obtain another alternative formof the First Law of Thermodynamics:
4lso,
press!reconstant
pd
dQc
=
pdVdcdQ v =
VdppdVd(pV) +=
VdpdcdQ p =
#
vp n$cc +=
n$pV #=
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Thermodynamics
oncept of Enthalpy
(ssume! 0eat (d@) is added to a system at constant pressure
Im"act! 20 The systemBs !olume increases (*C
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Thermodynamics
&orms of the &irst 3aw of Thermodynamics
For a gas of mass m For unit mass
dWdUdQ +=pdVdUdQ +=
pdVdcdQ v +=
VdpdcdQ p =
d&d!d' +=pdd!d' +=
pddcd' v +=
dpdcd' p =
where! " 5 "ressure 4 5 internal energy
' 5 volume # 5 workT 5 tem"erature 6 5 heat energy
7 5 s"ecific volume n 5 numer of moles
cv5 s"ecific heat at constant volume /828 9 kg-2:-20
c"5 s"ecific heat at constant "ressure /2;;< 9 kg-2:-20
=d5 gas constant for dry air /3>8 9 kg-2:-20
=? 5 universal gas constant />.@2
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Thermal )rocesses
#e will assume that all "rocesses we discuss
are Auasi-static B they are slow enough that thesystem is always in eAuilirium.
#e also assume they are reversile!
For a process to be reversible, it must be possible to
return both the system and its surroundings to exactly
the same states they were in before the process began.
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Thermal )rocesses
This is an idealied reversile "rocess. The gas
is com"ressedD the tem"erature is constant, soheat leaves the gas. (s the gas ex"ands, it
draws heat from the reservoir, returning the gas
and the reservoir to their initial states. The
"iston is assumed frictionless.
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Thermal )rocesses
#ork done y an ex"anding gas, constant
"ressure!
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Thermal )rocesses
If the volume stays constant, nothing moves and
no work is done.
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Thermal )rocesses
If the tem"erature is constant, the"ressure varies inversely with the
volume.
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Thermal )rocesses
The work done is the area under the curve!
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Thermal )rocesses
4n adiaaticprocess is one in which no heat
flows into or out of the system. The adiabatic PV
cur!e is similar to the isothermal one, but is
steeper. 5ne way to ensure that a process is
adiabatic is to insulate the system.
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(nother way to ensurethat a "rocess is
effectively adiaatic is
to have the volume
change occur very
Auickly. In this case,
heat has no time to
flow in or out of thesystem.
Thermal )rocesses
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Thermal )rocesses
ere is a summary of the different ty"es ofthermal "rocesses!
"ecific eats for an Ideal Eas! Constant
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"ecific eats for an Ideal Eas! Constant
)ressure, Constant 'olume
"ecific heats for ideal gases must e Auoted
either at constant "ressure or at constant
volume. For a constant-volume "rocess,
"ecific eats for an Ideal Eas! Constant
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"ecific eats for an Ideal Eas! Constant
)ressure, Constant 'olume
(t constant "ressure,
"ecific eats for an Ideal Eas! Constant
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"ecific eats for an Ideal Eas! Constant
)ressure, Constant 'olume
oth CVand CPcan e calculated for amonatomic ideal gas using the first law of
thermodynamics.
"ecific eats for an Ideal Eas! Constant
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"ecific eats for an Ideal Eas! Constant
)ressure, Constant 'olume
(lthough this calculation was done for an ideal,monatomic gas, it works well for real gases.
"ecific eats for an Ideal Eas! Constant
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"ecific eats for an Ideal Eas! Constant
)ressure, Constant 'olume
The )-' curve for an adiaat isgiven y
where
The econd Law of Thermodynamics
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The econd Law of Thermodynamics
We obser!e that heat always flows spontaneously
from a warmer ob1ect to a cooler one, although the
opposite would not !iolate the conser!ation ofenergy. This direction of heat flow is one of the
ways of e$pressing the second law of
thermodynamics:
When o()ects o* di**erent temperat!res are (ro!+ht into
thermal contact, the spontaneo!s *lo& o* heat that
res!lts is al&a-s *rom the hi+h temperat!re o()ect to
the lo& temperat!re o()ect. /pontaneo!s heat *lo&never proceeds in the reverse direction.
eat %ngines and the Carnot Cycle
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eat %ngines and the Carnot Cycle
( heat engine is a device that converts heat into
work. ( classic exam"le is the steam engine.
Fuel heats the waterD the va"or ex"ands and
does work against the "istonD the va"orcondenses ack
into water againand the cycle
re"eats.
eat %ngines and the Carnot Cycle
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eat %ngines and the Carnot Cycle
(ll heat engines have!
a high-tem"erature reservoir
a low-tem"erature reservoira cyclical engine
These are illustrated
schematically here.
eat %ngines and the Carnot Cycle
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eat %ngines and the Carnot Cycle
(n amount of heat Qhis su""lied from the hot
reservoir to the engine during each cycle. *f thatheat, some a""ears as work, and the rest, Qc, is
given off as waste heat to the cold reservoir.
The efficiency is the fraction of the heat
su""lied to the engine that a""ears as work.
eat %ngines and the Carnot Cycle
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eat %ngines and the Carnot Cycle
The efficiency can also e written!
In order for the engine to run, there must
e a tem"erature differenceD otherwiseheat will not e transferred.
eat %ngines and the Carnot Cycle
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eat %ngines and the Carnot Cycle
The maximum-efficiency heat engine is
descried in Carnots theorem!
If an engine operating between two constant-
temperature reservoirs is to have maximum
efficiency, it must be an engine in which all processesare reversible. In addition, all reversible engines
operating between the same two temperatures, Tc
and Th, have the same efficiency.
This is an idealiationD no real engine can e
"erfectly reversile.
eat %ngines and the Carnot Cycle
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eat %ngines and the Carnot Cycle
If the efficiency de"ends only on the two
tem"eratures, the ratio of the tem"eratures muste the same as the ratio of the transferred heats.
Therefore, the maximum efficiency of a heat
engine can e written!
eat %ngines and the Carnot Cycle
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eat %ngines and the Carnot Cycle
The maximum work a heat engine can do is
then!
If the two reservoirs are at the same
tem"erature, the efficiency is eroD the
smaller the ratio of the cold tem"erature to
the hot tem"erature, the closer the efficiencywill e to 2.
=efrigerators, (ir Conditioners, and eat
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=efrigerators, (ir Conditioners, and eat
)um"s
#hile heat will flow s"ontaneously only from a
higher tem"erature to a lower one, it can e
made to flow the other way if work is done on
the system. =efrigerators, air conditioners,
and heat "um"s all use work to transfer heat
from a cold oGect to a hot oGect.
=efrigerators, (ir Conditioners, and eat
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g , ,
)um"s
If we com"are the
heat engine and therefrigerator, we see
that the refrigerator
is asically a heat
engine runningackwards B it uses
work to extract heat
from the coldreservoir /the inside of the refrigerator0 and
exhausts to the kitchen. +ote that- more heat is exhausted to the kitchen than is
removed from the refrigerator.
=efrigerators, (ir Conditioners, and eat
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g , ,
)um"s
(n ideal refrigerator would remove the mostheat from the interior while reAuiring the
smallest amount of work. This ratio is called the
coefficient of "erformance, C*)!
Ty"ical refrigerators have C*) values etween
3 and H. igger is etter
=efrigerators, (ir Conditioners, and eat
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g , ,
)um"s
(n air conditioner is
essentially identical to a
refrigeratorD the cold reservoir
is the interior of the house or
other s"ace eing cooled, andthe hot reservoir is outdoors.
%xhausting an air conditioner
within the house will result in
the house ecoming warmer,Gust as kee"ing the refrigerator
door o"en will result in the
kitchen ecoming warmer.
=efrigerators, (ir Conditioners, and eat
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g , ,
)um"s
Finally, a heat "um" is the
same as an air conditioner,
exce"t with the reservoirs
reversed. eat is removed
from the cold reservoiroutside, and exhausted
into the house, kee"ing it
warm. +ote that the work
the "um" does actuallycontriutes to the desired
result /a warmer house0 in
this case.
=efrigerators, (ir Conditioners, and eat
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g , ,
)um"s
In an ideal heat "um" with two o"erating
tem"eratures /cold and hot0, the Carnot relationshi"holdsD the work needed to add heat Qhto a room is!
The C*) for a heat "um"!
%ntro"y
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"y
( reversile engine has the following relation
etween the heat transferred and the reservoir
tem"eratures!
=ewriting,
This Auantity, QJT, is the same for oth reservoirs,
and is defined as the change in entro"y.
%ntro"y
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"y
For this definition to e valid, the heat transfer
must e reversile.
In a reversile heat engine, it can e shown
that the entro"y does not change.
%ntro"y
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"y
( real engine will o"erate at a lower efficiency
than a reversile engineD this means that less
heat is converted to work. Therefore,
(ny irreversile "rocess results in an
increase of entro"y.
%ntro"y
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"y
To generalie!
The total entropy of the universe increases whenever
an irreversible process occurs.
The total entropy of the universe is unchanged
whenever a reversible process occurs.
ince all real "rocesses are irreversile, the
entro"y of the universe continually increases. If
entro"y decreases in a system due to workeing done on it, a greater increase in entro"y
occurs outside the system.
%ntro"y
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y
(s the total entro"y of the universe
increases, its aility to do work decreases.
The excess heat exhausted during an
irreversile "rocess cannot e recoveredD
doing that would reAuire a decrease in
entro"y, which is not "ossile.
*rder, &isorder, and %ntro"y
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%ntro"y can e thought of as the increase in
disorder in the universe. In this diagram, the
end state is less ordered than the initial state B
the se"aration etween low and high
tem"erature areas has een lost.
*rder, &isorder, and %ntro"y
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If we look at the ultimate fate of the universe in
light of the continual increase in entro"y, we
might envision a future in which the entire
universe would have come to the same
tem"erature. (t this "oint, it would no longer e"ossile to do any work, nor would any ty"e of
life e "ossile. This is referred to as the Kheat
death of the universe.
*rder, &isorder, and %ntro"y
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o if entro"y is continually increasing, how is
life "ossile ow is it that s"ecies can evolveinto ever more com"lex forms &oesnt this
violate the second law of thermodynamics
+o B life and increasing com"lexity can exist
ecause they use energy to drive their
functioning. The overall entro"y of the universe
is still increasing. #hen a living entity sto"s
using energy, it dies, and its entro"y canincrease rather Auickly.
The Third Law of Thermodynamics
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(solute ero is a tem"erature that an oGect
can get aritrarily close to, ut never attain.Tem"eratures as low as 3.; x 2;->: have een
achieved in the laoratory, ut asolute ero will
remain ever elusive B there is sim"ly nowhere to
K"ut that last little it of energy.
This is the third law of thermodynamics!
It is impossible to lower the temperature of an obect
to absolute !ero in a finite number of steps.
ummary of
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#hen two oGects have the same tem"erature,
they are in thermal eAuilirium.
The first law of thermodynamics is a statement
of energy conservation that includes heat.
The internal energy of a system de"ends only
on its tem"erature, "ressure, and volume.
( Auasi-static "rocess is one in which thesystem may e considered to e in eAuilirium
at all times.
ummary
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In a reversile "rocess it is "ossile to return
the system and its surroundings to their initialstates.
Irreversile "rocesses cannot e undone.
The work done during a "rocess is eAual to thearea under the curve in the PV"lot.
The work done at constant "ressure is
The work done at constant volume is ero.
The work done in an isothermal ex"ansion is
ummary
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(n adiaatic "rocess is one where no heat
transfer occurs.
The value of the s"ecific heat de"ends on
whether it is at constant "ressure or at constant
volume.
$olar s"ecific heat is defined y!
For a monatomic gas at constant volume!
For a monatomic gas at constant "ressure!
ummary
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In a )' "lot, is constant, where
For a monatomic ideal gas,
The s"ontaneous flow of heat etween oGects
in thermal eAuilirium is always from the hotter
one to the colder one.( heat engine converts heat into work.
%fficiency of a heat engine!
ummary
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( reversile engine has the maximum "ossile
efficiency,
The maximum "ossile work!
=efrigerators, air conditioners, and heat "um"s
use work to transfer heat from a cold region to a
hot region.
ummary
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Coefficient of "erformance of a refrigerator!
#ork done y an ideal heat "um"!
Coefficient of "erformance for a heat "um"!
ummary
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Change of entro"y during a reversile heat
exchange!
Total entro"y of the universe increases whenever an
irreversile "rocess occursD total entro"y is
unchanged after an ideal reversile "rocess.
%ntro"y is a measure of disorder.
The heat death of the universe will occur when
everything is the same tem"erature and no more workcan e done.
It is im"ossile to lower the tem"erature of an oGect
to asolute ero in a finite numer of ste"s.
-
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