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Complete Netes
Devendra Peoria SirFirst and Second laws of thermodynamics. Applications of first law to close and
‘open systems. Second law and Entropy. Thermodynamic properties of pure
substances: Equation of State and residual properties, properties of mixtures: partial
molar properties, fugacity, excess properties and activity coefficients; phase
equilibria: predicting VLE of systems; chemical reaction equilibrium.
What is Hermodynamcs ?
ewe | + [Brome
Heat Particle in
metron
> Powes developed from heat:
> It deols wth change i) energy or entropy or with
tmsersion of heat to Wark o¥ work vo heat:
> Powes developed from heat:
> It deols wrth change 17 energy or entropy ox with
sygersion of heat to Wk oF Work To heat.
> Thermodynamics tel Us whelber the reaction is possible:
08 Avb
AreB—3¢
> But rt does nob tel us about Conversion, extent vt
reaction, equiliorium Gust of Not oY ATI Muth AL Convert
to c.System i- A devtce oY a Combination of devTces which
conten & Quantity of matter which being Steved.
Surrounding :- Apart prem System every bing is Surrounding.
Universe = System + Sureouacing-
Propertress Decoriptive thavactorectic. of the System 1S prapesties.
© Jntensive Pooperties :-
Independent off mass.
Examples: TP, P, 4,0 ete:
® Extensive Pespesties
> Examples: mass, volume , E'S (U,H,G,A,S)
Depend, on mass.
> Pny Extensive property When dinde wth mass become
intensive — Gpecifre, valume = Vo oo
Toes of systems:-
Ange devrce whion has a quantity a matter
and which iS being Studved,
( Closed System + Only enerdy Ca!
(Open syctem + Both mass and, energy can be exchanged
Gi) Isolated System : Neither ‘mass? Aor ‘energy’
in be exchanged,Tempecature !- Temperature is @ thermal potential off System
responsible for heat teanshor-
Temperature Conversion:
ee ae. oner
re . * ‘
0% atau 82 ee
TE) = 32 T(k) 27S _—T(R) = 491-67
a Se a
37845-87315
212-32
6169-49167
Compressive force perpendicatay to the unst area-
e x
uz untae Pe
nut a,
Pats = Patm + Prouge,
Pass = Pam — Ry
Latm = (01325 Pa = 760 mmHy = 760 tH = 10-3 m 40
‘Tes off Energy i-
© Macroscopic : ( Potential energy & kinematic energy)
© Microscope: (Internat, Energy)
kinetic Enexgy:- The energy Pessessed by a body by urtue of its
moti 1s omtled the Kinetic enelgy- If a body of m moves uth
@ veleaty v we kmetic Orergy (LE) possessed by the bidy is given,
Ke =f mvePotential Energy:- The energy potsesred by a body by untue of itt
Location is called potentral Energy I¢ @ body of mass m is at
GQ elevation of h above the datum plane, the prtentiaL Energy (PE)
Possessed by me body. is given oy
PE =mgh
Mechani cat B. i
Mecnemleet BOOP roe. pe a op
Internal Energy :-
It is the microscepic intesmolecutar motion off
electrons oF Sphhs of electrons, intes atomre interactim, vibration
os Deansatio fF mojecufes.
2 Uw Ue Canit be measwed directly only the change in au
Gan be Measured
Vd Ve,Vive
dws Bak
diss 1B i ldxl cone
Hee Och os NTE
ses PAC)
ve
dus -p( av
Giy In Expansion
a> Ve
Shaded aren
:
we fra
dw = IPL dz | cos
B= 160" ( Force & displacement in pposite dccten)
w= - Naz
a
saws —p Cavdw= IPlide| cose
O= 160° (Force & displacement in opposite dreetrmn)
ow = - IPI aR1
ve
awe —p Sav
> On compression, upsk dome is +ve,
werk is dome om the System by the summpunding--
> On Expansion, weak done is -ve,
wok 1S done by the Gyttem on the surmunding.
Note:~
® The ratio of an extensive property to the
per unrt mass) is atled the Specibic property.
mass Corthe property
Totes Votume ovo me
™
cpeaie Volume 9 = =O 5
® The vatio of an extensive property to the mole number Cos the,
Propesty pew mee) is called, the molar propecty-
Fetal Volume _ Vg
Mele Number
Molay Vetume
akeQue:- Class iby the pettowing pavpesties
© pressure
W Temperoture
Wd Volume,
Wy dnternay Energy
WD Volume per mole
Oi) mass
ip Pnthalpy per uit mass
Extensive pospesty + ci) Gy Lv)
Antensive Propecty ! G) Gi)
Specigre prepesty + ip
Molar propesty Ww
Theymodynamic Equitsbeium
"Por a system to be in a State of
Unermadynamic equilsbrium rt Sheuld Smultensucly Satishy the ortine
gr termal equiubrum, mechanical exuilebr'um ang chemiowd Equsibrtan
Thermal Equirbstum:
= =" dh there 1s no further change: in thermal condition,
(lempecature) of @ System; when +t iS Isolated, te System *S
Sud, to be m a State of thermal equilibrium.
3 In q stote of thermal equilibrium , there (s no temperature
gradient wrthin the Syctem-
> Th tw systems ave in thermal equilibrium Lith each other:
where Te Te denste the temperatures of the systems A 2B.(ly Mechanical, Bui erium :-
Ib there is no imbatance of forces in a
Eyitem ishen it ie isolated it 1s card to be Ina State of
Rechanicah Equibbrrum.
> Ib tn systems are in State of mechanical equilibrium wth each
other, the pressure of both systems 4 rdentical,. That fs,
Pa = Pe
Where Pa & Pg denote the prestwe of Syrtems AR,
Chemicob Equilibeum?—
Uy the cemposrtton off Syetem doe net undergo
amy change due to aghusion, mass transher cy chemigt reaction
and i there is no tendeny fer Q change In (tS Chemical Composin™
then the system is (Solofed-
>The dibjerence in chemical potentral causes afusion, mass tania
oo themeol reaction.
>In w State of Chemical equitkbrum the chemicae potential 'S
unigsem throughout the Syrten-
as ue
there UM ond 44j8 denste the chemical Potential sty Componest
Com syctemsHeat :-
ae
The heat interechon occas by uMtue of temperature dibpecce
aercrs te brondary:
lice werk, 1% Gusts only AS energy im transient foom ton
me bodg te another or between System ot te carmurclng
Resor law of Thesmodya i
Ug © body ‘Aa’ 1s in Thermal equilib
vium wrth body “8 anc. bedy ‘6’ In thermal equilrbrium with body 'C)
then body ‘c* is also in themat equlubrium wrth A-
State B Path dependent Vatrable & t-
> Properties thot doe not clepend, upon the path by uth
th veaches a State Such quantrty are know as State
vavrables-
> They are also kaw as point punctrons. & generally rpreerted,
os exact dibjerertiols.
For ex: Temperature , pressure, volume efe.
> the quanhhes which depend upon the path fpllared by the
System ae Enon as path fenctioy.
For example > BR Ww are the path functors in thermodyranses.
We -Pav Q= TasF> degree of freedom
C3 number of Compound
P23 number of phases
¥> number of independent chemical reaction
S82 Special Conctvamt = 4 (Por Immisrbie Setston &
azeotrops)
P+2
> Gibbs phase rule gires the degree of freedom Cor the number of Inde-
Pendent thesmodynamic Prperties) hk a System- These propesties ae
intesie properties only. Mey Cannot be extensive praperties.
Process :-
=
When a System Changes from @ Specired intral equilrbrua,
Ctate +o another, equilibrium state, the path fetiewed by the Sytem,
in renching mak equilinum tate prem the given inttal State is
adted the process:
Quasi - Static Process t-
Se
A process whey take place very Slowly
with infinitesimal dnving. force 18 calied @ Quasi- Stabe process.‘ble Processes i-
3A thermodynamic process 1 dard to be reversible t& The process
can be tumed, back Such tht both the System and the summunding
retum to their orginal States, nth no othes change anywhere else”
the umverse- :
> In reakity, no Sud processes as reversible process can exist , thus,
the reversible processes can easily be defined as tdeakizations 62
models of real processes. ‘
> hey help us ia incarnng the maximum ebfrcrency a Syctem can
provide in teak warking Conditrons and thus the target design Gat
can be set.
Examples :-
3 Extension of Springs
> Slow adiabatic compression or expansim of gases
> eleePolysis (uttyno resrstance of eleetrotyte)
3 Gerchonless motton of Solids
> Hour isothermal compresscon or fepansion ols gases
Lvveverssible Processes i-
> An Preversible process Gan be defined, ac 4 process In wtuth the
System and the SurrPuadugs do not Return to ther original state.
Once the process f¢ Iartroted-Examples :-
> Relative motton ut pietrom
> Throttng.
> Heat transfer
> Diftusin
> Clectricnty ploir throwth a redrstance-
First lax ob thermodynamics:
Toute's Experiment t-
> True placed karwn amount of water, o% and mercury in an
insulated, Container and ogetated Hod wth a rotating ctrver:
> The amount of ome om the flad by stirrer were accuretly measyred,
and the temperature chargec of the fluid were carefully noted:
> He found for each plurd tat a fixed amount of work Was required
pee ut mass pr every degree of temperature rice caused by CHT:
> Toute demonstrate that a quanhtotive relatimship exces betwren
Wot and heat, therefme heat 1s a pom of energy *> In Toutes experiment Energy wee added to fluid af wrtk and,
has lates tranchered from the phd as heat
> lt was the basis f% porbdotio of ccept of intesnad
enex od .
> Heat & work can be Stored in the Gyetem aa internal energy.
> Wore dre om tho syttem wrth inorease the molealar actirty
Uke heat:
A ( Enevgy of the syetem) = R+tw
D> Thal energy orange of a dosed System esuale the net oneryy”
transfered into rt as Reat and wrk.
First La
“Energy can neither be created ney be desboyed, when
it drvappears in one form , it must reappear at the same time iv
other tprmy.
AEnergy of syttem) + 4 (Energy of Surromdung) = 0
Grergy Babance for closed Systenrt-
> Since, no Streams enter ov Leave a doled System no mtertal enogy
te tronspated acrest the boundary of the eyctem -
>» Closed System often Underge procestes that cause no change.
Im the System other than its intesnal Energy
outs ath Ut=nU @ mu
vtz nv amv
aM) =@+WEnthotpy
anole!
It is a meacurement of energy in a thermodynamic syctem.
It is equal to the product of internat energy of the syrtem plus the
product of presture and, volume. % includes internal energy
SH= tve . endothermic reaction
OH= Ve, exothermic reaction
> U4s on— intevinsie— propesty-
wer Entei He U+ Pv
The diggereatral term is
dH= du+ dcpv)
Signipeance: It is used in batanceg pr plow Processes as
Opplied to exchangers, evaporators, distitiatren colsums,
pumps , compressivs, turbines, engines etc. het calculation ots feat
& work.
The amount of heat required to rite the temperaty
ob 1 by % 1 mole of @ gas IS known as heat tapacity.
c= dh
qT
Mion c= IaHeal capacity of constant volume ® pressure!
We know thot ,
For monoatomic gases
Ut= 3 y,pat= Spy =28
Znrot = Sp 2 uk
At Constant Pressure t-
Av= Q@tw
Q= sU-W
= 4U+aley
aor
= su+aly) _ Znroty nrot
oT orSU=atw
Q=ou-0
Sv= 4u-" _ au~o Be lhc
ar or
2s =
Se Zan , whan
Cp-ey=R
We know 4H = OU + acpy)
OH= AU + Pov +vaP
OH= Q-Pav+t Pav +vaP
OH=Q! (at constant Pressure)
aoImplied Psvperty Relations t-
H= U+PV
dH= du+ dCPv)
Types ob Thermodynamic Process t-
© Isobaric Process:
> Processes (© Which pressure is Constant-
P> Constant
va
AU=QHEW we -p fav
Ms® Isochowic Process :-
oe ae
> Volume (§ Constant
du= 6+
® Isothermat Processt~
mi ——
“Pdv =0
3 Temperature (6 constant
ou=
BH = 0
We know,
Fer ideat gases,
p= at
Wd.
Sovar
foer
=-Pdv
Pav
PU= RT = ConstontFor ideal gases, Pi, =P2¥, > Yes fr
Pa
We - RT &o(21)
® Aobstic Process
Y= Ratio of heat capenty
Per odabatre Prevess Q=0 ou=Q+W)
= GAT +Pdv = 0
daz cydt + RTqy = 0
v
wat =- RT
v
pvt = conctWe kano PVERT nS
Pu? = conct
The quid wrthin te Controt volume is the thermodynamic
gyctem for Whech mass and energy balances are written.
& inftow © outfios
General mass batance ;
Mass inflms — mass outflmx + generation consumption
= Accumutation
~A = Accumutatin
Accl+ ae=0
dmey G3
—— + alin) =
yen fs) = 0
hfs = Me Pig ty
fs > Flowing. streamdmey
ae + a (P4Aps = 0 KeeatienstyfEauation)
> If Steady State, thea
a (PuUA)p, = 0
frat, — fila, = 0
m= PU2Ar= Py AL
Energy Bakance +
| Control surgace
pron--—---- ee.
t
'
'
> Flowing Stream hare energy assowated with them in its,
internal, potential ® netic eneigy. forms.> Each unit macs of 4 Stream cares with it a totoe energy
(u+sus #2)
The net energy transported by fouwing Stream ic
-a[(ur ges 82) Jp
1 Cm Wey -a[(v tue ‘J + Q4K,
wae A [Cot awteas ay, + e+ oe
> Piston wok is the work dome by this piston in the meving
uut mass is (PV) & wotk dome is m(PV)
dCmWey _ a . Q+ 0
=" ~a[(v+gurege a] + @+ Ip
> Piston wrk is the work dome by this piston in the mevigg
unt mass is (PV) & wotlk doe is (PV)
> Another foim of wok 1s Shaft work.
4.6m UD ow ( i. ‘] ee
= -al(utsursgz)o] + Q4+ Ws - CPV Mf
dt ( S +32) fs
Loony af (wegeese) i] = Q+Ws
at 46Case) Centre off mass of control volume 16 Stationary .
ake & PE =0
d(mWey
+ OCH) = Q+ te
ae fs
dy Mass Balance por Steady floor processes.
alte dure, © aes
a [uaguregz] = OtwWs
diving by ™,
th KE=PE=0Thermodynamic. foperties s6 five Substances +
Pure Suostance- In geneval a pure Substance is one uu
consists of a Single chemical Species Ske M0,
We, Na, 02 ete.
Phaser- A system swhich 1s uniform thraghout beth in chemucak
composition and physical State, is cated & phase
2A poe substance can exist in three different states of
Prysicol oggregatian -
Example: Water can be found as sed (ice), Lquid, and gas
Coulee, 2. water 8, vapeur. or cteam)
> The thermodynamic prpesties which are in unde use are
Pressure (P), molar /Specipre vetume (») temperature (T), enthalpy (4)
and entropy.ic).
> ‘The widely wed and most Omvenient method of representing
the thermedynamic data, ae:
© GrephicaL representation of data ia the form of diagrams.
® Tabular representation or presenting the data in the poem oh
tobles
@ Mothematical repesentation of date im the tum of
Guatrons.The most undel¢ used thermodynamics diagvoms for a pure
Lubstance ares
> P-v dragrem 2 T-S dhagram
~* H-s dragram
PHA diagran,
2 P-T diagram
~ Tv dagram
Saturated Wquid i-
3A Uqud @ “uch is in equilibrium wits its
own vapour at a Speefrc temp] pressure fs Glled Sofureted
Liqued-
2 That 1s a Uquid ot its boiling point at Cpeubied presrox
1s a, Soturated trquedt-
2 ot PrLatm, T= 10% , water fs w Saturated dqud-
Seturated, vapouy f-
A Vepmy whch wis in equilbyum tert it
Liquid at @ Specipe temperature | presure iS Glled Saturated
vapour:
2 That; is vapor at HS Undensing temperature at spouted preivre
‘sa saturated vaprur.
Over Degree of eedam fer pure Substance oxting as
& Soturated Yaqui, Gi Soturated vapout ”Saturation temperature:
The temperature at whith a Uqud bails
(or equiborivey wits itt com Myowr) at & Speufed prestyr «Ss
Cetted, Saturation temperature.
Latuvation Pressure s—
Tre pressure, of w Speqfred temperectue,
at which the ecquid baIlS. (oy in equilibsium wis itt mn vepove)
ig Calted Satwation pressure.
2 at Latm(PH=101-226 kha) water bes at (00°C.
fo, at P= 101-325 kta, Satwetion temperture of water
= loo,
7 Gk (o%, the Scfuvatron pressure of wetey 1S 101-225 kPa.
Sometimes, the Safwrotion pressure is Cbled, UmpoUr prepgsure-
The Stote at which alg three phases- Setiq
Liquid and, Capo Coenst in equisbnum
Point -
is colted the trpAe
Que: DoF ot triptd point 2
Ang: Zero
» therefore , tripple pomt exSts ot & defnite pressywre & tenpes~
ature.
> The Wipple print wy Wate, J8 P= O-6i Pa. &
T= 0-0/%e = 973.1 KCriticag Point i
3 Critical Pont represents the Aighest temperature
Gnd, pressure above Which Liquid Can nob exist:
> At @ te critreal point the Uqud and vepmur gre
ind ting-us shable-
> Properties of Saturated Liquid and saturated, vepour ae
ideptiat ot cntical point
> If © gas is to be condensed Cuquiped) ab constant tempestire
by the appticatron of presswes its temperature Must be bela
the crtical temperature:
> If a gap re to be Uguifred by Coding at Conctant presiire
by the application of tempemture, rts pressyre must te selnr
te O1foh pressure-
Supetheated Vapour t-
> A vapour excting at @ temperature abmeve the Saturation
tempesature ot a Specifred prestute is Clled Superheated,
Vapour -
7 Steam ot (01-325kRa & isore is a Supesheated vapeu7-
Subcovled Liquid i-
+A Uquid ot a temperature below its Satusaton temperatec,
at Specified premwe iS Gket Subcorled Liqurd,BT Diagram'-
=S =I
Ps
© + T-2 > Solid - Lquid, equitidsium relationship ( Pusion curve)
@ +T-t > Gublimatron curve @ +T-c > Vaporization curve
® +7 > AN tree Cines meet at the triple Point, where the Tree phates
coexist in equilibrium:
© +c Is the oriticel port
> Te, Pe ave heighest pressure and temperatwe ab which the
pure themicel Species can exist in vapour andy Lequed epuilibum.
© +c Is the oritical pont
> T, P are heighest pressure and temperature ab which the
pure themical Species can exist im vapour and Ligue, @guilr buen.
> Poth AB lead from the Liquid, rege to the gay rN Lrit
crescing @ phase boundary -
> On the otber hend , paths which oress boundary. R-c induwe a
Wapourization Step, where an abrupt Change from Liquid to gas
Oceyry.3 A phase iS generally considered a Liquid phase if vapourization
yesults from pressure reduction At constant temperature
> A phase iS Considered gas, iff Condensation recultt from temperstine.
deduction at ConStant pressyre-
Vapour phase can also be condensed, by Compression at Constent tempert
3 The reyI0n 1D Which T>Te, is bom es Supescntiat pusd:
> Slope of fusion Curve tex Water is Negetive-
ae) °T-2' Por off othey Substances the Slope off fusion curve
wi be positive -
PT 3 metting point T
saturated liquid line: x=0
saturated vapor line: x=1Quality
We need to define a new thermodynamic property: Quali
total mass of mixture
mass fraction of the gas,
mass fraction of the liquid
myvy + Mg,
= =(l-a)y +20,
uy
°y9
(l-a)uy tau, =u tou, > 2
h = (1-a)hy+ah,=hy+chy a=
s=(1-
sy +2 8, = by + 28> T=
Pv Diagva
critical point
Sofurated, Vapor
fig: PV diagram jes waterIce is heated pum -1s%c to orc (1 to 2) At point to2.
melting. ofr (ce takes place.
‘The system is again heated, O'C to 4° tHe Bere isa
decseace in volume of water.
On purges heating prom 4% to to0'c, the Urlume of water
iS increased & ot loo’ phase Change off water «wecry
& vapor phase iS than ebtuined-
On PU chiagvam, boundaries becomes areas, be- MEGiONS Where,
two Phases, S/L, Liv, S/v Co-ewSt in “quilibvium.Isotherms :-
> The fovizontay, Segment of tach isotherm represents ale
Possible mixtures of Liquid and, Vapour in &™ ranger form
too, Uquid at the Leff end +o (00% vapow ot right end-
> the cus of these end points i$ the dome - Shaped cured
Loboled, Bcd, the feft halls off Which (@ to C) represents
Single phase (Saturated) Liquid ab them vapowi2ation (Dating)
temperature.
> Ther vignt tally (C00), smgte -phwe ( Saturated) vapour at
Thuy tondensation bempesawed.
> Isotherm in the Subtovled Uquid region Gre vesy steep,
becqure Liquid ottumes changes trttle int) large change in
presture.fi mathemoticaL expression of the type
which decoribe the p-v-T behawtous oF
of stote-
f(P.u.T)=0
Substances is -calted an
equation
Jour ¢-
= Boyle's tax States that the motay volume (vy) of
inversely with pessure (P) when temperoture (1)
@ gas varies
is held constant.
v at or Pu = Constant
Chawles law
charles taw States that
is directly propectional to
the molar volume ob @ gas
is help conctant -
tempesoture hen the pressu7ve
vat
( the pressure exerted by a 92s is dnectly Prvpoetronal
to temperature when the uvlume ‘s held Conctant .
PATaeat Gas Equation of State:
The tdeak gas equation of state given by
Pv = RT ve melar votume
[pv = oat] SRT V= total Velume
N= number of moles
R= unnersel gas constant
=8-314 T/met K
= 0-214 br|kmdk
T= temperature
Assumptions KTG i-
4. The volume orcupred by the goo metemfes 1S nEqlibrble
tempared to the urlume aqvaslabie 492 Pee motion
2. The molecules are independent of eath ofhey and do not
exert ang attyactive porces.
> The sdeak gas Laur is only an approcumation oF ideatizakien
“& the bthureu of gases, SE
> LEIS appbcable at lme pressure and Ryn temperate
Where the densiy 1s Suppioenty Lrg
In generat he P-U-T dehauiom, of real Gases dibfess from
that predicted by the (deal gas laus-
Compressible substance i-
DAN Substances - Sold, Liquids and gases. ~ Change their
Speeric /metay uttume when they are Subjected to Q change
in temperoture and prescure
> Is the change in the ustume is quite Significant the Sabsc-
tance is colled, Compre ssible-‘Notes by Devendra Poonia Sir
V= vt, Pp)
dv = (24), a7 + w) ap
devieting by ov
avs (ed 2) ap
Via au ),a7 + (3) 4
Bat -k dP
Velume Expensivtty B=
Lothermal Compre scibility
Unit off ‘B’ = kot
Unt of '&' = Pam
> Pox tmeompressible Hurd
B&k =0
No read Hurd 18 Puly incompressible
> There iS No P-U-T eqn of state fam fx an
incompressible flurd, because ‘v' *S independent of
“T° @ 3p.
k (Pe-P,)CUBIC EQUATION OF STATE! (Vander nmal's Equation) :-
Cuore EQUATION Fee Unnier als ae
> The ideat gas las is only an approximation ox idealization
to the P-v-T
behaviour of gases. and it
is applicable at Cox
densities only.
> The P-v-T behaviour of real gases dibfer trom that predicted
by the ideot gas taw-
» In 1672 Vandes Woals proposed an equation of state utuch
takes into account
4 The unavailable volume $92 molecutay motion, that fs the
excluded volume and,
Tne attractive perces between the molecules whith leads to
a reductim in pressvre exerted by the gas.
a Pils is the pessure the gas would fave
~ exested in absense of the otftvactrte
forces -
as moleclar attraction
Viz=Web , the Pee volume avarlable fet Mmelecutar
motto ss Cv—-bD
b> moleculer size
P+ 2 ) we) = RT
ve+ Here a & b are catted Vander Walls constants. and they depend
on the ratwe of the gas.
+ When they ae 2ex0 , the ideal gas equation is recovered
> The van der waals equation of State 1s Cubic in volume and
in general it gives three values of volume (Vv) at @ given
temperature and presswre-
> TOT 2 there 1S onlg one real value fee velume-
> Tc Te > Ht gives three real valueS YE, Vi and Vg het volume.
> Segment 12345 iS not in agreement wt» Ceperimental observatiay.> The practiotly reolizable vouation of volume indicted by
the doted Une !-8-S-
2 In Segment 234 the van dos Wwabls equation Sheng that the
Utlume increases with inveasing presswre ot tmstant temperakie
hwhich 1S not reabistre-
> the Sytem chodd actully tolls the dotted Shight tine
Palh I-23-S in the region.
» The velume Vi which iS predrcted by the van dey Wants equation
%§ Stofe (S$ inadmissible.
> Of the tee seal values the smaltest value Ug represeats Re
Witvme of the Liquid phase and Largest value Vg repeseats the
volume of the gas phase.
Conditims Which must be Sotisired by wey equation of Statet-
© ‘The oF a ‘sotenm on PveV diagram must be negetive-
That 1s (3F) <0. In omer wards the ‘Sotrermat Conpressitty
be -L (av
4 (3). >0
@ It Shotd reduce to the seat gas tur PU=RT ac Pro
® At the criticog point, the criticag isotheam must exhibit @ pou
OF inffexion. Stated mathematic ally
i)
e (2) =>
awe TeThe cyiticag iSotherm must exfubit a pat of inflexian at the
enticot point. Mat is, it Should Sotisty the Condstions .
2
(2) 20 on (#)=°
awh, wh,
The Von dey wat equation of State Can be wrtten «s
Rt a
Peet _ =
wa;
eric — 8, Sh =
Thee bore (3). Ger * ve iQ
ee. ae —o
(y-6)? v2
ote), | Re ba i
wey (u-y vS
ART = & —6a
(u-5)? 4
Diiding ean® by earO
2 > 2 >
%-b Wy
At cntte£ point, the Von dey Woals equatim of state rs
orutien as
Be Sew —o
(and veSubstitute the value of Ve in e9rciy and en Gl
> Theregme . we can estumte the values of Pe, Te and Ye fom a
knoutedge of the Vander wmals tonStont -
> Altesnatnely, me an determine the Conttant a and 6 bom
@ knndedse oF PB Te.
a= 2WRedb na
Go S
8 4 27h
Critical Compressrbibty
z= > Freten fou ae gases.a= ARR a:
eo 2
8 ‘ 278%
ba Re
8Pc
Critical Compressibibity,
z= 2 Fretor fou ale gases.
Viriak equation off State :-
—— Visio equation of state which ‘s expressed
as @ power Sexes in reciproaae volumes,
> 8.C,p ete. are Enmon as Second, viriok Cooppicent, third virial Coeppioent,
tourts visit coepfent etc.
> The uiviok Coobfrerents express the deviation from idest gas behav
and they depend on the nature the gaS and temperature only.
> The Second viviok coepficcent takes mto account to body. interectien:
Ad the third uTsial Coehtuent tokes into account thee body
interections etcThe advantages of the virial equation off state is that rt can
be made to represent the experimental P-v-T data Accurately by
inextasing- the number off terms in the pwer sewes cepending.
™ Complexity of the Substonce-
The uivial equation of State is Sometimes expressed aS a powey
Series in presswe as
1+ B/P + cP +
The virial Coepfiuents 8’, c', 0’ are related to virial Coefprelents
B.c.D of the pressure explicit utrial equation of State
The volume explicit virial equation of Stete is given by
Py
sr = NF IP HCPA + OTB Fm
ar
= & y PR or P3R:
po Ty SRPr oe + TERT —@Equacion © ~- Equation@
uw
Bb CRT
ee ee, er van [SE Ot eat 4 PRT. 4.
+ RT Sry ORE cet ORT
aa ie Bee]
+ per [ ar ger, cet, DRT, ..
v ear One —®
Now, we find that both equatims O&@ are expressed, as powes
Sexies is reciprocal volumes. Comparing the Uke tems we yer
the following results :
Terms of 4, , Re
Sof gives: Ot
Terms of L gives: SRT. g'a(ar)* c'crry?
va oa fa
C= B'BRT + C'CRT)*
C= B+ ctr)
c= C78?
Qr*
Terms of tS) gives:
ort. Bic (aT), 2ecrCer)? o'(ant
vt ve ve vt
u
BRT | nece-eveT , DiCen)t
vie) ve vebiz p-2ec +203
(anys
Compressibilsty factors t-
the Compressibitity factor Z is defined
as the vatio the actual volume to the udlume predicted by
ideak gas law at the Same temperature and presswe-
ee Actual Volume
Ustume predseted oy Ideal 92S
v
z= es ee
(rip) Rr
4 For an ideal gas 2
at att temperatures and preasyre.
> Fox a rect gas Z can be different fom varty-
> The value of Z imdrcates the extent of dewratron trom the rdeot
gas law.
fhe reduced temperature of 2 Substance * defaced as “he ratio of
the tomperatine of the Substance to its crrtrcal tempesature-
Reduced temperature T= LT
Te
Reduced Pressure ene
Reduced volume W=THEORM oF CORRESPONDING, STATES -
a The lus of Consesponding states
telts that abt ffusds when considered et ‘the Same values of reduced
temperature and reduced, pressure will hare the Same value of
redyced volume-
> That me wl pus Aaving Ue Same value of 7 and Py ave Sard
to be in concsponding States.
“
DAN fuds when compared at the Same reduced, temperature &
reduced pressure, have Oppreximately “he Same compressibility
factor & all deviate fr0M sdeag-gas behaviour to abut Same depee?
> Thig theosm is very nemrig exact pf the Simple fluids CArgon, keypton,
© Xenon) Systematic observations are observed for move Complece-
Huds.
Experimental observation shows that compressibility factors Z for
different fluids exhibit similar behavior when correlated as a
function of reduced temperature T, and reduced pressure P_
7-1. P=P/P,
This forms the basis for the fwo-parameter theorem of
corresponding states
Theorem of corresponding states: All fluids, when compared at
the same reduced temperature and reduced pressure, have
approximately the same compressibility factor, and all deviate
from ideal-gas behavior to about the same degree.Corresponding states correlations of Z based on this theorem
are called two parameters correlations as they are
dependent on two reducing parameters Tc and Pc
Although these correlations are very nearly exact for the
simple fluids like argon, krypton _and_ xenon, systematic
deviations are observed for more complex fluids.
the logarithm of the vapor pressure of a pure fluid is approximately linear in the
reciprocal of absolute reduced temperature.
(tag Pe) é
ACY Te)
If the two-parameter theorem of corresponding states
were generally valid, the slope $ would be the same for
all pure fluids.
This is observed not to be true; each fluid has its own
characteristic value of S, which could in principle serve
as a third corresponding-states parameter. And that was
acentric factor
For complex fluids, we carry out the study of another
parameter “acentric factor (w)" along with the Te and
Pe.
[tog pcan ~ ugh]
= 10 ~ tog (PEt) 0-7+ Figure. | Approximate temperature : Slope = -23
dependency of the reduced vapour (ie 0)
Pressure
+ However, all vapor-pressure data for the simple fluids
(Ar, Kr, Xe) lie on the same line when plotted as log P.
vs. 1/ T, and that the line passes through log P= -1.0
atT,=0.7.
* Data for other fluids define other lines whose locations
can be fixed in relation to the line for the simple fluids
(SF) by the difference:
+ where Pat is the reduced saturated vapor pressure, T, is
the reduced temperature, and S is the slope of a plot of
log P= vs. 1/T,.The acentric factor for a pure chemical species is defined with
reference to its vapor pressure.
We W108 ~ Lg (est, = 07
two-parameter theorem is strictly applies only to a fluid (liquid or gas) comprised of
spherical molecules. The deviation of fluids containing nonspherical molecules, or those
with polar groups, from their spherical counterparts is correlated with the acentric factor.
The definition of w makes its value zero for argon, krypton, and xenon and
experimental data yield compressibility factor for all the fluids that are
correlated by the same curves when Z is represented as a function of
reduced temperature and reduced pressure. This is basic premise of the
following three parameter theorem of corresponding states
Three Parameter Theorem
All fluids having the same value of acentric factor, when compared at
same reduced temperature and same reduced pressure, have about the
same value of reduced compressibility factor Z, and all deviate from
ideal-gas behaviour to about same degree.‘Notes by Devendra Poonia Sir
Second Laur of Thermodynamics ;-
Limitation of the Pisst tour:
2 First Lug of thermodynamics deals wth energy changes
involved in @ process
> It does not tere whether a preprsed Change umuld oefually
Gecure oF nots
2 Ue it occurs, what is the diveetion of thonge.?
> Major Lmitation : Its inabitry to deat with the direction of
the process.
Direction of Change t-
For example, tina of woter Brom a top of mountain to
the bottom.
« Anitiab potentiag energy gets amvested tv kinetic energy
> Pirst law sottepied, the total energy remains unchanged.
+ Pqually be satisfied in the reresse Procese in which the
water plows upumds cmtinously.
> Heat Hoos tom @ body ot hughes temperate to lower,
temperoture-
> Heat uth never bine from lower to Aigher temp - unthout
Cxternal werk.> According to pet Law, energy gained by Cold body must be
equal to energy Lost by tot body.
> First Lux doesnt preditt bunshes ob heat fpom hot to cold
body.
> Umitatons of test law led to development off fecond Law
ob thermodynamics, which deals with diecho of change.
Oibherence Between Heat & work :-
> Guatrtative dibgerence between heat & work occurs, when
we consider Converting heat energy tp other form of energy
> Possible to convert ome frm of woik to another ( Such ac
atectricol to mechanical) bith 1007 ebbierency .
> Comersion of Reak into work ik Linuted to vecy le values.
> During emversion eb heat into work, a partion of tre energy
becomes unavailable , not capable ob being ‘transpsrmed into
wefut form.
> Uy temperotoe increase, heat increases 2 thersefwe the
ehticency also incrences
First Cour of thermodynamics AuU= @4+W
At constent temperature , T= Const-
Q=-w (Fox an ideag gas)
Stotement 1 does not Say thet heat connot be converted into wk.© Kelvin Plank's Statement i-
a tt 1s impossible % Constuct an
engine thet operating omtinususly Cin a cycle), with produce no
ebyect other than -teanshes of heat OM a Single thermal reserma
ot a unbfirm temperate & the performance of an eqyel gest
Ob wet
® Clausius statement :-
a 1t is impossible to constuk a heal pump
teat epesating fontinously , unite Prduce nv sthen ebpect other than
the pansher ob feat pom a lower temperature body to a
Higher temperatwe one-
Thermat Reservioy:-
Layge body from which a fate quantety ob
energy can be extracted oy to whieh a finte quanhty of energf
Gan be added as heat unthout changing its temperature.
SQUICE! A thermak reservoir at hgh temperature Yom which the deuce
recewe the energy as heat:
‘Low temperature reservioy tO which a device rejects the energy
0S heat:Heat Engines t=
Devices oF machines thet produce work from feat |
a cyouc process.
> An steam prwee plant, in which the working Hud (Steam) periodicatly,
returns to itt ovigmat state
Safrated,
eau
at hig
yp >
© Liquid water at ambient temperature is pumped into &
boiler at Ah pressure:
® Heat prom a fuel is transfered in the boiler to the water
Converting re to hugh temperature steam at the borler pressure
@ Eneigy is transjoed as that wmk jrom the eam to the
Surveunding- by the device Such as a turbine, in wich the
cteam expands to reduced pretsure & temperature:
® Exhaust steam from the turbine is condensed by transper
% heat t the surroundings, pronding Uquid water for rebum
W the borler, thus Completing the cycte-