918

Wpe.ggatferfitptE during
lectures

Part Review of Classical Thermodynamics

1 Use materialproperties 1stLaw 2ndLaw to determine
bounds or limits on processes at equilibrium
2 Correlate equilibrium material properties measured
with other properties we need
You can typically Other properties
youneed
N.TTfTI U S HA G M

Reviewconservationquations G 1 3
Mass AntoineLavoisier 1743 1794 first todemonstrate
Momentum IsaacNewton 1642 1726 ma F

Energy WilliamRankine 1820 1872 first to use phrase

9ggtine.to control volume

nea

StepTwo Balance contributions to changing quantity O

Q water compound Teslas people
ft
or surfaceboundary
I I
entering

I is
inside a
onsite a
Ising rate ofconsumption is

MacroscopicBalances
 M total mass inside the CV

É'm
Frothed
Misses
dat
k I flow rate mass is conserved
mass time

Ma mass of species a in a mixture inside CV

Tf stging t Fa
net rate of generation of a
of
massflow rate
a in stream K IE Mfg
let's sum over all species
skies date
É'sEigaE't IM

IfEmadts2gesp m
EMna mix É'm
dmz
stg'm Et
TEE o

linear momentum Mayesvelocity

IIE
Generation
dI Destruction
or

O linear momentum
is conserved
 O linear momentum of species a Maka

draft
tfEkintmate of linear momentumgain
by species a

my I'maka Ek FEI
in order to conserve total linear momentum EÉMF0
O E energy of a material
E U Emv t my
internal kinetic potential
energy energy energy
statefunction
examples
heightabove somefixed
Higher reference
deceleration of
gravity
m4 q0 potential
Inergfelectrostatic

dafuttmutm4
É mk Utter't4 Pi
I
specificinternal fry
specificvolume
E Miss
energy eggs pressure
9 13

Egg pdf
ÉÉea
Égenerate
W
W work done TO
netrate of on or by energy
heatentering work done pressure tonserve
the CV on the cv on or
surface
This is the only macroscopic energy balance you will ever
need
MEEEwont III
t
a IEfne Effacetension
power A surface area
voltage current outdistance

S entropy of a system
t
i s

rate dueto Entryfw

rate due to
Qr radiation
energy
materialflowing at cusurface
heatflow absolute
across C Vsurtax across c V TR
surface temperature
5k specificentropy of emitting
E Iggy Iggy jutetemperature source

Example Metal ball weighing 40kg at 4500C is cooled by placing

it in an adiabatic tank containing 150kg of involatile oil at
20 C Determine the common temperature of the oil Epo
267kg k and metal Cp m 0.57kg k

I
drawn around the entire system
stage tgfgymy.is 97 0 M constant
closed M MmtMo
system
EnergyBatance
ft Uthman FMÉ UtEv74 PM IQ Wk Pdt
adiabatic
dm Ek esggoric
Ut mu'tmy 0 integrate between initial final states

day at
ft Imo at
ft 4 It
m 0

I itI it
ein
Ufinzl Uinitrl 0

Ufinal UM final t do final

Uinitial Um initial No Initial
so conservation of energy requires

qq.gq.si
Cpa Cred heat
capacity
ii i e

assume
Er E Eisconstant DI Ev DT

relationship between internal energy temperature

DU MAN ME AT substitute into

MmEm Tina Tminitial t Modo
tiny To initial 0

40kg o.si c
tmi iiioc E
150 9 Fk
2.6 Tana 20 E 0 741 C
 21

i i
is

igB5gm
qq.IE massinsidec.u dff
Mm

thetiimic
iiiiiiii.mn
addthis.IT sEEtfi Patton hi Pat
fitEg Go
adiabati
Go
d4 nm Antrim Pdf integrate

kitted.im iga fiip

ae UfimiPfiiiiftdf
Uinitial

Theballenters
Instant
fftamnetyffffggy
pressure

the oiladiabatically company ganging

to retain all its initial
initial energy
map PCVfyII.gg
Ufinal Uinitial Mm Um
F in.tn
 Motofinal t Mmdmfine so conservation of energy requires

Moldo.fm
UmffUmin
Nqmitizl tMm

same as above
0

ConclusionThe choice of the control volume made

no difference to the final answer Perhaps
the first choice was easier

ED Epo Tix entropia a turning towards

Epott trope turn conversion

Sf Sit If measured in an isolated state

Sf Sit ftd4 Clausius inequality

In an isolated system e.g The whole universe
dq 0 so AS 0
If there is a change in an isolated system the change
must be spontaneous A spontaneous process must lead to
an increase in
entropy in the universe
15 0 only at equilibrium where reversible
can
changes occur

Mcfffffis property that can be used to determine

a
the energy available for useful work
measures the tendency of a process to proceed in a
particular direction
Entropy is a state function
 Entropy can be balanced
dat t.mn sit t's'Q t
9 Sgen

Secondlawofthermodynamic

Sgen O at equilibrium

Sgen O away from equilibrium

9 15 ConsequencesRApplicationsoft hehan
Production of work generally requires heat to flow from
a hot reservoir to a cold reservoir for steady state

Ic processes

steady state nothing changes with time

cyclic process that repeats the same sequence of
states each time returning to the same
initial state
It is impossible for a cyclic operating device to
produce work from a single temperature

Let's prove this by assuming it is possible then

show it either violates conservation of energy or
it Violates The Second Law
Kelvin
PlanckDevice w

constants É
EI t.IT tatw peat
To
5In
Go
closed
uittay pi
Go
isochoric
process
dat Q W let's integrate over the time
of one cycle

fidget Stadt It wat

T.ae e
FEI Qcyclet Wayne 0 Qcycle Weycle
cyclic

É sEÉm
9 Q Sgen
Eked
dark
To
Sgen integrate over one cycle

fitftdt ft de t fitsgendt

Ff Qayt t Sgen cycle

To Qu t Sgen culet

Sgencycle
at Zynga Qcycle 0

Sgen O Sgen cycle 0

Therefore Queue so to obey the second law
 The heat must flow out to obey the 2nd Law
This violates our proposition so the device cannot exist

Read about the Clausius device

Tz Tz T

operates without work

I
Y t
2 Reversible process
3 Min Max work for a process
4 Thermo identities how to relate different properties
5 Using Jacobins

Ifgy _fno with time

changes dato
stationary process no changes in kinetic or potential energy
closed process no flow of mass thru CV
isolated process no flow of mass heat radiation work
thru CV
Isochoric process constant volume
isothermal process constant temperature
isobaric process constant pressure
adiabatic process no flow of heat
 dark process no flow of radiation
isenthalpic no change in enthalpy
isentropic no change in entropy
reversible process Sgento

IYE.IT
rgtentumflows
s occur with gradients I
IT 71 IP Fx 4,82
T temperature I velocity P pressure
momentum flow It IP
heat flow 2 IT
Sgen It II IP
If gradients are small then Sgen is even smaller
often Sgen O

Examplesota'ReversibleProcess
Uniform slow of a fluid
compressionexpansion

slowly changing process laminar flows without diffusion

chemicals in reaction equilibrium
forward rate rn reverse rate rn

phase changes at state of a

phase boundary
melting of a solid to a liquid
freezing of a liquid to a solid
well designed turbines compressors nozzles
 t
irreversible reactions
a
shock waves

any process in which friction is important

mixing fluids of different temperatures Nor compositions

45 Mass Balances EnergyBalances Entropy Balances to

very important classical Che processes

IIE

ÉPÉE 73 150 atm

A waste stream of pure coz is being sequestered underground

This requires compression in two stages from P latm to
13 150atm Treat coz as an ideal gas with constant heat
capacity Assume both compressors are well designed
insulated There is negligible pressure drop across the
intercooler the gas temperature entering the first
compressor equals the gas temperature entering
The second compressor
a Determine the intermediate
pressure Pa that
minimizes the work rate done by the compressors
 WitNz
b Find how much work is done by each compressor
c How much heat is done by the intercooler

A.IT ttet compressors adiabatic

are reversible
since well designed

assume intercooler is isobaric

assume the process is at steady state
a Find Pz That minimizes W this

digital so
Iya o tp
strategy calculate W wz then find Pr such that

await 0

t.mg I m miso or mi mim

Yo
steady state

EIEIIIFFE.in aegxteD ta
o
w P
Go
Isochoric
adiabati
steady state stationary steady state
O M U PT t Nz Azt RV W
Y I
 a tw Wi milia A
MEEE MCAFEE

similar for second compressor WE m Hy 113

so W this m In It My Its we know IT II TP

W WE militate Pr H T P My Ts B 173
T P2
sin ie ti is a state function so we can treat Iz ti Hy It's
as two steps DT at constant
pressure
DP at constant temperature

Italia HGR tHrlTaR

ftp 8p
ICtd
o
for ideal
Ip Tz Ti y gas

similar for Hy tt
9 20
With MERIT T Tz Ti
far is exhausted but we haven't yet used
Our strategy so
an
entropy balance From Chapter 4 Egn 4.4 3 for AS
of TP variables
gas with
an ideal as would have
we

for the first compressor

EEst.gg fl.w
isentropic
Qeeti.s
process
relation
 can I justify this
Q
If SEEMp
sit Sgen
to
steady state
adEbatic
É Tfeversible
process

in 52 51 0 so we must have 51 52
This is isentropic process
t
I Bp likewise for compressor

E E
Withe MEET E 1 7 1 ineptftp It E E1
d
M
wttp mcp t Epp pi I É pilot p.tl
J
b Work done by
fPP
compressor
F50atm Pz 12.2 atm

W m IF It MCF Tz Ti
c Heat removed by intercooler
Energy balanie with C V around The intercooler
Q Mep T Ta

TP ft only for an ideal gas

1Ygefetrmtetikmax.mum
eE.ie
energy available
for work by a system Different systems have different
constraints

Exampled Let's consider a closed system that remains

as it evolves from

IFIY.IE eliztchoriotdrk

I II.it Efin aemxter

o
tan Pdt
Go

Q W

E1jjIE
IE H tsge
ed
isothermal To
dark
8 d solve for W
Of Sgen eliminate Q

Q TIF TSgen
W
ft I dat tf TSgen

Tats in this feet

rg
A Helmholtz energy
Hermann von Helmholtz 1821 1894 German Physician Physicist
who made important contributions the mathematics of the eyed vision
conservation of energy electrodynamics classical thermo
 W dd T Sgen

To get work done by the system Who

The 2nd Law requires Sgen O
So to get work done by the system we must have t O
Ad
To getthe maximum amount of work
W 9ft TSgen
to To To so design a reversible process

If I integrate from state I to state 2

Wmax Az A Wreversible at constant T V

Exampled Take the same system isolate it so Wo

All the system can do is go to equilibrium What is the condition
for equilibrium
We
d
TSgen O TSgent ft
Iggy
A decreases until Sgento A becomes constant
A is at a at equilibrium
minimum

Atm
mum at constant TV closed system
dA O equilibrium
da o stable equilibrium
Examples Let's think about a closed stationary dark system
That remains isothermal isobaric What is the maximum
work the system can do

EIIIE.fi tginWtzrHtPD totw Pdt

Tostationary Oclosed
 811135,557 4
Sen
Fationary
Edark
Solve for W eliminate Q
W Htt Pdt Q
Q TIF TSgen
W 4ftPE Tff TSgen TP are constantconstraints

U PU TS TSgen
Henthalpy this
Inte
G Gibbs energy free
Josiah Willard Gibbs more about him later
W E TSgen
To get work done by the system we must have W 0
The 2nd Law requires Sgen 20 so we must have 8 10

To get the maximum work done by the system design a

reversible process so Sgento

W'may ft for W co we must have def co or Gt
Integrate from state I to state 2

Wmax G G

Exampley If we now isolate the system so that W O what

is The condition for equilibrium
We def T'Sgent TSgent
Iggy
 So while Sgen O we must have Gh until Sgent at equilibrium
Then dat 0 G constant
Therefore G reaches a minimum at equilibrium state
for a closed system at constant TP
d 6 0 equilibrium
0670 stable equilibrium
9 23
Examples Now consider the system in Example3 with no

work assume a reversible

process
EnergyBalance It Wt Pdt E Q Pff
Go I
EntropyBalance If Sggy If
Tdf Pdt T P constant

integrate between any two states feat tffdt pfÉdt

DU TAS P AV first written by Gibbs
Gibbs MasterEquation
U S V are state functions that don't depend on path so the
Gibbs Master Equation is valid between any two states
that have the same T P

Now consider U as a function of S V

du Is as 8T sdV This is the chain rule just math

du Tds Fdr This is Gibbs MasterEan

for both be true we must have

T 8r and P Es
similarly IH Tds Vdp 6.2 6
dA PIV SIT 6.2 7

IG SIT VIP 6.2 8

and there are more relationships between
P V T S H A G Cp Cv etc
Read thru chapters 6,7 for derivations of other identities
so you can relate partial derivatives used in thermo
understand how to compute properties from an equation of state
equationofstate P P ut or K V PD

Understand the criteria for equilibria stability

UsingJacobianstoderivethermorelationship
Why It makes life easier
there are msm
qq.IE1 Ils

all of these
fI LEI lfsl 1 CEE Eh
equivalent to just JLP V JETS
are

What's that JC stuff differentiated property kept

J constant
property

In general in
A Jacobian transforms material properties from one set of
independent variables to another set of independentvariables
IFI can be treated like rational fractions

E s
J xx O X is any property

J x y JLy x x y are any properties

You can do algebra with J's

III EET I
Chain rule applies
dx may NAZ J XD MJ YD N JEZ a
x is any property
So let's look at the first Maxwell Relationship

1 1 1851
III IES
I I You getthe same result
T from all 4 Maxwell
JETS TIP u relationships

Strategies relating thermo relationships in terms of measuredproperties

JEST J V P Maxwell relationship

JLSP Cp because Cpt f p
t
IET JE D TIP
JLSV Cr
JIAN JIA a J A a J Ga Master equations
Example to Calculate a Joule Thompson Coefficient
Pe
How do you calculate Ep using
jy only properties we can
equation of state
P V T Cp Cr
measure

Assume the process flow is stationary pipe is insulated

so process is adiabatic Assume steady state

Mitten
To
to mint moat
M MINI M out

state
none

E1weEIF HIm.cat ggPDiaEw

Go
adiabatic
Go
steady state neglect Isochori

o
É'm.cat EY'multi 0

MIN MIN Moat out

0 M HI HAO
HIN Hout
Isenthalpic process
so we need to calculate F it
in terms of P V T Cp Cr
use dH Test VIP
F ftp J H D TJESDTVJLP.AT
jIEIFIf.noosea
Maxwell
choose a
t
P

EHIFEIFEI to
top

E
strategy JLSP

JEST
Cp
JEU P
p
Maxwell
tIÉ py
EM
CEI TTEIY.IE IIFIEIII

of
ITCH r

easy right
Chapters Mixtures
D extensiveintensive specific molar partial molar properties
2 new concepts with
partial molar properties
3 criteria for equilibrium

In pure substance single phase systems The state is

completely specified by
2 intensive state variables
extensiveproperties V S U H A G increase proportionally
with amount of material
intensive properties V 5 I II A G independent of system
size normalized by mass
YS H HAE independent of size
normalized by moles
size state are specified by fixed either mass or moles
with two intensive properties
UCTP N I ACTP
For asingle phase mixture of C components the state is
specified by fixing two intensive variables all but one
mole fraction or mass fraction
Extensive
U U T P Ni Na Ne u IEYT.xu.ieD
I I TP W Wa Wa
Is it necessary true
Eixidice
thighs Yurecomponent property

No A describes only wi interactions but not in j

AmyD ICTPXuxa Xe D
Section 8.1 shows us
É Xi Li TP
ACT Pina Xo É Xi ftp.njti
Thot ti of pure i
This defines a partial molar property

it 8M ftp.nj ti fAt p.Njti

Ti Ti TP I Ji VI TP 1
We can write partial molar properties for any intensive
thermo property O
don'taccept
É Oi TP E N ftp.py substitutes
T t
These matter
TP
O
D
NE
É Xi ICTP
extensive is
E

Oi partial molar property of 0 per mole of i

in mixture
I this isnot the individual contributionof species i
to O it represents the variation in O as i
is added to the mixture

AmexE
change
E
total
É XiQi pure i
by math E Exc Ei

AME É Xi Ei Ei
 NTherearenewoncepts
i thermo relationships between partial molar properties
2 chemical potential
G Gibbs Duhem Ean
1 Do all the thermo relationships between Ei also
pertain to Ei
Yes fany
ftp.mi
8anyHit.p.N
C p
Ep Epi Jp yes
2
eemtgtftff.tt q E t py so use chain rule

da ftp.ndtt 8tymdPtE 8Tilyp.m dNi

If I historically
called chemical
potential Mi Gi

GIFT ftp.njj 8I s.v 8Ni 8

njI p s Njti it.v Nito
Mi
this is notthe same as Ii Efi pn G
 any property one
9dI.in t n tg n g
dINE
É d Ni E
É Eid Nit É Nida
b NE depends on CTP Ni differentiate using chain rule

d NE NC 8Ft.ndPtE8vil
p.n.tn pgg
c subtract divide by N WE
pnot E t.net
xidEi 0

Generalized Gibbs Duhem Equation

YfdtpeIdent relationship describing the

WYaedit.tt
state dependence of the property 0
consistency check for experimental data theories
criteria for chemical phase equilibria
methyl formate
ethanol at.at
methyl formate
atgust
miffy
methanol CHOH
Are these data
thermodynamicist
tent
 See Gibbs Duhem Ean O V
we've done this expt at T P constant dt d Po

F pig 8 ge tExidti o

so we must have that

É did ti o

how do we get dti use chain rule

d Ti
É Ig ox
Jdx
x exit x dx 0
since dx is arbitrary
X 8 Xz8 dx o positive negative zero

we must have for all compositions for good data

x 0
x x
Fifty

As minimum for
i
equal at constant NT V
i same for
materials

Minimum
4 purge
mixtures
For any system in equal with Phase I RI
TI TI continuity of temperature
PI pit a
pressure
Git Git partial molar Gibbs energy
No magic These were derived for closed systems from
energy balance entropy balance Gibbs Duhem Esu

Sgep O at non equilibrium Sgento at equilibrium

Rtos
Reactiggytabripps rapist p
stoichiometric coefficients a p p r

In Chapter 2 we write reactions

Rto St
Ig Vi I to
p
AA p B

stoichiometric coefficients Vi o for products

Vi co for reactants
species Ii
Conversion in terms of moles Ni Vi
initiates yo Xp
extent of
reaction
in moles
X is the same value for all reactants products
At equilibrium at constant T P we know G is a minimum
G
É Yi
Gi É Nitrox Gi
at equilibrium we must have 8 FO
It Vi Gi 0 regardless of how many rxns

Complication M independent reactions at TP const

Ie Vij E O j 1,2 M reactions

Vij stoichiometry for species i in reaction j

GibbsphaseRule
Let's think about the most general description of equilibrium
between number of components phases
any
reactions
Let fo phases regions of equilibrium composition state
C components species
M reactions
How do you know when you can specify a fixed equilibrium
state between all possible properties degrees of freedom
minimum
unkpngypertffersmo
for each phase 2 intensive properties
C l mole fractions

p a c 1 PC CH

EYII.int Eimp itiremts

between all phases
TI TE T a TP f 1 constraints
6 continuity of pressure between all phases
PI PI PHI PP P D constraints
3 continuity of Gi across each phase for each species
Cfp 1 constraints
4 for each to be in equilibrium
reaction
we have M constraints

Vi 5 0

degrees of
of freedom trip gig constraints
 F Platt Pt p i Clp 1 M

F C M f 2

degrees of freedom required to fix an equal state

10
For this lecture separate recordings of
1 Exam I answer key
2 C BET 49.1 9.4 Done with classical thermo
3 Mathematica tutorial
 Yi
7f.EE YabutEEiE GTdirectly
it can't be measured
Ideal Gas Mixtures difference between real
Ideal Mixtures ideal mixture properties
Real Mixtures Excess properties
É Fugacity pressure of an ideal gas that has the
same temperature chemical potential
of the real gas
Activity coefficient
Correlation methods which types of correlations for which
types of mixtures
IdealGasMixture IGM NRT holds each i
Pill
since the entire mixture is ideal PK NRT
P ÉPi Pi partial pressure of i
N
E Ni
what about the other properties
Internal Energy UI'm Hi Dmx I'm O

Atom T Vx
É Xi GEET V no interactions
between i d j
The same is true for enthalpy volume
GM GM
Dmx O
Im KI O
would you have thought
Entropyiscompletely different of this without
thermo
statistical
Since there is no energy of interaction the change in
entropy upon mixing is like expanding each componenti
from Vi Ni RIP
to the mixture volume V É Nif Vi Xi V
 to calculate DmxS use the MasterEgn 6.2 17

E
de
IEEE CEI
isothermal mixing
Wfff Maxwell
Relationship
ds 87 for an ideal gas PE NRT
PI RT Et I
dE
mixture
Ed I R d Int
mixture
gpure df p fpure
dink
5
Effete É'M Sit R In
Egg
Rin Xi

remember DMS S É Xiwhat

Si
it x 1
happens
A mixStam R É Xi In x AmexStam O
0
what happens if Xi
In Q problem
Formula for E I follow
GM GM GM
GI HI GMT PKI TSI
since Dmx HIM DM KIM 0

DmxLIAM TD mix SIAM

EMT P E EE XiGEETP RTE Xilnxi
Fureomponenthangeonmixing