Open steady flow systems

Conservation of mass

Easimi Eiusnii
in the fig
in tmz ing

Conservation of energy
stream
i internal energy per unit mass of each

Net rate into the system

infinite Eiji 5
 i PV work

Swiniet Pdv

wince P d
p Jin
outlet
Pini

h KE PE

mid ring z
streams
combine the total energy transfer due to flowing

infinite it Pii t EE t 8Zi qq.j.msleftPijtuftgzj

Define enthalpy I Et PF

ni hit t 8 Zi ftp.g.jmjhi tufztgzj

Es
of energy biansfer
Mechanisms independent of flow streams

Ci 1 Shaft work Ivs

Cii Heat exchange Oi
 By combining all the firms

offsets ni it Ift 821 ingests hit uIzt8Zj

vis t Q

second law
Sword 3 0

i Entropy carried by the streams

Easini i EiremiI
Ii Heat exchange with surroundings
contributes tsar
Each heat exchange term

sword Eiasinisi Eustis EE wr

 Heat Engines
It's a machine that absorbs heat from a source

damps heat to a sink and performs some

macroscopic work

They operate in cycles

Let's assume that each cycle consists of
I Transfer of energy from the hot source at Tt
I Transfer of energy to a cold sink at Tc

TH
QH
HE W

r Qc

Tc

I First step
ds world DS t dssar

ASfored ASI t ASEarr

Integrate
I
ASword ASI Qt
TH
work WI AEI Qa
I ASwotted as t Assifrr
I
ASworld as t E
Tc

work WI AEI 1 Qc

Over one complete cycle

ASword A Satoru t A Satoru

aft as
Eff FE
W WIT WII
AEI t AE't Qf t Qc

AS ASI AS O
cyclic nature
AE AEI f AEI

0
ASworld t
off
W Qu 1 Qc
Efficiency M watt

y tQtat i QfYt
0
Apply 2nd law Asword 9 t 30
0
It
I I 1 TEH

n Ei Et H

Bounded by a maximum

Maxima is only a fit of only Tc TH

 Baths
If the body is infinitely large lathy reservoir
T is constant
heat transfer is differential and reversible
any
Teath Idseach ISQian
Aseaq Oath
teach

Types of processes
adiabatic no heat transfer
reversible
If adiabatic and
SQ Tds
ds o adiabatic and isentropic

dswo.ru DS t dssarr 3 O

when dswored 0 process is reversible

Reversible means quasi static

dswored 0
Real process
O
ds SEE reversible dswored

dswored o i Real process

SQ o adiabatic
adiabatic
DS o isentropic and reversible
 Extremamotworkf
First law AE Qt W

differential change
let's consider a
DE DS
d swore DS t dssarr

SQsarr SQ n Surround
I
system
Assume that the surrounding
is an ideal heat bath i Tsurr
DS SQsure SI
um TSarr
Tsar
dswored DS
Sarr

DS
DE SW
Tsurr
IS world 7
dESw_ o
ds
Tsurr
Sw C Tsurrds DE

Sw is bounded by a maximum
f
Sw DE Tsarrds minimum
 Special processes
Quasi Static happen infinitely slowly at each
point in time the system is in a local equilibrium
FE is valid at each point in the path
DE Tds Pdv

Reversible process
should be no dissipative frictional
Additionally there
forces

P Peat
SWreu Pdv
a rev
DE SQreu Pdu airst law for
process

SQreu Tds
Compare
SQrev
DS
T

8
For an ideal reversible process ds

For a real process 8 IS

as SET
 consider process whose
a initial and find States

are known
2 different isothermal paths

her timer
SQirrev isothermal
SQrev

Sandexam
For an ideal gas AE O

E ECT N for an ideal gas

Q w
w Ssw
Edu NKBT Ln
 Calculation of work

work is the energy interaction due to which

there is an observable change in the system
at a macroscopic level

Change macroscopic constraints involve forces

of
attention will be on forces external
to
Primary
the system
General definition of work
Sw text d
Feet

Consider a gas filled piston cylinder

assembly
F
In
Sw Fe.edu
SW teat dCnA Pextdv

text P Sw Pdv limiting case

example Pact dependence of work heat

Eon
888880
11
T

State1 v T State 2 Vz T
Pathi sweep all the sand instantly
text O
W E O
AE Q

Path 2 sand is removed slowly grain by grain

text O
w so
Q AE w
 FIRST LAW

we need to analyze what happens if a system

changes from one state to another called
a process
the process is characterized by a path
series of changes that takes the system from
one state to another

E S V N T P re changes are independent

path
A

tiny
First Law
DE SQ t SW for closed systems

in which interactions can occur

Two
ways energy
called work
SW part of energy interaction
SQ denotes the part due to heat

CT P Tz PI
IE Ez E can be calculated
 Integrated form
AE Q t w

Mathematically Latse are inexact differentials

For these there exists no function g that
satisfies

ga f g ft Pel g Iti R
T P

Note such a function exists for energy

de E Te Pe ECT P

µ
Example
L
Nf NL
x

df dn n
0
displacement f dn
Nl

Sg I dnt
Mgsg to
N N n

g M
Id n t f C da 2 Nz Ni
U2
 Fundamental equations
Entropy version DS f DE t
f du
MpdN
Energy version DE Tds Pdv th DN
de
T S v N
OT
yn
OE
ar Pls v N
s n

OE
Tn Mls v N

E S V
linearly with system size
N
extensive scale
intensive independent of system size T P M

E TS PV t UN By Euler's theorem

Proof E XS XV XN DE CS v N
Take X derivative on both sides
RHS E S V N

HS oEH ygdN
_06 dEHf Yg 064

QE XS AV XN dCAN
dCdn ox

oekfygygdnl s.todfydIgdMv
dECds dv dN
NdCXv
X is an arbitrary number For D I we have

Els v n s defqv.NL v t dEfSn N

T Sv N S P S v N V t MIS V N N

E TS PV t UN
s
IT V NTI
Intensive forms
Most commonly we use the per molecule basis

energy per particle

e En s E v NI
DE G V N E XS XV XN

Take X IN In Els v n E E In In
e f ECS v n E EN NI 1

e e CS ie ft of 2 independent
variables
 transform
How does the fundamental equation

E S U ECSN.VN
N
EISN.VN
N

in OEHI.gg dHI
ds

IN DE
OS
N T

1 In OEHNFY.fi dHdI

N p
In

de Tds Pdu

How to calculate µ
E TS PV tu N
F F T
Ts Ne Pv t n

µ e Te t PU

u e
us Edie
if e sie is known


S E V N G E V N

R G
would

Second law o
At constant E V N equilibrium

mean that would show a value of for

when

which I and hence s is maximized

is an unconstrained degree of freedom

What happens if S, V, N are constant?

at eqbm observed value of

S CE v N G

is given as

o 87 o

leg
Tg yn EVN

E S V N G at eqbm how do you get the

observed value of G

E variation Effy 8 gffgle Tffgle

DE O extremam

Tg
in

check derivation

834 T
text

0 (Energy minimum principle)

Second law: At equilibrium, E is minimized at constant S, V, N

conditions with respect for any unconstrained degree of

Second law and internal constraints

v N
S NCE

ICE V N internal constraint

l

- An alternate version of the second law:

S E V N1internal constraint s S CE N

- what are internal constraints ?

• Physically imposed

• Natural

—> Internal constraint" is anything that prevents the system

from having access to all microstates
E V N G

S EV N G kg Lnr

G can have values G Ge

S E v N
GI E S CE v N G

G value of G that maximizes S

Alternate view of the second law :

At equilibrium, S is maximized at constant E, V, N

conditions where the maximum is found with respect to

any internal perturbations of the system, or unconstrained

internal degrees of freedom.