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THERMODYNAMICS

ME-321

Vladimir Soloviev

THERMODYNAMICS

SYSTEM

All aspects of ENERGY and energy transformation (science of energy)

Macro-thermodynamics (classical)

matter is assumed to be continuum

Micro-thermodynamics (statistical)

matter consists of discrete atoms

Kazimir Malevich
The Black Square, 1915

A region in space or a quantity of matter

boundary

system

surroundings

Open system (control volume)

heat
work
mass

PROPERTY

Closed system (control mass)

Isolated system

heat
work

Any characteristic of a system is called a property.

Intensive property

mass-independent:

{T ,P, ,v,u,...}

(lowercase letters)

Extensive property

mass-dependent:

{m,V ,U ,E,...}

(upper case letters)

Specific property

property per unit mass:

{v = V

m ,u = U m ,e = E m,...}

Independent properties

{T ,v} , {P,v} , {T,h} ,

STATE

Set of all properties of the system defines a state

EQUILIBRIUM

Equilibrium is a state of balance. System can remain at equilibrium state indefinitely.

Thermodynamic equilibrium state: the system is in equilibrium regarding all possible
changes of state; i.e. it maintains thermal, mechanical, phase, chemical etc. equilibria.

T ,P,V ,m,u,e,v,s,h,... }

property 1

STATE POSTULATE

The state of a simple compressible system

is completely defined by two
independent intensive properties

state

property 2

PROCESS

Change of a system from one state to another (transformation).

State 1

1 = 2

path

cycle

process diagram
State 2

Quasi-equilibrium process

a system is close to equilibrium at any moment of process

Steady-flow process

no change with time

Unsteady-flow process

transient

Uniform

no change with location

Iso- process

particular property remains constant (isothermal process)

EXTENSIVE

PROPERTIES
Mass

intensive

[ kg ]

Temperature

[K ]

Pressure

[ kPa ]

Density

H O

kg
m3

V 1
=
m

m3

kg

m
V

SG =

Volume

m3

v=

Internal Energy

[ kJ ]

u=

U
m

Total Energy

[ kJ ]

e=

E
m

Enthalpy

H = U + PV

[ kJ ]

h = u + Pv

kJ
K

specific weight
specific internal energy

kJ
kg

kJ
kg

specific total energy

(heat content, total heat,to heat)
at constant pressure
at constant volume

kJ
kg K

Quality

specific volume

kJ
kg K

kJ
kg K

cp
cv

Entropy

specific gravity (relative density)

N
m3

kJ
kg

s = g

Specific heats

Blaise Pascale
( 1623 1662 )

x=

mvapor

quality is defined only for

saturated liquid-vapor mixtures

mliquid + mvapor

Paris Museum of Measures and Arts

dP
= g
dz

Pascal's Law

Po = Patm

(1-20 )

in this equation the positive direction of z is upward

Manometer

Barometer
Po = Patm

fluid of
density

P0 = 0

gas

P = Po + gh

dP
= g
dz

P = Po + gh

fluid of
density

h
Patm

Patm = gh

positive direction
of z is downward

Pabs = Patm +Pgage

Pabs = Patm Pvac

Pabs

T ( K ) = T ( oC ) + 273.15
T ( R ) = T ( F ) + 459.67
o

T ( F ) = 9 5 T ( C ) + 32
o

Pgage = Pabs Patm

Patm

1 atm = 101.3 kPa

Patm
Pabs

Pvac = Patm Pabs

1 atm =

14.7 psi

Conversion of [psi] to [Pa]

[ psi ]

F
A

[lbf ]
in 2

[lbm] ( 32.174 )
=

ft
2
s

in 2
m
kg
ft
( 32.174 ) 2 ( 0.3048 )

lbm
s
ft
2
2

1
ft
m
2
in 2
( 0.3048 ) 2
144 in 2
ft

[lbm] (0.45359 )
=

(0.45359 ) ( 32.174 )
1
( 0.3048 )
144

m 1
kg s 2 m 2

m 1

= 6894.7 kg 2 2
s m

1
= 6894.7 [ N ] 2
m

[ N ] = kg

= 6894.7 [ Pa ]

[ Pa ] =

m
s 2

N
2
m

weight

F = m g

Chapter 2

ENERGY

Total Energy

[ kJ ]

Specific total energy

e=

E
m

kJ
kg

(2-1)

Total energy E is the sum of all forms of energy: thermal, mechanical,kinetic, potential, electric, nuclear, etc.
Thermodynamics deals only with the change in total energy, E .
Microscopic

Macroscopic

( kinetic energy of molecules )

thermal energy ( heat )
( phase energy, binding forces )

sensible

related to molecular structure.

Sum of all microscopic forms
is called internal energy U

latent
chemical
nuclear

with respect to some outside frame.

Mechanical energy.

system moving with the velocity V

z = elevation

kJ
kg

(2-1)

V2
2

kJ
kg

(2-2), (2-3)

Specific potential energy

pe = gz

kJ
kg

(2-4), (2-5)

[ kJ ]

Specific total energy

= u + ke + pe

kJ
kg

(2-6), (2-7)

[ kJ ]

Specific total energy

=u+

V2
+ gz
2

kJ
kg

(2-6), (2-7)

U
m

[ kJ ]

Specific internal energy

u =

[ kJ ]

Specific kinetic energy

ke =

Potential energy PE = mgz

[ kJ ]

Total energy

Internal energy U

Kinetic energy

KE = m

V2
2

= U + KE + PE

=U +m

V2
+ mgz
2

Equation (2-6) in SI units:

work

force dist

= N m = kg

m
m2
m = kg 2
2
s
s

Energy flow associated with a fluid flow

Mass of volume V
Mass flow rate

amount of mass flowing through

a cross section per unit time

Total energy flow rate

m [ kg ]
E [ kJ ] = U [ kJ ] +

V 2 m2
m
V2
+ m [ kg ] g 2 z [ m ]
+ mgz
m
2 s 2
s
2
=
+
U
kJ
[
]
[ kJ ]
1000
kg m 2
1

1000
s2
kJ

p.54

= V

[ kg ]

m

= V
= AcVav

kg
s

E

= me

= me

kJ

s = kW

kJ
[ ]

(2-8)

(2-9)

dot above a symbol indicates time rate m=

dm
dt

MECHANICAL ENERGY OF FLUID FLOW

is the form of energy which can be converted to mechanical work completely and directly by an ideal mechanical device.
It consists of energy of flowing fluid (called flow work or flow energy), kinetic energy (KE) and potential energy (PE) .

flow
enegy
KE
PE




Mechanical energy of flowing fluid:

Emech

Power (rate of energy transfer)

= m

+m

V2
+ mgz
2

[ kJ ]

E
mech

P V2

= m
+
+ gz
2

emech

Emech

P P V 2 V12

= m 2 1 + 2
+ g ( z2 z1 )

[ kJ ]

E
mech

P P V 2 V12

= m
2 1 + 2
+ g ( z2 z1 )
2

kJ

s = kW

(2-13)

emech

kJ
kg

(2-12)

kJ

s = kW

E
E
mech =
t

kJ
kg

V2
+ gz
2

(2-11)

(2-10)

Mechanical energy change of

incompressible flow ( = const ):

State 2
State 1

P1 , ,m

P2 , ,m

V2

V1

z1

z2

P2 P1

V22 V12
+ g ( z2 z1 )
2

ENERGY TRANSFER
Examples 2-4,2-5,2-6

Heat Transfer

Heating of a Potato in an Oven

energy transfer due to temperature difference

air

heat

Work Transfer

energy interaction not caused by a temperature

Mass Flow

transfer of energy carried by moving mass

Work and Heat:

1.
2.
3.
4.

heat
heating element

Work and heat are recognized at the boundary (boundary phenomena).

Systems possess energy, not work or heat.
Associated with a process, not with a state.
Path functions (depend on path of process), not point functions which depend on state.

SIGN CONVENTION

electrical
work

positive
to the system

system

negative
from the system

HEAT

energy transfer between system and surroundings

Modes of heat transfer

heat
heat
addition

dT
dx

conduction

Q
cond

= kA

convection

Q
conv

= hA (Tsurface T fluid )

radiation

Q
rad

4
4
= A (Tsurface
Tsurroundings
)

rejection

Heat

Heat transfer per unit mass

Rate of heat transfer

Q

Total heat transferred during process

WORK

due to temperature difference

[ kJ ]
Q
m

kJ
kg

kJ

s = kW

t
t2

t2

t1

t1

Q
( t )dt =

(2-14)

(2-15)
(2-16)

= Q
t

if energy crossing the boundary of closed system is not heat then it must be work
Work = energy transfer associated with force acting through the distance (W = F s )
Work

Work done per unit mass

Power (work done per unit time)

W

Exact differential of a property

dT

[ kJ ]
kJ
kg

W
m
W
t

(2-17)

kJ

s = kW

2
1
Change in temperature
T=T2 -T1 is the same for any

State2

Temperature change during the process:

process between the states

dT = T2 T1

State1

Inexact differentials

T1

dT

T2

W , Q
2

Work done during the process:

= W12

work W12 or heat Q12

transferred during process

between states 1 and 2

Total heat transferred during process

Q
1

= Q12

W depends on path

can be different for different

paths of the process

2-6 THE 1st LAW OF THERMODYNAMICS CONSERVATION OF ENERGY PRINCIPLE

Energy can be neither created nor destroyed during a process.
It can only change forms.

The net change in the total energy E of the system during a process
is equal to the difference between the total energy entering Ein and
the total energy leaving Eout the system during that process.
Eout

Eout

E2

E2 E1 = Ein Eout

E1

James P. Joule (1818-1889)

Ein

Change in Total Energy

conservation of energy
for any system and
any kind of process

Ein

E = E2 E1

[ kJ ]

(2-32)

E = Ein Eout

[ kJ ]

(2-35)

E

[ kW ]

(2-36)

V22 V12
+ g ( z2 z1 )
2

(2-33)

in E

out
= E

E = m u2 u1 +

E

=
E

E
t

(energy crossing the boundary can be in the forms of heat, Q, work, W, and mass):

Ein Eout = ( Qin Qout ) (Wout Win ) + Emass ,in Emass ,out
  
Qnet ,in

Closed system

E
t

E = m [u2 u1 ]

Stationary system

Open system

V 2 V12
= m
u2 u1 + 2
+ g ( z2 z1 )
2

=
E

Wnet ,out

(2-34)

Emass ,net ,in

(energy crossing the boundary is in the forms of heat, Q, and work, W, only):

Wnet ,out

E = Qnet ,in Wnet ,out

Cycle ( E = 0 )

Qnet ,in = Wnet ,out

Q = Q
t

Q
net ,in = W
net ,out

W = W
t

1=2

Qnet ,in

1st Law of Thermodynamics

V2
State 2

fixed mass m

dE
= Q
net ,in W
net ,out
dt

V 2 V12
Qnet ,in Wnet ,out = m u2 u1 + v2 P2 v1 P1 + 2
+ g ( z2 z1 )
2

[ kJ ]

V 2 V12
Q
net ,in W
net ,out = m
u2 u1 + v2 P2 v1 P1 + 2
+ g ( z2 z1 )
2

[kW ]

V 2 V12
Qnet ,in Wnet ,out = m h2 h1 + 2
+ g ( z2 z1 )
2

[ kJ ]

enthalpy
h u + Pv

V 2 V12
Q
net ,in W
net ,out = m
h2 h1 + 2
+ g ( z2 z1 )
2

[kW ]

(5-38)

steady flow
V1
State 1

z1

z2

2-7 ENERGY CONVERSION EFFICIENCIES

Perfomance =

Combustion efficiency

combustion =

Lighting efficacy

lighting =

Desired output
Required input

(2-41)

Q
Heat released during combustion
=
HV
Heating Value of the fuel burned

(2-42)

Amount of light output [lumens ]

Electricity consumed [W ]

MECHANICAL AND ELECTRICAL DEVICES

Pump efficiency

mech =

E
E
Emech ,loss
E
Mechanical energy output
= mech,out = mech ,in
= 1 mech ,loss
Mechanical energy input
Emech,in
Emech,in
Emech,in

pump =

E
mech , fluid
Mechanical energy increase of the fluid
=
Mechanical energy input
W
shaft,in

loss,out
W
dEsys
dt

m

P1 < P2

P1

P2

(2-36)

= E
in E
out

m

pump =

E
sys
W
shaft ,in

W
shaft ,in W
loss ,out

W

= 1 loss ,out


Wshaft ,in
W
shaft ,in

shaft ,in
W
P2 P1

E
sys = m


out
E

= V
( P2 P1 )

(2-13)

shaft ,in
W

pump

P P
m
2 1

=
W
shaft ,in

V
( P2 P1 )
W

shaft ,in

Overall efficiency

pump-motor = pump motor

efficiency of pump-motor combination

(2-49)

attraction = viscosity

3 1-4 PROPERTIES OF PURE SUBSTANCES

Pure Substance

fixed chemical composition

Phases

solid, liquid, gas

small attraction, random motion

molecules arranged in lattice

Phase Change Process

1

T
P = const

5
2

P = 1 atm

P = 1 atm
T = 100 C

T = 200 o C

saturated

saturated

superheated

liquid - vapor
mixture

vapor

vapor

P = 1 atm

v=

V
m

P = 1 atm

P = 1 atm

T = 10 o C

T = 100 o C

compressed

saturated

liquid

liquid

Phase diagram

T = 100 o C

T-v diagram

P-v diagram

critical
point

critical
point

superheated
vapor

compressed
liquid
saturated
liquid-vapor
mixture

P = const

Psat

Tsat

saturated
vapor line

Tsat = temperature

Psat = pressure

at which phase

at which phase
is changed at
given temperature

is changed at
given pressure

saturated
liquid line

v=

V
m

v=

T = const

V
m

v=

V
m

evaporation

melting

P-T diagram

critical
point

critical

Psat , kPa

point

critical point

liquid-vapor
saturation

LIQUID

curve

SOLID

triple point

101.4

Table 3 - 3 p.122

Table 3 - 1 p.116
VAPOR

100

sublimation

Latent Heat of Melting (Freezing)

Latent Heat of Vaporization (Condensing)

Tsat , o C

( energy absorbed during melting )

Q = mh fg

= mh

fg
Q

[ kJ ]
[ kW ]

( energy absorbed during evaporation )

3-5 PROPERTY TABLES

H = U + PV

subscripts

h = u + Pv

[ kJ ]
[ kJ kg ]

enthalpy
(specific) enthalpy

saturated liquid

v f specific volume of saturated liquid

hf

enthalpy of saturated liquid

saturated vapor

vg specific volume of saturated vapor

hg

enthalpy of saturated vapor

v fg = vg v f

h fg = hg h f

latent heat of vaporization

fg difference

and TABLE A - 5 - Pressure table

Saturated Liquid or Vapor

Saturated liquid-vapor mixture

T, C

quality:

x=

mass of vapor
total mass

Psat = 3.169kPa

x=

T = 25 o C

mg

y yf

Tsat

y fg

y = y f + xy fg

vf

v=

vg

V
m

Superheated Vapor:

yf

yg

x=0

x=1

y can be v, h, u, or s

Compressed Liquid:

P = 10kPa = 0.01MPa

P = 5 MPa

Tsat

Tsat

vf

vg

v=

V
m

v v f @T

v=

V
m

approximations:
v v f @T ,
u u f @T ,
h h f @T
for low or moderate pressures

h h f @ T + v f @ T ( P Psat @ T )

LINEAR INTERPOLATION

T1
y1
T

y2

T2

T2

If T is given:
linear

interpolation

T T1
( y2 y1 )
y = y1 +
T2 T1

T1

If property y is given:

T = T1 +

y y1
(T2 T1 )
y2 y1

y1

y2

BI-LINEAR INTERPOLATION
P1

<

<

P2

T1

T1 < T < T2

y11

y 21

y12

y 22

T2

If P and T are given:

bi - linear
interpolation

If P and property y are given:

y1 = y11 +

T T1
( y12 y11 )
T2 T1

t1 = T1 +

y y11
( T2 T1 )
y12 y11

y2 = y21 +

T T1
( y22 y21 )
T2 T1

t2 = T1 +

y y21
( T2 T1 )
y22 y21

y = y1 +

P P1
( y2 y1 )
P2 P1

T = t1 +

P P1
( t2 t1 )
P2 P1

3-6 IDEAL GAS is a gas obeying the Ideal-Gas Equation of State

1
V

Boyle (1662) , Mariotte

P~

Charles, Gay-Lussac (1802)

P = mRT

Ideal gas equation of state

PV = mRT

Pv = RT

Ru = 8.314

kJ
kPa m 3
kmol K = kmol K universal gas constant

kg
kmol

Clapeyron-Mendeleev

PV =

1
V

m
Ru T
M

PV = NRu T

Pv = Ru T

m = const

m
M

V
=
N

U
N
H
=
N

PV
PV
1 1
= 2 2
T1
T2

[ kPa ]

gas constant (Tables 1,2)

molar mass (Table 1)

( molecular weight )
mole* number

[ kmol ]

Properties per unit mole:

m3

kmol
kJ
kmol

kJ
kmol

Constant Volume
1

P is the absolute pressure,

kJ
kPa m3
=

kg K
kg K

= Ru M

h
Closed System

T is the absolute temperature, [ K ]

Ideal-Gas Equation of State

molar specific volume

internal energy
enthalpy
P2

T
2

P1 P2
=
T1 T2

P1

V = const
1

v
T , oC

Ideal Gas Tables **

Water vapor as an ideal gas

Percentage of error
vtable videal
vtable

100

in assuming steam
to be an ideal gas

A-17
A-18
A-19
A-20
A-21
A-22
A-23

v, m 3 kg

Robert Boyle

Edme Mariotte

Jacques Charles

Joseph Gay-Lussac

(1627 1691)

(1620 1684 )

(1746 1823 )

(1778 1850 )

Mole is a unit of measurement for amount of substance; 1 [ mol ] = 6.022 10 23 molecules ( Avagadro number )

Amadeo Avogadro

(1776 1856 )

Air
Nitrogen N2
Oxygen O2
Carbon Dioxide CO2
Carbon Monoxide CO
Hydrogen H2
Water vapor H2O

B.P.E.Clapeyron

Dmitri Mendeleev

(1799 1864 )

(1834 1907 )

For ideal gas, u (T ) and h (T ) depend on temperature only,

therefore, Tables A 17-25 are the temperature tables

3-7 COMPRESSIBILITY FACTOR deviation from ideal-gas

Ideal Gas

1=

Pvi .g .
RT

For ideal gas

vi.g . =

RT
P

v = Z

RT
P

Compressibility factor

Z=

Pv
RT

For real gas

Reduced properties

TR =

T [K ]
Tcr [ K ]

reduced temperature

PR =

P
Pcr

reduced pressure

v
T
R cr
Pcr

pseudo-reduced specific volume

vR =

Z (TR ,PR )

Principle
of

= Z vi.g .

(3-19)

(3-20)

(3-21)

is the same for all gases

Table A-15, p.932

corresponding

Z ( vR ,PR )

states

is the same for all gases

Figure 3-49 Comparison of Z factors

Table A-15 Generalized compressibility chart

Example 3-11

Find specific volume of R-134a at P = 1.0 MPa and T = 50 o C = 273.15K (superheated vapor)

Table A-1

kJ
Pcr = 4.059 MPa , Tcr = 374.2 K , R = 0.08149

kg K

Table A-13

vexact

Ideal gas

vi.g . =

Z-factor

TR =

= 0.021796
RT ( 0.08149 )( 323 )
=
=
P
(1000 )

0.026333

Exact value
Error:

20.8 %

Error:

2.7 %

A 15
( 273.15 )
( 1)
T
P
=
= 0.863 , PR =
=
= 0.246 Z 0.85
Tcr
Pcr ( 4.059 )
( 374.2 )

v = Z vi.g . = ( 0.85 )( 0.026333 ) = 0.02238305

Work is the energy transfer

between system and surroundings

4-1 PdV WORK MOVING BOUNDARY WORK

during the process

A
pressure at the
inner surface

Work out is used for something outside:

rotate the shaft, overcome friction, etc.

F = PA

of the boundary

force acting on
the moving boundary
kN 3

3
kPa m = m 2 m = kN m = kJ

dS
dV



W = F dS = P ( A dS ) = PdV

dV = AdS

Boundary work done during the process

(4-1)

differential boundary work

Work done during a cycle

= W

[ kJ ]

12

12

Wnet > 0

= PdV

W
W

V1

Wnet < 0

(4-2)

V2

V
difference between the work done by the system
and the work done on the system

total boundary work is equal to the area

under the path (depends on path)

( 4-3 )

Direction of boundary work

compression

expansion

W <0
work on system

W >0
work by system

dV < 0

dV > 0

out

in
P

V2

Constant pressure process

V1

V1
P

W = P (V2 V1 ) < 0
2

W >0

W <0

W = P (V2 V1 ) > 0
1

V2

W = PdV = P (V2 V1 )

W <0
W
in

V2

Boundary work
in the 1st Law

compression

assume the only work

is the PdV work Wboundary

W <0
W
out

V1

V1

Qnet ,in Wboundary

expansion

V2

sign will be adjusted

automatically

4-1 BOUNDARY WORK FOR POLYTROPIC PROCESS OF GASES

closed system, m=const

n,C are constants

n
PV
1 1 = C

ln P

PV n = C
P=

C
Vn

ln P = n lnV + C

P2V2n = C

n
1 1

n
2 2

PV = P V

n=0

P = const isobaric

n=1

T = const isothermal ideal gas

n=k

s = const

isentropic

n=

v = const

isochoric

lnV

W
V

V2

V1

PV n = C polytropic process

n1

= PdV = C V n dV
1
=
( CV21 n CV11 n )
1 n

PV = mRT

C = P1V 1n = P2V 2n

P2V2 PV
1 1
1 n

ideal gas

PV
PV
1 1
= 2 2
T1
T2

P
T2
= 2
T1
P1

1
n

( 4.9 )

V
= 1
V2

n 1

PV
1 1 = mRT1
mR
(T2 T1 )
1 n

P2V2 = mRT2

PV = C process

= PV
1 1 ln

( 4.10 )

n=1

P
PV
1 1 = C
1

P=

C
V

V
C
dV = C ln 2
V
V1
1
V2
V1

= P2V2 ln

V2
V1

= PV
2 2 ln

P1
P2

For ideal gas: PV = mRT = C T = const

( 4.7 )
(isothermal process)

2
P2V2 = C

V1

n=0

= mRT ln

V2
V1

= mRT ln

P1
P2

PV
1 1 = P2V2

V2

P=C

isobaric process

(constant pressure process)

2
P = const
W
V

V1

V2

= P (V2 V1 ) = P m ( v2 v1 )

( 4.6 )

(Not a flowing fluid, no flow work)

ENERGY BALANCE FOR CLOSED SYSTEMS (m=const) ,

Qnet,in = Qin Qout

Energy can cross the boundary

of a closed system only
in the form of heat or work

E
Wnet,out = Wout Win

1st Law of Thermodynamics

Qnet ,in Wnet ,out = E

[ kJ ]

Q
net ,in Wnet ,out = E

[ kW ]

t
Q=Q

(4-17)

t
W =W
State

Qnet ,in Wnet ,out = U 2 U 1 + m

2
2

2
1

V V
+ mg ( z2 z1 )
2

KE and PE

relative to some
reference frame

V2

State

Qnet ,in Wnet ,out

V 2 V12
= m u2 u1 + 2
+ g ( z2 z1 )
2

z2

V1

z1

Stationary system:

Qnet ,in Wnet ,out = U 2 U 1

[ kJ ]

Wnet ,out

KE = PE = 0

Qnet ,in Wnet ,out = m ( u2 u1 )

[ kJ ]

qnet ,in wnet ,out = u2 u1

kJ
kg

Qnet ,in
u1

For a cycle:
E = 0

Qnet ,in

u2

[ kJ ]

= Wnet ,out

1=2

Q
net ,out = W
net ,out

Constant pressure process P = const

Boundary work:

Wb
V2

Wother

[ kW ]
Wboundary = P (V2 V1 )

Q (Wboundary + Wother )

= U 2 U1

Q P (V2 V1 ) Wother

= U 2 U1

Q Wother

= U 2 + PV2 (U 1 + PV1 )

 
H2

H1

V1
P = 100

P = 100

Q Wother

= H 2 H1

Q Wother

= m ( h2 h1 )

(4-18)

4-3 SPECIFIC HEATS

Specific heat

Specific heat depends

energy required to raise the temperature

of a unit mass by one degree

kJ
kg K

cv

at constant volume

cp

at constant pressure

kJ
kg K

on how the energy is

added to the system
Joseph Black

Energy balance of closed stationary system for process

1) without any work

= u2 u1
at constant pressure


2) with a boundary work at constant pressure, wb ,

= u2 u1 + wb = u2 u1 + P ( v2 v1 )

= h2 h1

v = const

v = const

P = const

T + 1o

P2

P = const

P1

T + 1o
T

v1

v2

v1

Relationship between the transferred heat and the change of temperature

u (T ,v ) ,

v = const

u
u
du =
dT +
dv
T
v

v2

Definition of specific heats

u
q = u =
T
T

u
cv =

T v = const

kJ
kg K

du

v = const

du

dT v

dT

h (T ,P ) , P = const

h
h
dT +
dP
dh =
T
P

h
q = h =
T
T

kJ
kg K

h
cp =

T P = const

dh
dT

P = const

dh

dT p

P2 P1

IDEAL GAS

Pv = RT

Internal energy u (T ) is a function of T only (Joules experiment),

then h = u + Pv

Pv = RT




q w = u2 u1 V2 V1

Ideal Gas cv ,c p

u (T ) + RT h (T ) is a function of T only
c p (T ) ,cv (T ) in Table A-2b,c

for any process,

cv =

cav at (T1 + T2 ) 2

In Table A-17:

cv ,av (T2 T1 )

u = cv T

h = h2 h1 = c p (T ) dT c p ,av (T2 T1 )

h = cp T

du
dT

du = cv dT

dh
dT

dh = c p dT

u = u2 u1 = cv (T ) dT
1

not only at constant

pressure or volume

cp =

h = u + Pv

Table A-2 a,b,c

= u (T ) + RT

dh
du
=
+R
dT
dT

cp

cp

= cv + R

(4-29)

k=

cp

= cv + Ru

(4-30)

specific heats on a molar basis

cv

specific heat ratio (4-31)

"Nothing comes
from nothing"

5-1 CONSERVATION OF MASS

Parmenides 500BC

Change of mass within CV during the process

inlets

outlets

min

control
volume

mout

Ac

Mass balance

mCV

= min mout

[ kg ]

(5-8)

m2 m1 = min mout

mCV
t

in m

out
=m

kg
s

(5-9)

mCV

=
dV
t
t CV

rate of
change
of mass

Conservation of mass

dmCV
dt

kg
s

in m

out
= m

 

dV + CS V ndA = 0
t CV

(5-17)

t = time interval

Ac

differential volume

Differential mass flow rate

dV = ( dAc )( L )

through the differential area dAc

 flow

V velocity

of the inlet (exit) surface area Ac

=
m

m
t

dV
t

dAc L
= Vn dAc
t

(5-2), (5-3)

Mass flow rate through the area Ac

dAc

normal
vector

 

Vn = V n
normal
velocity

of incompressible fluid ( =const )

or for the case of uniform density ( =const ) over cross-section Ac

= m

=
m
Ac

V dA
n

= Vn dAc

Ac

Ac

1
=
Ac

V dA A
n





m

Volume flow rate

V

Steady Flow (SF)

mCV
=0
t

= Vavg Ac

= Vavg Ac

Vavg
v

Ac

= vm

V

v

kg
s

m3

s

( 5.7 )

= Vavg Ac ( 5-5 )

( 5-4 )

= V

m

Ac

Vavg

Mass flow rate

m =V =

V
v

m
= V
=

V

v

mCV = const

1
m

Incompressible Flow ( =const )

3
m

2
m

m

in

out
= m

(5-18)

V
= V

in

(5-20)

out

1 +m

2 =m

3
m

Steady Flow Single Stream (SF SS)

1 =m

2 =m


m
Incompressible Flow ( =const )

V1

V2

1
m

2
m
A1

A2

1V1 A1 = 2V2 A2

(5-19)

V1 A1 = V2 A2

(5-21)

5-2 FLOW WORK FLOW ENERGY

work required to push the mass

into or out of the control volume

control volume

= F L = ( P A) L = P ( A L ) = P V

= P V

= Pvm

= Pv

flow work can be treated as

the energy of a flowing fluid

F = PA

(5-23)

W = P v m

Flow Work
equation is the same whether
the flow is to or out of the C.V.

Total energy of the flowing fluid

ENERGY TRANSPORT BY MASS

Internal
Energy
m, P, V

Flow
Energy

U
+ PV +


H

+ Pv
u



KE

+ PE

mV 2
+ mgz
2

V2
2

+ gz

(5-27)

Units for mechanical energy terms

ke + pe =

m
V 2 m2
+ g 2 z [ m]
2 s 2
s
m2
2
1000 s
kJ
kg

kJ

kg

h +

V2
+ gz
2

Total specific energy

V2
= m h +
+ gz
2

(5-28)

Amount of energy transport by mass

E

V2
= m h +
+ gz
2

(5-29)

Rate of energy transport by mass

(5-27)

of flowing fluid

Energy Balance for Steady Flow Single Stream (SF SS) in a Pipe
Ac

control volume
the rate of energy transport

Vavg

m
s

by mass of flowing fluid

 p T
E = mc

through the control volume

of uniform cross-section Ac

 out = mc
 p T =
E = E in E out = m hin mh

( V

avg

Ac ) c p T = c pVavg Ac T

5-4 STEADY FLOW DEVICES

net ,in

steady state single flow

Nozzle ( A1 > A2 )

2
2

net ,out = m
h2 h1 + V2 V1 + g ( z2 z1 )
W

Q

Energy balance for

steam

inlet

T1 = 500 o C

=0, W

= 0 , pe = 0 , ke 0
Q

Usually:

P1 = 4MPa

kJ
V22 V12 m 2
1 kg
2
2
2
s 1000 m
s 2

increases velocity
P2 = 1MPa

at expence of pressure

exit
o

T2 = 400 C

V1 << V2

m

v1 = .07

v2 = .31
h2 = 3260

h1 = 3435

m
m
=

P1 > P2

V1 A1 V2 A2
=
v1
v2

0 = h2 h1 +

V22 V12
2

Diffuser ( A1 < A2 )
increases pressure
by reduction of velocity

air

P2 = 100kPa
exit

T2 =

V1 >> V2

Ideal Gas

P1 = 90kPa

P2 v2 = RT2

T1 = 10 o C

P1v1 = RT1

inlet

c p (T2 T1 ) h2 h1 =

m

m

V12 V22
2

h1 = c pT1
u1 = cvT1

P1 < P2

Compressor (pump, fan) ( P1 < P2 )

h2 = c pT2

that V1  V2 0

u2 = cvT2

to increase the
pressure of a fluid.
Requires power input.

m
=

m

P1 < P2

V1 A1 V2 A2
=
v1
v2

( if cooled )
Q

Turbine ( P1 > P2 )

= m
( h2 h1 )

w = h1 h2

W


m

=0, W

0 , pe = 0 , ke 0 ( but small )
Usually: Q

Produce power output.

V1


m
P1 > P2

W

Turbines convert energy

of flowing fluid into work.

W

z1

=0, W

0 , pe = 0 , ke = 0
Q

Usually:

Compressor is used

W

m

often it is assumed

V2 > V1

z2

m
=

m

V1 A1 V2 A2
=
v1
v2

W

= m
( h2 h1 )

w = h1 h2

P1 = 2000kPa

For steam turbine:

Inlet:

steam ( A-6 )

Outlet:

sat. liq.-vapor mix. @ Tsat and Psat

inlet
o

T1 = 500 C
P2 = 15kPa
exit

T2 = 54 o C
v1 v2

5-5 ANALYSIS OF UNSTEADY-FLOW PROCESS

hi

min

MASS BALANCE

The net mass transfer to the Control Volume during the process 1 2

he
ECV

mout

mCV

min

final

initial

total mass

total mass

state

state

entering

leaving

the system

the system

the system

Assumption of uniform-flow process:

m1 )CV

change in
the mass of

( m2

in

out

properties at the inlets and outlets

hi and he
are constant during the process:
averaged value

he =

he ,1 + he ,2
2

ENERGY BALANCE ( for

ke = pe = 0 )

Change in total energy:

ECV = U 2 U 1 = m2 u2 m1u1

Qnet ,in Wnet ,out

m h

e e

out

m h

i i

( m2u2

m1u1 )

( 5-46 )

in

SINGLE STREAM
W

m2 m1

= mi me

Qnet ,in Wnet ,out

= me he mi hi +

me

mi

( m2 u2

m1u1 )

If work includes the boundary work at constant pressure

Qin Wother = me he mi hi + ( m2 h2 m1 h1 )

W = Wother + Wb = Wother + P (V2 V1 ) = W + P ( m2 v2 m1v1 )

Example 5-12

Charging of a
rigid tank by steam

steam
Pi = 1MPa

insulated
rigid tank
Q=0

Ti = 300o C

P1 = 0
P2 = 1MPa

Mass balance:
0
0

= mi me
m2 m1

CV
Energy balance:

Qin Wout

me he mi hi +

(m u

2 2

m1u1

A-6

A-5

kJ
hi = 3051.6 u2 = hi = 3051.6
kg
u g @ P =1MPa = 2583 < u2 = 3051.6

A-6

T@ P =1MPa and u2 = 456 o C

m2 = mi

u2 = hi

kJ
kg

sup .vapor

W =0
V = 1 m3

Find T2 ,m2

m3
v2 @ P =1MPa and u2 = 0.33
kg
m2 = V v2 = 1.0 0.33 3 [ kg ]

6-2 THERMAL ENERGY RESERVOIRS

Qin

SINK

Energy reservoir is a hypothetical body

of large heat capacitance ( mc p >> 1)
that can supply (source) or absorb (sink)

SOURCE

finite amounts of heat without any change of temperature

Qout

6-3 HEAT ENGINES

Heat engine is a device, which converts heat into work

TH
energy balance for HE

QH

QH = QL + Wout

Heat

Wnet,out

Engine

Wnet ,out

QL
QL

1.

Heat is received from a source at TH

2.

Part of heat is converted to work.

3.

Remaining heat is rejected to a sink at TL

4.

Heat engine operates on a complete cycle.

TL

STEAM POWER PLANT

The steam power plant is an external-combustion engine

furnace

Qin

(6-1)

Wnet ,out = Wout Win

TH
system boundary

Qnet ,in = Qin Qout = QH QL

boiler

working
fluid

Esys = 0

Wnet ,out = Qnet ,in

Win

closed system cycle

Wout
pump

turbine

(6-2)

Wnet ,out = Qin Qout

condensor
Qout

waste energy

Q



net ,out = Q
W
in
out

TL
surroundings

THERMAL EFFICIENCY

th = Thermal Efficiency =

th =

th =

Wnet ,out
Qin

net ,out
W


Q
in

Net work output

Total heat input

Qin Qout
Q
Q
= 1 out = 1 L
Qin
Qin
QH

Q






Q
Q
Q
in
out
= 1 out = 1 L






Q
Q
Q
in
in
H

THE SECOND LAW OF THERMODYNAMICS

Lord Kelvin
(1824-1907)

Kelvin Planck Statement:

Max Planck
(1858-1947)

Rudolf Clausius
(1822-1888)

It is impossible for any device that operates on a cycle

to receive heat from a single reservoir and
produce a net amount of work

TH
For heat engine to operate, the working fluid has

QH
Violation
of the 2nd Law:

to exchange heat with heat sink as well with the heat source.
If QL = 0 , then th = 1

Heat

Wnet,out

Engine

QL
= 1 , therefore, the 2nd Law claims that
QH

no heat engine can be 100% efficient:

th < 1

Clausius Statement:

No device can operate on a cycle and produce effect

that is solely the heat transfer from
a lower-temperature body to a higher-temperature body

TH
QH
Violation

There are devices that can transfer heat

of the 2nd Law:

from lower-temperature reservoirs to higher-temperature reservoirs

but they have also to consume some energy Win

QL
TL

1) Assume that Kelvin-Planck statement is violated

Equivalence of
two statements:

2) Attach heat engine to refrigerator

TH

TH

TH
QL

QH + QL

QH

QH

3) Violation of Clausius statement

If some device
violates one statement,

Heat
Engine

it also violates

th = 1

QH =Wout

Refrigerator

Heat
Engine

QH =Win

combine in a single device

th = 1

the other statement,

QL

and vice versa.

QL
TL

TL

TL

6-4 REFRIGERATOR

Refrigerator transfers heat

from a low-temperature medium to
a higher temperature medium

Objective: remove heat from a refrigeration space

Q

surroundings

TH
QH

Vapor-compression
condensor

refrigeration
cycle

QH = QL + Win

working
fluid =
refrigerant

compressor

throttle

COPR =

Win

Win
evaporator

QL

QL
TL
refregerated space

HEAT PUMP

COPR =

Desired
Output

Heat pump transfers heat

from a low-temperature medium to
a higher temperature medium

living space

TH

QL
QL
1
=
=
QH
Win
QH QL
1
QL

Q
Q
1
L
L
=
=








Win
QH QL
QH

1
Q
L

Objective: supply heat to a living space

Desired
Output

HEAT

QH
Vapor-compression
condensor

refrigeration
cycle

QH = QL + Win

working
fluid =
refrigerant

compressor

throttle

COPHP =

QH
QH
=
=
Win
QH QL

1
Q
1 L
QH

COPHP =

Q
Q
H
H
=

in

Q

=
W
Q
H
L

1


Q
1 L


Q
H

Win

Win

evaporator

QL

QL

TL
cold reservoir

COEFFICIENT OF PERFORMANCE

6-5

PERPETUALMOTION MACHINES
PMM1

violates the 1st law of thermodynamics

PMM2

violates the 2nd law of thermodynamic

COP =

Desired output
Required input

Planck, p.86
112. A process which can in no way be completely
reversed is termed irreversible, all other processes reversible.
That a process may be irreversible, it is not
sufficient that it cannot be directly reversed. This is the
case with many mechanical processes which are not irreversible
(cf. 113). The full requirement is, that it be
impossible, even with the assistance of all agents in nature,
to restore everywhere the exact initial state when the process has once taken place.
The propositions of the three preceding paragraphs, therefore, declare, that the generation
of heat by friction, the expansion of a gas without the performance
of external work and the absorption of external
heat, the conduction of heat, etc., are irreversible processes.
115. Since there exists in nature no process entirely
free from friction or heat-conduction, all processes which
actually take place in nature, if the second law be correct,
are in reality irreversible ; reversible processes form only an
ideal limiting case.
116. The second fundamental principle of thermodynamics being,
like the first, an empirical law,
we can speak of its proof only in so far as its total purport may be
deduced from a single self-evident proposition.
We, therefore, put forward the following proposition
as being given directly by experience :
It is impossible to construct an engine
which will work in a complete cycle, and produce no effect except
the raising of a weight and the cooling of a heat-reservoir.
Such an engine could be used simultaneously as a motor
and a refrigerator without any waste of energy or material,
and would in any case be the most profitable engine ever
made.
It would, it is true, not be equivalent to perpetual
motion, for it does not produce work from nothing, but from
the heat, which it draws from the reservoir.
It would not, therefore, like perpetual motion, contradict the principle of
energy, but would, nevertheless, possess for man the essential
advantage of perpetual motion, the supply of work without cost ;
for the inexhaustible supply of heat in the earth, in
the atmosphere, and in the sea, would, like the oxygen
of the atmosphere, be at everybody's immediate disposal.

The Carnot Cycle (Heat Engine)

6-7 THE CARNOT CYCLE

The Reversed Carnot Cycle (Refrigerator, Heat Pump)

TH

TH

QH

QH

TH
Q=0

Wnet ,out

TH
Wnet ,in

Q=0

Q=0

2
3

QL

Sadi Carnot (1822-1888)

V1

The Carnot Cycle consists

V4

V2

Reversible Processes

V3

V1

V2

W
V2

2
2

V4

TL
V

V3

TL
3

V3

V2

V3

V4

continues
to expand

-Q

-W

QL

gas

TL

TL

of 4 reversible processes

Q=0

the paths coinside

V4

V1

heat transfer is due to infinitely

small difference in temperature

at thermal equilibrium

V1

gas

Irreversible Processes
insulated

insulated

T > 0

QH
heat transfer is due to finite

difference in temperature
heat generation by friction

6-8 CARNOT PRINCIPLES

QL

Isothermal expansion
at TH
heat QH is added

Adiabatic expansion
Q=0
Temperature dropped to TL

Isothermal compression

Adiabatic compression

at TL

Q=0
Temperature raised to TH

heat QL is rejected

Efficiency of two Heat Engines operating between the same two reservoirs at TL and TH
TH

C1

irreversible < reversible

IR < R

Violation of Carnot Principles

yields violation of the

IR

R1 = R2

R1

R2

2nd Law of Thermodynamics

C2

reversible 1 = reversible 2
TL

6-9 THE THERMODYNAMIC TEMPERATURE SCALE

For reversible heat engine operating between TL and TH :

QL
T
= L
QH
TH

Kelvin Scale of Absolute Temperature

6-10 THE CARNOT HEAT ENGINE The efficiency of heat engine operating on a reversible Carnot cycle between TL and TH :

C = 1

6-11 THE CARNOT HEAT PUMP

QL
T
= 1 L
QH
TH

Carnot Heat Pump:

COPCHP =

1
Q
1 L
QH

Carnot
Efficiency

C is the highest possible efficiency

of the heat engine operating between
two reservoirs at TL and TH

Carnot Refrigerator:

1
T
1 L
TH

COPCR =

1
1
=
QH
TH
1
1
QL
TL

INSTITUT NATIONAL DES SCIENCES APPLIQUEES, LYON

2nd LAW OF THERMODYNAMICS ramification

Kelvin-Planck

Clausius Inequality

Clausius

TH

TH
Q

=0
T rev

for all

cycles

W
Q

TL

TL

impossible

impossible
Q
=

Carnot

Carnot
Cycle

T

Q
T

+
3

Q
T

for any
reversible
cycle

QH QL
Q Q T

= L H L 1 = 0
TH TL
TL QL TH

7-1 ENTROPY Clausius: I propose to name the quantity S the entropy of the system, after the Greek word [trope], the transformation

Q
dS =

T rev

T
reversible process

(7-4 )

definition of the differential of entropy

Q = TdS
T

dS

S1

S2

S = S 2 S1

Q
=

T rev
1

change of entropy during rev. process

kJ
K

total entropy

kJ
kg K

specific entropy (entropy)

T
reversible process

Q = TdS

s=

S1

S2

S
m

7-2 ENTROPY CHANGE AND ENTROPY GENERATION

Reversible

Arbitrary process

Q
T

Q
T

Q
2 T rev =

dS

+ S1 S 2 0
2

S 2 S1

(7-7 )

Entropy change S
can be negative,
but entropy generation
S gen cannot:

INCREASE OF ENTROPY PRINCIPLE

2

S 2 S1 =

S1

S3

entropy change

S = S1 + S 2 + S 3

In statistical thermodynamics
entropy is treated as a measure
of molecular disorder

S = k ln p

entropy transfer with heat

S gen

(7-9 )

S gen 0

(7-10 )

( Sisolated )rev = 0

entropy generation

Entropy of irreversible

S2
entropy is an extansive property:

Sisolated > 0

isolated system ( Q = 0 )
is increasing
during a process

The Universe is
an isolated
system

Entropy (disorder)

of the Universe
is increasing

(7-11)

7-5 T-S DIAGRAM

Q
dS =
( 7-4 )

T int rev

Internally reversible process

= TdS

For internally

( 7-14 )

reversible process

( 7-15 )

the internally

T
2

Internally

reversible

Heat transfer during

TdS

process

reversible process

Tds

( 7-17 )

Area = Q

S1

S2

Isothermal Process

= T0 ( S 2 S1 )

( 7-18 )

= T0 ( s2 s1 )

( 7-19 )

T0

isothermal
process is
internally
reversible

q
S

S1

S2

7-4 Isentropic process ( S = const ) T

2
isentropic process
reversible adiabatic

Q=0

is associated with

internally reversible

isentropic process

adiabatic process

1
S

S1 = S 2

Example 7-6

Carnot Cycle

QH

TH

Qnet ,in

= Wnet ,out

Wnet ,out

= QH QL

Wnet ,out = QH QL

TL

QL

S1 = S 4

S 2 = S3

h-s diagram (Mollier diagram, p.345) is useful for analysis of steady-flow devices
h
1

h1
measure
of work

w = h

For adiabatic steady-flow devices:

nozzles, turbines, compressors, etc.

output

h2

q = T s

s
Richard Mollier (1863 1935)

s1

measure of the
irreversibilities

s2

For isothermal processes

7-7 GIBBS EQUATIONS THE Tds RELATIONS

Start with closed system

Q W = dU

W = PdV
Q = TdS

energy balance

TdS = dU + PdV

h = u + Pv
dh = du + Pdv + vdP

for reversible process

boundary work
for reversible process
u = h Pv
du = dh Pdv vdP
(1839-1903)

Tds = du + Pdv
1st Gibbs Equation

(7-25 )

Gibbs equations do not depend

on the type of the process
(reversible and irreversible),
they are valid both for
closed and open systems (p.350),

1
P
ds =
du +
dv
T
T

Tds = dh vdP

because they include only properties

2 nd Gibbs Equation

ds =

1
v
dh
dP
T
T

ENTROPY CHANGE

(7-26 )

ISENTROPIC PROCESS, S=0

7-8 LIQUIDS AND SOLIDS cv = c p = c , dv = 0 (incompressible substance)

ds =

1
dT
du = c
T
T

s2 s1

= cavg ln

Isentropic process ( s1 = s2 ) is an isothermal process :

T2
T1

T2 = T1

Pv = RT , du = cv dT , dh = c p dT

7-9 IDEAL GAS

Isentropic process
P1

ds = cv

ds = c p

dT
dv
+ R
T
v

1st Gibbs Eq

dT
dP
R
T
P

2nd Gibbs Eq

T1
P2

T2

s1 = s2

Constant specific heats:

cv ,avg , c p ,avg at Tavg = T1 + T2

2

Isentropic process (polytropic process with n = k )

Table A-2

P1

T
1

s2 s1

T1

T
v
= cv ,avg ln 2 + R ln 2
T1
v1

( 7-33 )

P2
T2

s2 s1

s1

s2

= c p ,avg ln

T2
P
R ln 2
T1
P1

( 7-34 )

T2 v1
=
T1 v2

k 1

T2 P2
=
T1 P1
P2 v1
=
P1 v2

Exact Analysis

s2 s1

= s2o s1o R ln

s o = c p (T )
0

=C

Specific
heat ratio

k=
k 1
k

cp
cv

R = c p cv

TP (1 k ) k = C

R
= k 1
cv

cv =

1
R
k 1

cp =

k
R
k 1

Pv k = C

Isentropic process ( s1 = s2 )

P2
P1

( 7-39 )

where, the temperature dependent part of entropy is defined by:

T

Tv

k 1

dT
dT
, s2o s1o = c p (T )
T
T
1

s2o = s10 + R ln

P2
P1

s o ,Pr ,vr

( 7-38)

Table A-17

v2 vr 2
=
v1 vr1

(7 50 )

relative specific pressure and volume:

P2 Pr 2
=
(7 49 )
P1 Pr1

7-10 REVERSIBLE STEADY-FLOW WORK

inlet state

outlet state

qrev wrev = dh + dke + dpe

Energy balance

qrev = Tds = dh vdP

2nd Gibbs equation

wrev = vdP dke dpe

w
2

Reversible work output for

wrev ,net ,out = vdP ke pe

(7-51)

steady-flow and closed systems

P
turbine

P1

wrev ,out = vdP

wrev ,out

(7-52 )

turbine

turbine

( for ke = pe = 0 )

P2

vdP

wrev ,in =

compression

compressor

v2
P

in derivation, we assume that both

processes are between the same states

wrev ,net ,out wact ,net ,out

turbine
wrev ,out wact ,out

P1

v1

Steady-flow devices

wrev ,out wact ,out

deliver the most and

consume the least work
when the process is
reversible

turbine

actual
reversible

P2

wrev ,in wact ,in

compression

qact wact = dh + dke + dpe

qrev wrev = dh + dke + dpe
qact qrev wact + wrev = 0
wrev wact =

qrev qact
Tds

wrev wact
T

v2

v1

7-11 Compression work for ideal gas (p.364)

isothermal ( n = 1)

Ideal gas

v = cP

1
k

wcomp ,in

wcomp ,in

n 1

nRT1 P2 n
n

=
R (T2 T1 ) =
1
n 1
n 1 P1

temperature

Q=0

wcomp ,in

minimum
heat transfer

Eq.7-9

= sgen 0

k 1

kRT1 P2 k
k

=
R (T2 T1 ) =
1
k 1
k 1 P1

isentropic ( n = k ) is increased

P2

Equations 7-57 a,b,c

Pv = RT

Pv k = const

polytropic ( 1 < n < k )

T = const

qact

wrev wact

Isentropic process

= ds

Polytropic process
Pv n = const

v = cP

1
n

P1
Qout maximum
heat transfer

v
By cooling compressor, the requiered work input
can be minimized to achive the same pressure increase

Incompressible fluid ( v = const , 7-51)

Isothermal process
Pv = const

v = cP 1

wcomp ,in = RT ln

wrev = v ( P2 P1 ) ke pe

P2
P1

(7-54 )

Bernoulli equation (steady flow of incompressible fluid through the simple pipe without friction)
inlet state

outlet state

pipe

P2 P1

w=0
Flow through the pipe which involves no work interaction

V22 V12
+ g ( z2 z1 ) = 0
2

(7-55 )

Danila Bernoulov

(1700 1782 )

ISENTROPIC EFFICIENCIES

is a measure of the deviation of actual process from the corresponding isentropic process

Turbine

P1

h1
wa

ws

T =

w
actual work
= a
isentropic work
ws

T =

h1 h2a
h1 h2s

C =

w
isentropic work
= s
actual work
wa

C =

h2 s h1
h2a h1

P2

h2 a
h2 s

2s

2a

actual

isentropic

Compressor and pump

P2

actual 2 a

h2 a
isentropic

h2 s
wa

2s

ws

h1

P1

1
s

P =

v ( P2 P1 )
h2a h1

Nozzle

N =

P1

h1
wa

ws

h1 = h2a +

P2

h2 a
h2 s

V2
actual KE at exit
= 2a2
isentropic KE at exit
V2 s

2s

V2a2
2

2a

actual

isentropic

N =

h1 h2a
h1 h2s

compressor

pump

7-13 ENTROPY BALANCE

There is no conservation of entropy law, but we can established the entropy balance

T
1

by heat

by heat

T1

Sin

T2

s2 s1

= sin sout + sgen

kJ
K

S out

S gen

kJ
kg K

S system

dS system

S2

S1

= Sin Sout + S gen

by mass

by mass

S 2 S1

kW
K

=
Sin S
out + S
gen

dt

S system = S 2 S1

Entropy can be transferred with heat and with mass, and cannot be transferred with work

Entropy Transfer

S heat =

Q
T

S mass = ms

energy transfer which is not

accomponied by entropy transfer
is work
S work = 0

Heat transfer at constant temperature T

Heat Transfer

solids,liquids,
ideal gas:
Q = mcv T

S heat ,in =

Heat transfer when T of a system is variable

2

Q
T

T2

S heat

T1

S heat ,out =

=
k

Qk
Tk

Qk

Tk

m,cv

= mc

v T
Q

Q
T

S

heat

=
k

Q
k
Tk

Mass Flow
inlet

= s m =
S t

S mass

= ms

S mass

= mi si me se

outlet

mi si

me se

S
mass
CLOSED SYSTEMS ( ms = 0 )

Tk

Sgen

Ssur

Qk

Sgen = Ssys

Sgen =Ssys +Ssur

Qk

treated as an adiabatic system





adiabatic closed system

system + surroundings

Q
k

me se
S gen

T
k

Q
k

S

gen

( se si )
=m

SF SS adiabatic

Q

Tk

S

Steady Flow
gen

( se si )
=m

T
k

SF SS

+ S
gen

Qk

Scv

mi si

= S 2 S1

dScv
dt

Qk

Tk

mi si

+ S gen

T
k

OPEN SYSTEMS

= ( Vn Ac ) s
= ms

Ssys

Q
k

T
k

+ mi si me se + S gen
i

i si m

e se + S
gen
+ m
i

i si m

e se +
S gen
+m
i

= S 2 S1

dScv
dt

= 0

9-1 GAS POWER CYCLES BASICS

Power cycles (heat engines) produce work from heat.

ideal

TH

cycle

QH
actual
cycle

Wnet ,out

Wnet ,out

QL
TL

th =

Thermal efficiency:
Ideal power cycle:

Air-standard cycle:

Wnet
w
= net
Qin
qin

th Carnot = 1

all processes are internally reversible

no friction

quasi-equilibrium expansion and compression

TL
TH

no heat loss between devices

negligible change in KE and PE

working fluid is air (ideal gas)

all processes are internally reversible

combustion process is modeled by heat transfer QH from reservoir at TH

exhaust process is modeled by heat transfer QL to reservoir at TL

kJ
cold air assumption: cv = 0.718 , c p = 1.005
, k = 1.4 , R = 0.287
kg K

Ideal air-standard cycle (internally reversible) is not, in general, a Carnot cycle (totally reversible)

QH = TH ( S 2 S1 )

9-2 CARNOT CYCLE

T

qH = TH ( s2 s1 )

QL = TL ( S3 S4 )

TH

TH

Carnot =
QH

Qnet ,in = QH QL = Wnet ,out

QL

QH QL
Q
= 1 L
QH
QH

Carnot = 1

TL

4
TH

S1 = S 4

S 2 = S3

qL = TL ( s3 s4 ) = TL ( s2 s1 )
Kelvin
scale

TL
TH

T (s s )
QL
q
T
= 1 L = 1 L 2 1 = 1 L
QH
qH
TH ( s2 s1 )
TH

T
wnet ,out = Carnot qH = 1 L
T

TH ( s2 s1 ) = (TH TL ) ( s2 s1 )

9-4 RECIPROCATING ENGINE (piston-cylinder device) Internal combustion engines

Mean Effective Pressure

Spark ignition engines ( SI )

Wnet

MEP =
Compression ignition engines ( CI )

MEP
mean
effective

Displacement volume

Wnet = MEP (Vmax Vmin )

Vmax Vmin

MEP =

pressure

V
Vmin

bore

clearance
volume

Vmax

volume

TDS
top dead center

stroke

BDS
bottom dead center

wnet
wnet
=
vmin
1
vmax 1
vmax 1

r
vmax

Compression ratio

V
V
v
r = BDC = max = max
VTDC
Vmin
vmin

displacement

Wnet
wnet
=
Vmax Vmin
vmax vmin

MEP =

wnet
wnet
=
vmin ( r 1)
vmax

vmin
1
vmin

RECIPROCATING ENGINES OVERVIEW

Reciprocating engine (piston-cylinder device)

Spark ignition engines ( SI )
Compression ignition engines ( CI )

Internal combustion engines

Wnet

mean
effective

Displacement volume

Vmax Vmin

Compression ratio

r =

pressure

MEP
Wnet = MEP (Vmax Vmin )

VBDC
V
v
= max = max
VTDC
Vmin
vmin

V
Vmin

Vmax

clearance

displacement

volume

volume

Mean Effective Pressure

MEP =

Wnet
wnet
=
Vmax Vmin
vmax vmin

bore

MEP =
TDS
top
dead
center

stroke

BDS
bottom
dead
center

MEP =

SI

spark-ignition engines

(combustion is initiated by a spark plug)

CI

compression-ignition engines

(combustion is self-ignited as a result of compression)

wnet
wnet
=
vmin
1
v
vmax 1
max 1

v
max

wnet
wnet
=
vmin ( r 1)
vmax

vmin
1
vmin

9-5 OTTO CYCLE SPARK-IGNITION ENGINES

Actual 4-stroke spark-ignition engine

P

http : // www.keveney.com / Engines.html

Beau de Rochas

Nikolaus Otto

(1815-1893)

(1832-1891)

3
ignition
expansion

ignition

compression

4
4

exhaust

1
intake

expansion
compression

exhaust

intake

( power )

Ideal Otto cycle (air-standard cycle)

P

compression

v1 v4
=
=r
v2 v3

3
ignition

ratio

isentropic
expansion

qin

4
qout
isentropic
compression

1
isentropic

V
v2 = v3

v1 = v4

isentropic
expansion

heat
addition
v = const

compression

heat
rejection
v = const

3
Energy balance (Otto cycle is executed in a closed system) :
v2 = v3 = vmax

cycle
isentropic
expansion

qin

23:

isentropic

= u = 0

wnet ,out = qin qout

qin = u3 u2 = cv (T3 T2 )
heat transfer at v = const ( w = 0 )

compression

( qin qout ) ( wout win )

v1 = v4 = vmin

qout

4 1:

qout = u4 u1 = cv (T4 T1 )

s
s1 = s2

s3 = s4

Isentropic processes 1-2 and 3-4 with v2 = v3 and v4 = v1 ( under cold air assumption ) :

T1 v2
=
T2 v1

thermal efficiency
of Otto cycle under
cold air assumption:

= 1 r 1 k

Typical
compression
ratios for
gasoline

k=

engines

k 1

1
r k 1

v
= 3
v4

k 1

T4
T3

T3 T4
=
T2 T1

cp
cv

Thermal efficiency of the ideal Otto cycle ( under cold air assumption ) :

T4

1
T T

= 1 1 1
T2 T3

1
T
2

argon
helium

air
CO2

actual engines

P2 v1
= = rk
P1 v2

th ,Otto

wnet
q
T T
= 1 out = 1 4 1
qin
qin
T3 T2

= 1

v
T1
= 1 2
T2
v1

k 1

1
= 1
r

k 1

= 1 r 1 k

thermal efficiency
of Otto cycle under
cold air assumption

Ideal gas

9-6

CYCLE

P v = RT

injection of fuel
and combustion

qin

Diesel cycle is executed in a closed system

2
P2 = P3

PV k = const
isentropic
expansion

wnet ,ou = qnet ,in

Rudolf Diesel

wnet,out

( 1858 1913 )

4
modelling

qout of fresh

isentropic
compression

of air only

air intake

2 3:

qin wout = u3 u2

v
v2

v3

heat transfer and boundary work at constant pressure:

v1 = v4

boundary work at constant pressure



qin = wout + u3 u2

= P2 ( v3 v2 ) + u3 u2

qin = h3 h2

= c p (T3 T2 )

= h3 h2

3
P = const

qin

2
4
qnet,in

4 1:

heat transfer at constant volume:

qout
v = vmin

= cv (T4 T1 )

qout = u4 u1
s

s1 = s2

s3 = s4

Thermal efficiency of the ideal Diesel cycle (cold - air - standard assumption ):
r=

v1
v2

rc =

v3
v2

compression ratio

th

cutoff ratio

under cold air assumption:

Diesel = 1 r

1 ( rck 1)

k ( rc 1)

c (T T )
wnet
q
1 T4 T1
= 1 out = 1 v 4 1 = 1
qin
qin
c p (T3 T2 )
k T3 T2

T4

1
1 T1 T1

= 1
k T2 T3

1
T2

Thermal efficiency of Diesel cycle

1 k

( 9-12 )

= 1

1v
= 1 2
k v1

k 1

T4

1
T1

T3

1
T2

k
k
1 1 ( rc 1)
r 1 k ( rc 1)
1
=

k r k 1 ( rc 1)
k ( rc 1)

Isentropic process 1 2:

T1 v2
=
T2 v1

Typical
compression
ratios for

k 1

T1 T4 1
=
T2 T3 rck 1

1
r k 1

gasoline
engines

Isentropic process 3 4:

Otto > Diesel

T4 v3
=
T3 v4

k 1

v v
= 3 2
v2 v4

k 1

r
= c
r

k 1

T3 k 1 T4
rc =
T2
T1

efficiency of actual
diesel engines

Constant pressure process 2 3:

efficiency of actual
gasoline engines

P2 v2 P3 v3
=
T2
T3

P2 = P3

v2 v3
=
T2 T3

T3 v3
= = rc
T2 v2
T4 T3 k 1
= rc = rc rck 1 = rck
T1 T2

9 -7

STIRLING CYCLE

qin

https://www.stirlingengine.com/

External combustion engine

TH

qin
v=const

regenerator
TH = const

Reverend Robert Stirling

regenerator

TL = const

TL

3
qout

qout
s4

(1790 1878 )

v=const

s
s1

s3

s2

v1 = v4

v 2 = v3

Carnot
Thermal efficiency of Stirling

th = 1

cycles

Ericsson

ERICSSON CYCLE

External combustion engine

qin

TL
TH

TH

P=const

regenerator

John Ericsson

regenerator

(1803 1889 )
qout

P=const
TL

qout
s4

qin

s
s1

s3

s2

v4

v2

9-8 BRAYTON CYCLE

Gas-Turbine Engines

Steady-Flow

Open Cycle

Closed Cycle

The Ideal Bryton Cycle:

T

qin = h3 h2 = c p (T3 T2 )

wcomp ,in = h2 h1 = c p (T2 T1 )

qout = h4 h1 = c p (T4 T1 )

wturb,out = h3 h4 = c p (T3 T4 )

Tmax
P = const

qin

4
2
Tmin

P = const

= h3 h2 h4 + h1

wnet ,out = qin qout

qout

= h3 h4 ( h2 h1 )

= wturb ,out wcomp ,in

s
s1 = s2

s3 = s4

For isentropic processes 1-2 and 3-4:

T2 P2
=
T1 P1

qin

P = const

k 1
k

= rP

k 1
k

P
= 3
P4

k 1
k

T3
T4

rP =

P2 P3
=
pressure ratio
P1 P4

s = const

s = const

T4 T3
=
T1 T2

4
qout

v
v2

v1

v4

B =

wnet ,out
qin

q
= 1 out
qin

T T
= 1 4 1 = 1
T3 T2

T1 4 1
T
1
= 1 T1
T2
T

T2 3 1
T2

Thermal efficiency of Brayton cycle ( under cold - air assumption ) :

B = 1
rP

k 1
k

George Brayton

(1830 1892)

10-2 RANKINE CYCLE

Vapor power cycles working fluid is alternately vaporized and condensed

qin

2
boiler

wout

win
pump

turbine

(1820 1872)
condensor

Energy balance for a cycle:

qout

w


q


net ,in

net ,out

qin qout ( wout win ) = 0

Energy balance for a single stream steady-flow devices:

incompressible fluid
1 2 Pump:

Ideal Rankine sycle:

win = h2 h1

win = v1 ( P2 P1 )

v1 = v f @ P1

h1 = hf @ P1

P2 = P3 = const

h2 = h1 + win

qin

2 3 Boiler:

qin = h3 h2

3 4 Turbine:

wout = h4 h3

4 1 Condenser:

qout = h1 h4

wout

P1 = P4 = const
win

1
qout
s1 = s2

s3 = s4

th =

wnet
q
h h
= 1 out = 1 4 1
qin
qin
h3 h2

Heat rate =

1 Btu
kWh

Coefficient of thermal
efficiency used in US

th =

3412 [ Btu kWh]

Heat rate [ Btu kWh]

Amount of heat supplied in [ Btu ]

to generate 1 kWh of electricity

11 REFRIGERATION CYCLES
Vapor-compression

Refrigeration heat transfer from a lower temperature region to a higher temperature region

TH

refrigeration
cycle

qH

remove heat from a refrigeration space:

working
fluid = refrigerant

COPHP =

Heat pump objective:

evaporator

supply heat to a living space:

qL
qL
1
=
=
qH
win
qH qL
1
qL

win

compressor

throttle

COPR =

Refrigerator objective:

condensor

qH
qH
=
=
win
qH qL

1
q
1 L
qH

qL

TL

11-2 REVERSED CARNOT CYCLE

T

QH = QL + Win

COPR,Carnot =

P = const
QH

qL
1
1
=
=
qH
TH
win
1
1
qL
TL

Win
P = const

win

COPHP,Carnot =

1
QL

QL

s
s3 = s4

qH
=
win

1
1
=
qL
T
1
1 L
qH
TH

s1 = s2

Vapor-compression refrigeration cycle working fluid (refrigerant) is

11-3 IDEAL REFRIGERATION CYCLE

vaporised and condensed alternately and is compressed in the vapor phase

T

P = const

COPR =
qout = h2 h3

qout

h1 h4
h2 h1

qH
=
wnet,in

h2 h3
h2 h1

qL
wnet,in

3
win

P = const

4s 4

win = h2 h1

1
qL = qin

COPHP =

4
qin = h1 h4

s
s3 = s4s s4

SF SS

s1 = s2

h3 = h4

( qin qout ) ( wout win ) = he hi

1 2 Compressor:

win = h2 h1

2 3 Condenser:

qout = h2 h3

3 4 Throttle:

h3 = h4

4 1 Evaporator:

qin = h1 h4

h1

h2