Thermodynamics

FE Review Session
February 24, 2015
 What is Thermodynamics?

 Application of three governing principles to individual

components or systems under consideration
» Mass Balance
» Energy Balance
» Entropy Balance
 Types of Systems

 Isolated systems have neither mass nor energy interactions

with surroundings
 Closed systems have energy interactions (heat transfer and
work) but no mass interactions
 Open systems have energy interactions (heat transfer and
work) as well as mass interactions
 Property and State

 Property is a particular characteristic of a given system

» Extensive properties are dependent on the amount of
mass in the system (m, V, U, etc.)
» Intensive properties are not dependent on the amount of
mass in the system (P, T, etc.)
» Specific properties are extensive properties per unit
mass and indicated by lower case letters (v = V/m, u =
U/m, etc.) Divide the system into smaller parts to
determine extensive or intensive

 State is defined using a set of properties

 State Principle: Need values of two, independent, intensive
properties to fix state for simple compressible substance
 Some Properties

 Absolute Pressure P (lbf/in2 or Pa)

 Absolute Temperature T (R or K)
 Specific Volume v (ft3/lbm or m3/kg)
 Specific Internal Energy u (Btu/lbm or kJ/kg)
 Specific Enthalpy h = u + Pv (Btu/lbm or kJ/kg)
 Specific Entropy s (Btu/lbm-R or kJ/kg-K)
 Specific Heat at Constant Pressure Cp (Btu/lbm-R or kJ/kg-K)
 Specific Heat at Constant Volume Cv (Btu/lbm-R or kJ/kg-K)
 Energy

 Energy consists of the microscopic internal energy (U) and

the macroscopic mechanical energy (KE and PE)
 Internal energy is related to microscopic kinetic energy
(translation, vibration, rotation, electronic motions) plus
chemical and nuclear energy
 Mechanical energy is related to bulk velocity and elevation is
a gravitational field

E  U  KE  PE
 Entropy

 Level of disorganization (disorder) in the system

Entropy is related to disorder Thermal energy is disorganized
(randomness)
Q 
dS   
2


1
 T  internally reversible

 For isothermal, reversible heat transfer only (e.g. Carnot

cycle or reversed Carnot cycle): Q = TS
 Entropy change calculations for pure substances require
property tables while for solids or liquids or ideal gases
simple equations can be used
 P-v and T-v Diagrams

Notice orientation of lines of constant T (on P-v diagram) and

lines of constant P (on T-v diagram)
Property Evaluation Table
 Compressed Liquid

 When P > Psat at given T or T < Tsat at given P

 P and T are independent
 Property tables may/may not be available
 v (T, P) ≈ vf at T
 u (T, P) ≈ uf at T
 h (T, P) ≈ hf at T + (vf at T)(P – Psat at T)
 s (T, P) ≈ sf at T
 C p = Cv = C
 u = CT
 h = u + vP
 s = C ln(T2/T1) Only absolute temperature (K or R)
 Two Phase Mixture

 In two-phase mixture, liquid and vapor exist in equilibrium

 P and T are not independent
 Quality is defined as the mass fraction of vapor phase
m
x g

y  y  x y  y 
f g
m m
f g f

v  xv  (1  x)v  v  xv
g f f fg

u  xu  (1  x)u  u  xu
g f f fg

h  xh  (1  x) h  h  xh
g f f fg

s  xs  (1  x) s  s  xs
g f f fg
 Superheated Vapor

 When P < Psat at given T or T > Tsat at given P

 P and T are independent
 No approximations; property tables must be used
 Compressible (Real) Gas
 Use reduced pressure and reduced temperature to obtain
compressibility factor using chart
Reduced Pressure Reduced Temperature
P T
P T 
R
R
PCritical
TCritical

 Compressibility factor is defined as

Ideal gas (Z = 1) when PR  0 at any TR
Pv
Z
or when TR > 2 at small values of PR

RT Air can usually be considered

ideal at temperatures above 266 K
at moderate pressures because its
critical temperature is 133 K
Compressibility Factor Chart
 Ideal Gas

 Ideal Gas Equation of State (Z = 1)

 Applicable at low pressure and high temperature relative to
critical point i.e. low density conditions

Pv  RT PV  mRT  nRT
Absolute temperature (K or R)
Absolute pressure not gage pressure

ft-lbf Btu
R R  1545  1.986
R lbmol-R lbmol-R
M J
 8314
kmol-K
 Ideal Gas (contd.)
 For an ideal gas, internal energy and enthalpy depend only
on the absolute temperature
 Use ideal gas tables to find property changes
u  u  u h  h  h
 
2 1 2 1

P
s  s  s  R ln
0 0
2
2
P 1

 For constant specific heat assumption

u  C T  T 
v 2 1
h  C T  T  p 2 1

Absolute temperature (K or R)

s  C ln
p  T
T 2

1
 R ln  P
P 2

1
 C lnv  TT2

1
 R ln  V
V2

1
 Special Processes

 Constant pressure (isobaric) P = constant

 Constant volume (isochoric) V = constant
 Constant temperature (isothermal) T = constant
 No heat interaction (adiabatic) Q = 0
 Constant enthalpy (isenthalpic) h = constant
 Constant entropy (isentropic) s = constant
 Adiabatic and reversible (isentropic) s = constant
 Isentropic Process – Ideal Gas
Process in which disorder (entropy)
 Constant Specific Heats remains unchanged  “ideal” process
Absolute temperature (K or R) ( k 1 ) / k k 1

T P v 
 
2 2
  1

T P
1 1 v 2

 Variable Specific Heats

Relative Pressure (Not Reduced Pressure) Relative Volume (No Reduced Volume)

p P v V v

r2 2
 
r2 2 2

p r1
P 1
v V v
r1 1 1

Relative pressure and relative volume

listed in air ideal gas tables; function of T only
 Open System Energy Balance
 Conservation of energy statement for control volume
h = u + Pv i.e. must consider flow work (Pv)

 V   V  dE
2 2

 
Q  W   m  h   gz    m  h   gz   CV

    dt
CV CV inlets
2 2 exits

 Mass entering the system increases energy content while

mass leaving the system decreases energy content
 Use appropriate sign convention for heat and work
interactions
» Heat transfer into system positive; heat transfer from
system negative
» Work into system negative; work out of system positive
 Open System Entropy Balance

 For an open system, entropy changes occur due to heat

transfer at the boundary, entropy production owing to
irreversibilities, and entropy transfer associated with mass
inflow and outflow
Mass entering increases disorder Mass leaving reduces disorder

Q dS
  m s   m s  S 
CV

i i e e gen
CV

T CV
inlets
dt
exits

Entropy generation due to irreversibilities

Due to heat transfer at boundary within the system
Absolute temperature (K or R)
 Closed System Energy Balance

 Special case with no inlets or exits (control mass)

Q  W  E Work Interaction

 U  PE  KE
(W) Heat Interaction
(Q)

Closed System
(E = U + PE + KE)

No Mass Interaction
(m = constant)
 Use appropriate sign convention for heat and work
interactions
» Heat transfer into system positive; heat transfer from
system negative
» Work into system negative; work out of system positive
 Closed System Entropy Balance

 For a closed system, entropy changes occur due to heat

transfer at all relevant boundaries and entropy generation
due to irreversibilities Entropy generation due to irreversibilities
within the system
Due to heat transfer
Q
at boundary
 S  Sgen
T b

Absolute temperature (K or R)
 Clausius Inequality

 For cycles (S = 0), we can write:

Results from applying the
entropy balance to a cycle Q Q 
S     
T  T 
gen
Absolute temperature (K or R)
b b

 Increase of entropy principle requires that total change in

entropy of the universe must always be positive

S gen ,total
 S  S
total system
 S surroundings

Stotal must always be zero (ideal reversible process) or positive ( real irreversible
process); Ssystem and Ssurroundings can be positive, negative, or zero
 Energy Interactions – Work

 For a reversible (quasi-equilibrium) process in open system:

W    VdP
2

Work is represented by the area under

W  V  P  P 
V =constant

process curve on P-v diagram projected

2 1
on the pressure axis

P=constant

W  0

n  PV  PV 
PV n =constant

W  1 1 2 2

n 1
 Energy Interactions – Work (contd.)

 For an ideal gas inside open system:

V
T  constant
 P
W  PV ln  2

  PV ln  P 
1

V   
1 1 1 1

1 2

T  constant

PV  PV
1 1 2 2

k  PV  PV   P 
( k 1 ) / k
Pv k  constant
k
W   RT 1   
1 1 2 2 2


k 1 k 1  P
1

1 
 Energy Interactions – Work (contd.)

 For a reversible (quasi-equilibrium) process in closed system:

W   PdV
2

b
1

V =constant Work is represented by the area under

W  0
b
process curve on P-v diagram projected
on the volume axis

W  P V  V 
P=constant

b 2 1

PV  PV
PV n =constant

W  1 1 2 2

n 1
b
 Energy Interactions – Work (contd.)
 For an ideal gas inside closed system:

W  P V  V 
V =constant P=constant

W  0 b b 2 1

T T V =constant
V V

P=constant
1 2
1 2

P1
P 2
T 1
T 2

V T  constant
 P
W  PV ln  2

  PV ln  P 
1

V   
b 1 1 1 1

1 2

T  constant

PV  PV
1 1 2 2
 Energy Interactions – Heat Transfer

 Conduction and Fourier’s Law


T1

» Conductive heat flux: q   k "

T
x
cond

where, x
T2
Important mostly in solids since ksolid > kliquid > kgas qcond ”

– qcond” = Heat flux in the direction of temperature

gradient (W/m2)
– k = Thermal conductivity in the direction of heat
transfer (W/m-K)
– dT/dx = Temperature gradient (K/m)
» Conductive heat transfer rate: T
q  q A   kA"

where, x
cond cond

– qcond = Heat transfer rate due to conduction (W)

– A = Area normal to temperature gradient (m2)
Energy Interactions – Heat Transfer (contd.)
Ts
 Convection and Newton’s Law of Cooling
» Convective heat flux: q "
conv
h
conv
T  T 
s 
u∞, T∞

where, Important at solid-fluid (liquid or gas) interface

– qconv” = Heat flux at the surface (W/m2)
– hconv = Convection heat transfer coefficient (W/m2-K)
– Ts and T∞ = Temperature of surface and fluid,
respectively
» Convective heat transfer rate:
q  q A  h A T  T
conv
"

conv s conv s s 

where,
– qconv = Heat transfer rate due to convection (W)
– As = Area of surface (m2)
Energy Interactions – Heat Transfer (contd.)

 Radiation Important at high temperatures; no medium required unlike

conduction/convection
» Radiative heat flux: "
where, 
qrad   Ts  Tsurr
4 4

– qrad” = Net radiation heat flux (W/m2)
–  = Emissivity of the given surface
–  = Stefan-Boltzmann constant (W/m2-K4)
– Ts and Tsurr = Absolute temperature (K) of surface and
surrounding, respectively Only for a gray surface in a large
» Radiative heat transfer rate: isothermal surrounding
q  q A   A T  T
" 4 4

where,
rad rad s s s surr

– qrad = Heat transfer rate due to radiation (W)

– As = Area of surface (m2)
 Some SSSF Devices

 Nozzles and Diffusers

» Single inlet and single exit
» No work interaction (passive devices)
» Usually adiabatic
» No potential energy change

V V 2 2

h  h 
i
i

e
e

2 2

Nozzle  increase KE (velocity) with decrease in enthalpy (pressure)

Diffuser  increase enthalpy (pressure) with decrease in KE (velocity)
 Some SSSF Devices (contd.)

 Turbines and Compressors

» Single inlet and single exit
» Usually adiabatic
» Usually no potential energy change
» Usually no kinetic energy change

w h h i e

 Pumps handle incompressible fluids (liquids)

w  c T  T   v  P  P 
i e i e

Turbine  decrease pressure (enthalpy) to produce work output (hi > he)
Compressor  to increase pressure (enthalpy) require work input (hi < he)
 Some SSSF Devices (contd.)

 Throttling Valves
» Single inlet and single exit
» No work interaction (passive device)
» Adiabatic
» No potential energy change
» No kinetic energy change

h h
i e
PP
e i

Enthalpy remains constant Pressure drops from inlet to exit

For ideal gas, no change in temperature from inlet to exit

For an incompressible fluid, temperature increases from inlet to exit
For a two-phase mixture, temperature decreases from inlet to exit
 Some SSSF Devices (contd.)

 Heat Exchangers
» Multiple inlets and multiple exits
» No work interaction (passive device)
» Usually no heat transfer to/from surroundings
» No potential energy change
» No kinetic energy change Exit Fluid 1

» Fluid streams do not mix

Inlet Fluid 2
Exit Fluid 2

In the absence of stray (to outside) heat transfer:

Heat gained by one fluid = Heat lost by the other fluid Inlet Fluid 1
 Some SSSF Devices (contd.)

 Mixing Chambers
» Multiple inlets and multiple exits
» No work interaction (passive device)
» Usually no heat transfer to/from surroundings
» No potential energy change
» No kinetic energy change
» Fluid streams mix directly
 Isentropic Efficiency – SSSF Devices

Exit pressure of both isentropic and actual process is same

w h h
  actual
 1 2

h h
turbine
Wactual w isentropic 1 2s
Wi sentropi c

 
V V  2 h  h
 2
2

1
2

1 2

V  V  2 h  h
nozzle

2s
2

1
2

1 2s
 Isentropic Efficiency – SSSF Devices (contd.)

Exit pressure of both isentropic and actual process is same

h P2

2a
w h h
2s   isentropic
 2s 1

h h
compressor

P1
w actual 2 1

 
V V  2 h  h
 1
2

2s
2

2s 1

V  V  2 h  h
1
diffuser 2 2

1 2 2 1

s
Basic Cycles – Heat Engine
Q  T
Net work output Q 
C
 C

  T
Q Q
H reversible only H

W
 thermal
  cycle H C

Q Q H H

Heat added

T T T
 thermal ,Carnot
 H
 1 C C

reversible
T T
H H

Absolute temperature (K or R)

• If thermal < thermal, Carnot  irreversible HE

• If thermal = thermal, Carnot  reversible HE
• If thermal > thermal, Carnot  impossible HE
 Basic Cycles – Refrigerator
Heat removed from
cold space

Q Q
COP   C C

Q Q
RF
W cycle H C

Work input required

T 1
COP  C

T  T T T   1
RF ,Carnot
reversible
H C H C

Absolute temperature (K or R)

• If COPRF < COPRF, Carnot  irreversible RF

• If COPRF = COPRF, Carnot  reversible RF
• If COPRF > COPRF, Carnot  impossible RF
 Basic Cycles – Heat Pump
Heat supplied to maintain
high temperature

Q Q
COP   H H

Q Q
HP
W cycle H C

Work input required

T 1
COP   H

T  T 1  T T 
HP ,Carnot
reversible
H C C H

Absolute temperature (K or R)

• If COPHP < COPHP, Carnot  irreversible HP

• If COPHP = COPHP, Carnot  reversible HP
• If COPHP > COPHP, Carnot  impossible HP
 Carnot (Most Ideal) Cycle

• Carnot power cycle has two isothermal

processes (heat addition and heat
rejection) and two isentropic processes
T
(expansion and compression) Carnot Power Cycle

• Reversed Carnot cycle is the basis for Heat addition at TH

1 2
refrigeration cycles such as vapor
compression cycle

• Power cycles always run clockwise on 4 3

property diagrams and refrigeration Heat rejection at TC
cycles always run anti-clockwise

• For any cycle, net work interaction s

equals net heat interaction
 Important Cycle Concepts
 Carnot cycle has maximum efficiency compared to any
other cycle
 For internally reversible cycles, heat transfer can be easily
calculated using Ts for isothermal processes
 For ideal cycles (all internally reversible processes), area
under the P-v diagram represents net work
 For ideal cycles (all internally reversible processes), area
under the T-s diagram represents net heat transfer
 Note ideal vapor compression cycle is not completely
internally reversible
 Throttling  irreversibility i.e. entropy increases
 Model for spark ignition
Otto Cycle (gasoline) engine

Compression Ratio constant specific heats

1 Mean Effective Pressure
 = 1
v V thermal ,Otto
rk 1
w q
r  1 1 MEP 
v v
 net net

v 1  
1
v V 2 2
T
1

 r
2
1

qin   u3  u2 
Heat addition 3
(v = constant)
q
 thermal ,Otto
1  out

q in 4
2

qout   u1  u4 
1
Heat rejection
(v = constant)

s
 Model for compression ignition
Diesel Cycle (diesel) engine

Compression Ratio constant specific heats

1  r  1  Mean Effective Pressure
k

 = 1  k r 1 
c

v V   
thermal , Diesel k 1

r  1 1 r c
MEP 
w

q net net

v V q v v
v 1  
1
2 2
 1  out
T
1 2
1
 r
qin   h3  h2  thermal , Diesel
q in
Heat addition 3
Cut-off Ratio (P = constant)

v V
r 
c
3 3

v V 2 2
4
2

qout   u1  u4 
Heat rejection
1 (v = constant)

s
 Model for power generation using
gas turbine engine
Brayton Cycle
Pressure Ratio
1

constant specific heats

P P = 1
r 
thermal , Brayton ( k 1 ) / k
2 3
r
p
p
P P T
qin   h3  h2 
1 4

Heat addition 3
q (P = constant)
 thermal , Brayton
1  out

q
in
4
2

qout   h1  h4  Heat rejection

1 (P = constant)

s
 Model for power generation in
steam power plants
Rankine Cycle

Heat is added in boiler Turbine produces power output

Q in  m steam  h1  h4  W  m h  h
turbine steam 1 2 

Heat is rejected in condenser

to the cooling water
Q out  m steam  h3  h2 

Wnet Wturbine  W pump

thermal   
Qin Q in
Q in  Q out Pump requires power input

Q in W pump  m steam  h3  h4   m steam  v3  v4  P3  P4 
Rankine Cycle (contd.)
q h  h 
  1 1 
out 3 3

thermal , Rankine
qin
h  h 
1 4
 Model for refrigeration or heat pump cycles

Vapor Compression Cycle

Q in Heat is rejected from refrigerant

COPRF 
Wcompressor in condenser to the ambient
Q out  m refrigerant  h3  h2 
Q out
COPHP 
Wcompressor
Compressor requires power input
Wcompressor  m refrigerant  h1  h2 
h3  h4
P4  P3

Heat is added to refrigerant in

evaporator from the space to be cooled Q in  m refrigerant  h1  h4 
 Vapor Compression Cycle (contd.)
q h h q h h
COP  in
 1 4
COP  
out 2 3

h h h h
refrigerator
win 2 1
heat pump
win 2 1
 Mass and Mole Fraction
 Mass Fraction Mass of ith species
m
x  i
i

Total mass of mixture

m total

x
i i
1
 Mole Fraction Moles of ith species
n
y  i
i
Total moles of mixture
n total


i
y 1
i
 Mass and Mole Fraction (contd.)
 Mixture Molecular Weight Total mass of mixture
m
MW    y MW
mix
total

i i
n total
i

Total moles of mixture

 Mass Fraction to Mole Fraction x i

MW
y 
 
i


x i

i
MW i

 Mole Fraction to Mass Fraction

y MW
x  i i

 y MW
i

i i i
 Mixture of Ideal Gases
 Partial Pressure and Partial Volume
Partial pressure of ith gas Partial volume of ith gas
P V
y  i
i i

Total pressure of mixture

P V Total volume of mixture

 Internal Energy, Enthalpy, and Entropy

u  xu
i i i
 
i
yu
i i
Mole-based specific property (kJ/kmol)

h  xh   y h
i i i i i i

Mass-based specific property (kJ/kg)

s  xs   y s
i i i i i i

Mass-based specific property = (Mole-based specific property)/MW

 Psychrometric Principles
 Dry air and water vapor behave as ideal gases at normal
pressure and temperature
 For two-component mixture, need three independent
intensive properties (pressure, temperature, water vapor
concentration expressed in terms of humidity)
 Specific Humidity (or Absolute Humidity or Humidity Ratio) of
moist air represents the mass of water vapor in given mass of
dry air
m p p
  0.622
vapor
 0.622
vapor vapor

m air
p p p
air vapor
 Psychrometric Principles (contd.)

 Relative humidity of moist air represents the partial pressure

of water vapor relative to the saturation pressure of water
vapor at the same temperature
y p v
 vapor
 vapor
 sat . vapor

y vapor , sat T ,P
p sat . vapor T ,P
v vapor T ,P

 Enthalpy of moist air

h  h  hair vapor
h  h T
vapor g db

In C
h C T
air p , air db

 Entropy of water vapor in moist air

s T , p
db vapor   s T   R
g db vapor
ln 
 Psychrometric Principles (contd.)
 Dew point temperature equals saturation temperature for
given partial pressure of water vapor
 Difference between adiabatic saturation temperature and
wet bulb temperature
 Adiabatic saturation process occurs at constant wet bulb
temperature and approximately at constant enthalpy
 Psychrometric chart useful for analysis of the various air-
conditioning processes using separate mass balance for
dry air and water vapor as well as energy balance
 Psychrometric Processes

 Simple heating and cooling ( = constant)

 Heating and humidification when outside air is cold and dry
during winter season
 Cooling and dehumidification when outside air is hot and
humid; evaporative cooling (cooling and humidification) when
outside air is hot and dry
 Mixing of moist air streams in air-conditioning ducts
 Cooling towers = 100% Humidification

Simple Cooling Simple Heating

Dehumidification

Increasing Dry Bulb Temperature

Psychrometric Chart
 Combustion
 Combustion between fuel and air is considered “complete”
when any combustible element is burned completely to its
oxide i.e. all carbon is burned to CO2, all hydrogen is burned
to H2O, all sulfur is burned to SO2
 100% theoretical air (stoichiometric air) is the amount of air
that supplies just sufficient oxygen for complete combustion
of all C, H, and S in the fuel
 Atoms are always balanced during chemical reactions; moles
may or may not be balanced
 Combustion (contd.)
 In “complete” hydrocarbon combustion
» Any available oxygen first reacts with H to form H2O
» Any remaining oxygen then reacts with C to form CO
» Any further oxygen then reacts with CO to produce CO2
» If oxygen (air) is excess, extra oxygen is left in products
 In reality, “complete” combustion never occurs due to
insufficient time and insufficient mixing
 Combustion (contd.)

 Air-fuel ratio represents the ratio of mass of air divided by the

mass of fuel
m n M M
AF   air air air
 AF air

m n M
fuel fuel fuel
M fuel

 Equivalence ratio represents the ratio of the actual fuel-air

ratio to the stoichiometric fuel-air ratio

 FA  actual

 FA
 = 1 for stoichiometric combustion
stoichiometric


  > 1 for fuel-rich combustion (deficient air)

  < 1 for fuel-lean combustion (excess air)