Thermodynamics

Symbol/Formula Parameter
M Molar mass (M/)
m Mass (M)
m Number of moles ()
n
M
E Energy or general extensive property
E Specific molar energy (energy per unit mass) or general extensive
e property per unit mass
m
E Specific energy (energy per unit mole) or general extensive
e  eM property per unit mole
n
P Pressure (ML-1T-2)
V Volume (L3);
Specific volume or volume per unit mass, v (L 3M-1) and the volume
per unit mole v (L3-1)
T Temperature (Θ)
 Density (ML-3);  = 1/v.
x Quality
U Thermodynamic internal energy (ML2T-2);
Internal energy per unit mass, u (L2T-2), and the internal energy per
unit mole, u (ML2T-2-1)
H = U + PV Thermodynamic enthalpy (ML2T-2);
Enthalpy per unit mass, h = u + Pv (dimensions: L2T-2) and the
internal energy per unit mole h (ML2T-2-1)
S Entropy (ML2T-2Θ-1);
Entropy per unit mass, s(L2T-2Θ-1) and the internal energy per unit
mole s (ML2T-2Θ-1-1)
W Work (ML2T-2)
Q Heat transfer (ML2T-2)

W u : The useful work rate or mechanical power (ML2T-3)

m : The mass flow rate (MT-1)


V2 The kinetic energy per unit mass (L2T-2)
:
2
gz: The potential energy per unit mass (L2T-2)

Etot: V2
The total energy = m(u + + gz) (ML2T-2)
2
Q : The heat transfer rate (ML2T-3)

dEcv The rate of change of energy for the control volume.(ml 2t-3)
:
dt
M Molar mass (M/)
m Mass (M)
m Number of moles ()
n
M
E Energy or general extensive property
E Specific molar energy (energy per unit mass) or general extensive
e property per unit mass
m
E Specific energy (energy per unit mole) or general extensive
e  eM property per unit mole
n
P Pressure (ML-1T-2)
V Volume (L3);
Specific volume or volume per unit mass, v (L 3M-1) and the volume
per unit mole v (L3-1)
T Temperature (Θ)
 Density (ML-3);  = 1/v.
x Quality
U Thermodynamic internal energy (ML2T-2);
Internal energy per unit mass, u (L2T-2), and the internal energy per
unit mole, u (ML2T-2-1)
H = U + PV Thermodynamic enthalpy (ML 2T-2); we also have the enthalpy per
unit mass, h = u + Pv (dimensions: L2T-2) and the internal energy
per unit mole h (ML2T-2-1)
S Entropy (ML2T-2Θ-1);
Entropy per unit mass, s(L2T-2Θ-1) and the internal energy per unit
mole s (ML2T-2Θ-1-1)
W Work (ML2T-2)
Q Heat transfer (ML2T-2)

W u : The useful work rate or mechanical power (ML2T-3)

m : The mass flow rate (MT-1)


V2 The kinetic energy per unit mass (L2T-2)
:
2
gz: The potential energy per unit mass (L2T-2)

Etot: V2
The total energy = m(u + + gz) (ML2T-2)
2
Q : The heat transfer rate (ML2T-3)

dEcv The rate of change of energy for the control volume.(ml2t-3)

:
dt
M Molar mass (M/)
m Mass (M)
m Number of moles ()
n
M
E Energy or general extensive property
E Specific molar energy (energy per unit mass) or general extensive
e property per unit mass
m
E Specific energy (energy per unit mole) or general extensive
e  eM property per unit mole
n
P Pressure (ML-1T-2)
V Volume (L3); we also have the specific volume or volume per unit
mass, v (L3M-1) and the volume per unit mole v (L3-1)
T Temperature (Θ)
 Density (ML-3);  = 1/v.
x Quality
U Thermodynamic internal energy (ML2T-2); we also have the internal
energy per unit mass, u (L2T-2), and the internal energy per unit
mole, u (ML2T-2-1)
H = U + PV Thermodynamic enthalpy (ML 2T-2); we also have the enthalpy per
unit mass, h = u + Pv (dimensions: L2T-2) and the internal energy
per unit mole h (ML2T-2-1)
S Entropy (ML2T-2Θ-1); we also have the entropy per unit mass, s(L2T-
Θ ) and the internal energy per unit mole s (ML2T-2Θ-1-1)
2 -1

W Work (ML2T-2)
Q Heat transfer (ML2T-2)

W u : The useful work rate or mechanical power (ML2T-3)

m : The mass flow rate (MT-1)


V2 The kinetic energy per unit mass (L2T-2)
:
2
gz: The potential energy per unit mass (L2T-2)

Etot: V2
The total energy = m(u + + gz) (ML2T-2)
2
Q : The heat transfer rate (ML2T-3)

dEcv The rate of change of energy for the control volume. (ml2t-3)
:
dt

Unit conversion factors

For metric units
 Basic:
o 1 N = 1 kg·m/s2;
o 1 J = 1 N·m;
o 1 W = 1 J/s;
o 1 Pa = 1 N/m2.
 Others:
o 1 kPa·m3 = 1 kJ;
o T(K) = T(oC) + 273.15;
o 1 L (liter) = 0.001 m3;
o 1 m2/s2 = 1 J/kg.
 Prefixes (and abbreviations):
o nano(n) – 10-9;
o micro() – 10-6;
o milli(m) – 10-3;
o kilo(k) – 103;
o mega(M) – 106;
o giga(G) – 109.
o A metric ton (European word: tonne) is 1000 kg.
For engineering units
  Energy:
o 1 Btu = 5.40395 psia·ft3 = 778.169 ft·lbf = (1 kWh)/3412.14 = (1 hp·h )/2544.5 =
25,037 lbm·ft2/s2.
 Pressure:
o 1 psia = 1 lbf/in2 = 144 psfa = 144 lbf/ft2.
 Others:
o T(R) = T(oF) + 459.67;
o 1 lbf = 32.174 lbm·ft/s2;
o 1 ton of refrigeration = 200 Btu/min.

Concepts & Definitions

Formula Units
Pressure F Pa
P
A
 Units 1 Pa  1 N / m2
1 bar  105 Pa  0.1 Mpa
1 atm  101325 Pa
Specific Volume V m3 / kg
v
m
Density m 1 kg / m3
  
V v
Static Pressure Variation P   gh   ,    Pa
Absolute Temperature T ( K )  T (C )  273.15

Properties of a Pure Substance

Formula Units
Quality mvapor
x (vapour mass fraction)
mtot
mliquid
1 x  (Liquid mass fraction)
mtot
Specific Volume v  v f  xv fg m3 / kg
Average Specific Volume v  (1  x)v f  xvg (only two phase mixture) m3 / kg
Ideal –gas law P  Pc T  Tc Z 1
 Equations Pv  RT PV  mRT  nRT
  Universal Gas Constant R  8.3145 kJ / kmol K
 Gas Constant R kJ / kg K
R M = molecular mass
M
Compressibility Factor Z Pv  ZRT
Reduced Properties P T
Pr  , Tr 
Pc Tc

Work & Heat

Formula Units
Displacement Work 2 2 J
W   Fdx   PdV
1 1
Integration 2 J
W   PdV  P (V2  V1 )
1
Specific Work W J / kg
w (work per unit mass)
m
Power (rate of work) W  FV  PV  T  W
 Velocity V  r rad / s
 Torque T  Fr Nm
Polytropic Process ( n  1) PV n  Const  PV 1 1  PV Pv n  C
n n
2 2


ln  2 
Polytropic Exponent P
n 
P1 
ln  1 
V
 V2 
 n=1 PV  Const  PV1 1  PV
2 2

Polytropic Process Work 1 J

W2  2 2  PV
( PV 1 1) n 1
1 n
1

 n=1  V2  J
1W2  PV
2 2 ln  
 V1 
Adiabatic Process Q0
Conduction Heat Transfer dT W
Q  kA , k =conductivity
dx
Convection Heat Transfer Q  hAT , h =convection coefficient W
Radiation Heat Transfer Q   A(Ts4  Tamb
4
) W

Terminology:
Q1 = heat
Q2 = heat transferred during the process between state 1 and state 2
Q = rate of heat transfer
W = work
1W2 = work done during the change from state 1 to state 2
W = rate of work = Power. 1 W=1 J/s

The First Law of Thermodynamics

Formula Units
Total Energy E  U  KE  PE  dE  dU  d ( KE )  d ( PE ) J
Energy dE   Q   W  E2  E1  1Q2  1W2 J
Kinetic Energy KE  0.5mV 2 J
Potential Energy PE  mgZ  PE2  PE1  mg (Z 2  Z1 ) J
Internal Energy U  Uliq  Uvap  mu  mliqu f  mvapug
Specific Internal Energy of u  (1  x)u f  xu g kJ / kg
Saturated Steam
u  u f  xu fg
(two-phase mass average)
Total Energy m(V22  V12 ) J
U 2  U1   mg ( Z 2  Z1 )  1Q2  1W2
2
Specific Energy e  u  0.5V 2  gZ
Enthalpy H  U  PV
Specific Enthalpy h  u  Pv kJ / kg
For Ideal Gasses Pv  RT and u  f (T )
 Enthalpy h  u  Pv  u  RT
 R Constant u  f (t )  h  f (T )
Specific Enthalpy for h  (1  x)h f  xhg kJ / kg
Saturation State
h  h f  xh fg
(two-phase mass average)
Specific Heat at 1  Q  1  U    u 
Constant Volume Cv        
m   T v m   T v   T  v
 (ue  ui )  Cv (Te  Ti )
Specific Heat at 1  Q  1 H   h 
Constant Pressure Cp        
m  T p m  T p  T p
 (he  hi )  C p (Te  Ti )
Solids & Liquids Incompressible, so v=constant
C  Cc  C p (Tables A.3 & A.4)
u2  u1  C (T2  T1 )
h2  h1  u2  u1  v( P2  P1 )
Ideal Gas h  u  Pv  u  RT
u2  u1  Cv (T2  T1 )
h2  h1  C p (T2  T1 )
Energy Rate E  Q  W (rate  in  out )
 E2  E1  1Q2  1W2 (change  in  out )

First-Law Analysis for Control Volume

Formula Units
Volume Flow Rate V   VdA  AV (using average velocity)
Mass Flow Rate V kg / s
m   VdA   AV  A (using average values)
v
Power W
W  mC p T W  mCv T m V
v
Flow Work Rate W flow  PV  mPv
Flow Direction From higher P to lower P unless significant KE or PE
 Total Enthalpy htot  h  1 V 2  gZ
2
Instantaneous Process
 Continuity mC .V .   mi   me
Equation
 Energy EC.V .  QC.V .  WC.V .   mi htot i   me htot e  First Law
Equation
 Q   mi (hi  1 V 2  gZ i ) 
2
dE
dt

  me he  1 V 2  gZ e  W
2 
Steady State Process A steady-state has no storage effects, with all properties constant with time
 No Storage mC .V .  0, EC .V .  0
 Continuity
Equation
m  m
i e (in = out)

 Energy QC .V .   mi htot i  WC .V .   me htot e (in = out)  First Law

Equation

 Q   mi (hi  1 V 2  gZ i )  W   me he  1 V 2  gZ e
2 2 
 Specific Heat QC .V . kJ / kg
Transfer q
m
 Specific Work W kJ / kg
w  C .V .
m
 SS Single Flow q  htot i  w  htot e (in = out)
Eq.
Transient Process Change in mass (storage) such as filling or emptying of a container.
  Continuity m2  m1   mi   me
Equation
 Energy E2  E1  QC.V  WC.V .   mi htot i   me htot e
Equation
  
E2  E1  m2 u2  1 V22  gZ 2  m1 u1  1 V12  gZ1
2 2 
 QC .V  m h i tot i
  2  2 
  me htot e  m2 u2  1 V22  gZ 2  m1 u1  1 V22  gZ1   WC .V .
 C .V .

The Second Law of Thermodynamics

Formula Units
All W , Q can also be rates W , Q
Heat Engine WHE  QH  QL
 Thermal WHE Q
efficiency
 HE   1 L
QH QH
 Carnot Cycle QL T
Thermal  1   1 L
QH TH
 Real Heat WHE T
Engine
 HE   Carnot HE  1  L
QH TH
Heat Pump WHP  QH  QL
 Coefficient of QH QH
 
 HP 
Performance WHP QH  QL
 Carnot Cycle QH TH
 
 HP 
QH  QL TH  TL
 Real Heat QH TH
Pump  HP    Carnot HP 
WHP TH  TL
Refrigerator WREF  QH  QL
 Coefficient of QL QL
Performance
 REF  
WREF QH  QL
 Carnot Cycle QL TL
 
QH  QL TH  TL
 Real QL TL
Refrigerator
 REF    Carnot REF 
WREF TH  TL
Absolute Temperature TL QL

TH QH
Entropy
Formula Units
Inequality of Clausis Q
 T
0
Entropy  Q  kJ / kgK
dS   
 T rev
Change of Entropy  Q 
2 kJ / kgK
S 2  S1    
1
T  rev
Specific Entropy s  (1  x)s f  xsg kJ / kgK
s  s f  xs fg
Entropy Change
 Carnot Cycle 1
2
Q
Isothermal Heat Transfer: S 2  S1  
TH 1
Q  1 2
TH
 Q 
Reversible Adiabatic (Isentropic Process): dS   
 T rev
 Q 
4
3 Q4
Reversible Isothermal Process: S4  S3   
3
 
T rev TL
Reversible Adiabatic (Isentropic Process): Entropy decrease in
process 3-4 = the entropy increase in process 1-2.
 Reversible Heat- 1  Q 
2
1
2
q h
Transfer Process s2  s1  s fg        Q  1 2  fg
m 1  T rev mT 1 T T
Gibbs Equations Tds  du  Pdv
Tds  dh  vdP
Entropy Generation Q
dS    S gen
T
Wirr  PdV  T Sgen
2 2
Q
S 2  S1   dS    1 S 2 gen
1
T1
Entropy Balance Equation Entropy  in  out  gen
Principle of the Increase of dSnet  dSc.m.  dSsurr    S gen  0
Entropy
Entropy Change
 Solids & Liquids T2
s2  s1  c ln
T1
Reversible Process: ds gen  0
Adiabatic Process: dq  0
  Ideal Gas 2
dT v
Constant Volume: s2  s1  Cv0 
1
T
 R ln 2
v1
2
dT P
Constant Pressure: s2  s1  Cp0
1
T 
 R ln 2
P1
T
Constant Specific Heat: s2  s1  Cv0 ln 2  R ln 2
v
T1 v1
T P
s2  s1  Cp0 ln 2  R ln 2
T1 P1
Standard Entropy T
C p0 kJ / kgK
sT0   dT
T0
T

s2  s1   sT0 2  sT01   R ln
Change in Standard P2 kJ / kgK
Entropy P1
Ideal Gas Undergoing an T2 P2
Isentropic Process
s2  s1  0  Cp0 ln  R ln
T1 P1
R
T  P  Cp 0
 2  2 
T1  P1 
R C p 0  Cv 0 k  1
but   ,
C p0 C p0 k
C p0
k = ratio of specific heats
Cv 0
k 1 k
T v  P2  v1 
 2  1  ,  
T1  v2  P1  v2 
Special case of polytropic process where k = n: Pv  const
k

Reversible Polytropic PV n  const  PV

1 1  PV
n
2 2
n

Process for Ideal Gas n n 1 n 1

P V  T2  P2  n
V 
 2  1  ,    1 
P1  V2  T1  P1   V2 

 Work 2
dV PV
2
 PV mR (T2  T1 )
1W2   PdV  const   2 2 1 1
1 1
V n
1 n 1 n
 Values for n Isobaric process: n  0, P  const
Isothermal Process: n  1, T  const
Isentropic Process: n  k , s  const
Isochronic Process: n  , v  const
Second-Law Analysis for Control Volume
Formula Units
nd
2 Law Expressed as a dSc.m. Q
Change of Entropy    S gen
dt T
Entropy Balance Equation rate of change  in  out  generation
dSC .V . Q
   mi si   me se   C .V .  S gen
dt T

where SC.V .   sdV  mc.v. s  mA sA  mB sB  ...


and S gen   sgen dV  S gen. A  S gen.B  ...
Steady State Process dSC .V .
0
dt
QC .V .
 m s  m s  
e e i i
C .V . T
 S gen

 Continuity equation QC .V .
mi  me  m  m( se  si )    S gen
C .V . T

 Adiabatic process se  si  s gen  si

Transient Process d Q
 ms C.V .   mi si   me se   C.V .  S gen
dt T
t
Q
  m2 s2  m1s1 C .V .   mi si   me se   C .V . dt  1 S 2 gen
0
T
Reversible Steady State Process
If Process Reversible & se  si
Adiabatic e
he  hi   vdP
i

Vi 2  Ve 2
w   hi  he    g (Z i  Z e )
2
V 2  Ve 2
e
   vdP  i  g (Zi  Z e )
i
2
If Process is Reversible 1 Q
and Isothermal m  se  si   
T C .V .
QC .V .  C .V .
T
QC .V .
or T  se  si   q
m
e
 T  se  si    he  hi    vdP
i
 Incompressible Fluid Ve2  Vi 2
v  Pe  Pi    g  Z e  Z i   0  Bernoulli Eq.
2
Reversible Polytrophic e

Process w    vdP and Pv n  const  C n

for Ideal Gas i
e e
dP
w    vdP  C  1
n
i i P
n nR
  Peve  Pv
i i Te  Ti 
n 1 n 1
Isothermal Process (n=1) e e
dP Pe
w    vdP  C    Pv
i i ln
i i
P Pi
Principle of the Increase of dS net dSC .V . dS surr
Entropy     S gen  0
dt dt dt
Efficiency
Turbine wa hi  he
  Turbine work is out
ws hi  hes
Compressor ws hi  hes
(Pump)   Compressor work is in
wa hi  he
Cooled Compressor wT

w
Nozzle 1 V2
 2 2
e
Kinetic energy is out
1 V
2 es
Note:

°F = (°C x 9/5) + 32

°C = (°F - 32) x (5/9)

°K = °C + 273

Q = mC∆T thermal energy = mass x specific heat x change in T

Q = mHf thermal energy = mass x heat of fusion

Q = mHv thermal energy = mass x heat of vaporization

∆L = αLi∆T change in length = coefficient of expansion x initial length x change in T

∆V = βVi∆T change in volume = coefficient of expansion x initial volume x change in T

∆U = Q – W internal energy = heat energy - work

Plausible Physical Name State Variables P V T ΔEth Q Ws W
Situations
Insulated Add weight Adiabatic PVγ = Const; nCvΔT > 0 -nCvΔT < 0 nCvΔT > 0
sleeve to or push compression TVγ-1 = Const Up Down Up
0
or rapid down on
process piston
Insulated Remove Adiabatic PVγ = Const; nCvΔT < 0 -nCvΔT > 0 nCvΔT < 0
sleeve or weight from expansion TVγ-1 = Const Down Up Down
0
rapid or pull up
process on piston
Heat gas Locked Isochoric V fixed; nCvΔT > nCvΔT 0 0
piston or PαT 0 >0
Up Fixed Up
rigid
container
Cool gas Locked Isochoric V fixed; nCvΔT < nCvΔT 0 0
piston or PαT 0 <0
Down Fixed Down
rigid
container
Heat gas Piston free Isobaric P fixed; nCvΔT > nCpΔT PΔV > 0 -PΔV < 0
to move, expansion VαT 0 >0
Fixed Up Up
load
unchanged
Cool gas Piston free Isobaric P fixed; nCvΔT < nCpΔT PΔV < 0 -PΔV > 0
to move, compression VαT 0 <0
Fixed Down Down
load
unchanged
Immerse Add weight Isothermal T fixed at nCvΔT = nRT*ln( nRT*ln(Vf/ -nRT
gas in to piston compression temperature of Up Down Fixed
0 Vf/Vi) Vi) < 0 *ln(Vf/Vi)
large bath bath, <0 >0
PV = Const
Immerse Remove Isothermal T fixed at nCvΔT = nRT*ln( nRT*ln(Vf/ -nRT*
gas in weight from expansion temperature of Down Up Fixed
0 Vf/Vi) Vi) > 0 ln(Vf/Vi) <
large bath piston bath, >0 0
PV = Const
Unknown Unknown No Name PV/T = nCvΔT ΔEth + ∫PdV = ± -∫PdV = ±
Const ? ? ?
Ws area under area under
curve in PV curve in PV
diagram diagram