Thermodynamics

MTX 220 Formules

Chapter 2 – Concepts & Definitions

Formule Units

Pressure Pa
F
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 
kg / m3
m 1
ρ= ρ=
V v

Static Pressure Variation Pa

∆P = ρ gh ↑= − , ↓ = +

Absolute Temperature
T ( K ) = T (°C ) + 273.15

Chapter 3 – Properties of a Pure Substance

Formule Units
Quality (vapour mass fraction)
mvapor
x=
mtot

(Liquid mass fraction)

mliquid
1− x =
mtot

Specific Volume
m3 / kg
v = v f + xv fg

Average Specific Volume (only two phase

m3 / kg
v = (1 − x )v f + xvg
mixture)

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 = molekulêre mass

kJ / kg K
R M
R=
M

Compressibility Factor
Pv = ZRT
Z
Reduced Properties ,
P T
Pr = Tr =
Pc Tc

Chapter 4 – Work & Heat

Formule Units
Displacement Work 2
W = ∫ Fdx = ∫ PdV
2 J
1 1

Integration 2
W = ∫ PdV = P( V2 −V1 ) J
1

Specific Work (work per unit mass)

J / kg
W
w=
m

Power (rate of work)

W&= FV = PV&= T ω W

• Velocity
V = rω rad / s

• Torque
T = Fr Nm

Polytropic Process
( n ≠ 1) PV n = Const = PV
1 1 = PV
n
2 2
n

Pv n = C

• Polytropic Exponent
ln  2 
P
P1 
n= 
ln  1 
V
 V2 

• n=1
PV = Const = PV
1 1 =P
2 V2

Polytropic Process Work

1 J
W2 =
1 2 2 − PV
(PV 1 1) n≠ 1
1− n

• n=1
 V2  J
W2 = PV
2 2 ln 
1
 V1 

Adiabatic Process
Q=0
Conduction Heat Transfer , =conductivity
W
dT k
Q&= −kA
dx

Convection Heat Transfer , =convection coefficient

W
Q&= hA∆T h

Radiation Heat Transfer

Q&= εσ A(Ts4 − Tamb
4
) W

Terminology
= heat
Q

= heat transferred during the process between state 1 and state 2

1 Q2

= rate of heat transfer

Q&

= work
W

= work done during the change from state 1 to state 2

W2
1

= rate of work = Power. 1 W=1 J/s

W&

Chapter 5 – The First Law of Thermodynamics

Formule Units
Total Energy
E = U + KE + PE → dE = dU+ d (KE +) d (PE ) J

Energy
dE = δ Q − δ W → E2 − E1 =1 Q2 −1 W2 J

Kinetic Energy
KE = 0.5mV 2
J

Potential Energy
PE = mgZ → PE2 − PE1 = mg( Z2 −Z1) J

Internal Energy
U = U liq + U vap → mu = mliq u f + mvap ug

Specific Internal Energy

u = (1 − x)u f + xu g kJ / kg
of
Saturated Steam u = u f + xu fg
(two-phase mass
average)
Total Energy
m(V22 − V12 ) J
U 2 − U1 + + mg( Z2 − Z1) = 1 Q2 −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
(two-phase mass h = h f + xh fg
average)
Specific Heat at
1 δQ  1  δU   δ u 
Constant Volume Cv =   =   = 
m  δ T v m  δ T v  δ T  v

→ (ue − ui ) = Cv (Te −Ti )

Specific Heat at
1  δQ  1 δH   δh 
Constant Pressure Cp =   =   = 
m  δ T  p m  δ T  p  δ T p

→ (he − hi ) =C p (Te −Ti )

Solids & Liquids Incompressible, so v=constant

(Tables A.3 & A.4)

C = Cc = Cp

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 = 1 Q2 − 1W2 ( change = +in −out)

Chapter 6 – First-Law Analysis for A Control Volume
Formule Units

Volume Flow Rate (using average velocity)

V&= ∫ V dA = AV

Mass Flow Rate (using average values)

kg / s
V
m&= ∫ ρVdA = ρ AV = A
v

Power
W
W&= mC
& p VT W&= mC
& v VT &
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
Equation
m&C .V . = ∑ m&i − ∑ m&e

• Energy  First Law

Equation E&C .V . = Q&C .V . − W&C .V . +∑ &
mi htot i −∑ &
me htot e

→ Q&+ ∑ m&i (hi + 1 V 2+ gZ i )=

2
dE
dt
(
+ ∑ m&e he+ 1 V 2+ gZe − W &
2 )
Steady State A steady-state has no storage effects, with all properties
constant with time
Process
• No Storage
m&C .V . = 0, E&C .V . = 0

• Continuity (in = out)

Equation
∑ m& = ∑ m&
i e
 • Energy (in = out)  First Law
Equation Q&C .V . + ∑ m & +∑m
&i htot i = WC .V .
&e htot e

(
→ Q&+ ∑ m&i (hi + 1 V 2 + gZ i ) = W&+ ∑ m&e h e+ 1 V 2+ gZ e
2 2 )
• Specific
kJ / kg
Heat Q&
Transfer q = C .V .
m&

• Specific
W&C .V . kJ / kg
Work w=
m&

• SS Single (in = out)

Flow Eq. q + htot i = w + htot e

Transient Process Change in mass (storage) such as filling or emptying of a

container.

• Continuity
Equation
m2 − m1 = ∑ mi − ∑ me

• Energy
Equation
E2 − E1 = QC V. − WC V. . +∑ mi htot i −∑ me htot e

( ) (
E2 − E1 = m2 u2 + 1 V22 + gZ2 − m1 u1 +1 V12 +gZ1
2 2 )

( ) ( )

QC .V + ∑ mi htot i = ∑ me htot e +  m2 u2 + 1 V2 2 + gZ2 − m1 u1 + 1 V2 2 + gZ1  − W
 2 2  C .V . C .V .

Chapter 7 – The Second Law of Thermodynamics

Formule Units

All can also be rates

W, Q W&, Q&
Heat Engine
WHE = QH − QL

• Thermal
WHE Q
efficiency η HE = = 1− L
QH QH

• Carnot Cycle
QL T
ηThermal = 1 − = 1− L
QH TH

• Real Heat
WHE T
Engine η HE = ≤ ηCarnot HE = 1 − L
QH TH

Heat Pump
WHP = QH − QL

• Coefficient
QH QH
of ′ =
β HP =
Performance
WHP QH − QL

• Carnot Cycle
QH TH
′ =
β HP =
QH − QL TH − TL

• Real Heat
QH TH
Pump β HP = ≤ βCarnot HP =
WHP TH − TL

Refrigerator
WREF = QH − QL

• Coefficient
QL QL
of β REF = =
Performance
WREF QH − QL

• Carnot Cycle
QL TL
β= =
QH − QL TH − TL
 • Real
QL TL
Refrigerator β REF = ≤ βCarnot REF =
WREF TH − TL

Absolute Temp.
TL QL
=
TH QH

Chapter 8 – Entropy
Formule Units

Inequality of Clausis
δQ
∫ T
Ñ ≤0

Entropy
 δQ  kJ / kgK
dS ≡  
 T rev

Change of Entropy
 δQ 
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 Isothermal Heat Transfer:
2
1 Q
S 2 − S1 = ∫
TH 1
δQ = 1 2
TH

Reversible Adiabatic (Isentropic Process):

 δQ 
dS =  
 T rev

Reversible Isothermal Process:

 δQ 
4
3 Q4
S 4 − S3 = ∫   =
3
T  rev TL

Reversible Adiabatic (Isentropic Process): Entropy

decrease in

process 3-4 = the entropy increase

in process 1-2.

• Reversible
1  δQ 
2 2
1 q h
Heat-Transfer
Process
s2 − s1 = s fg = ∫   = ∫
m 1  T  rev mT 1
δ Q = 1 2 = fg
T T

Gibbs Equations
Tds = du + Pdv

Tds = dh − vdP

Entropy Generation
δQ
dS = + δ Sgen
T

δ Wirr = PdV − T δ Sgen

2 2
δQ
S 2 − S1 = ∫ dS = ∫ + 1 S2 gen
1 1
T

Entropy Balance Eq.

VEntropy = + in − out + gen
Principle of the
Increase of Entropy
dSnet = dSc. m. + dSsurr =∑ δ S gen ≥0

Entropy Change

• Solids &
Liquids T2
s2 − s1 = c ln
T1

Reversible Process:
dsgen = 0

Adiabatic Process:
dq = 0

• Ideal Gas Constant Volume:

2
dT v
s2 − s1 = ∫ Cv0 + R ln 2
T v1
1

Constant Pressure:
2
dT P
s2 − s1 = ∫ Cp0 − R ln 2
T P1
1

Constant Specific Heat:

T2 v2
s2 − s1 = Cv0 ln + R ln
T1 v1

T2 P2
s2 − s1 = Cp0 ln − R ln
T1 P1

Standard Entropy T
C p0 kJ / kgK
s =∫
0
T dT
T0
T

Change in Standard
kJ / kgK
Entropy s2 − s1 = ( sT02 − sT01 ) − R ln P2
P1
Ideal Gas Undergoing
an Isentropic Process
s2 − s1 = 0 = Cp0 ln T2 − R ln P2
R

T1 P1 T P  Cp 0
→ 2 = 2 
T1  P1 

but , = ratio of
R C − Cv 0 k − 1 C p0
= p0 = k=
C p0 C p0 k Cv 0

specific heats

k −1 k
T v  P2  v 1 
⇒ 2 = 1  , = 
T1  v 2  P1  v 2 

Special case of polytropic process where k = n:

Pv k = const

Reversible Polytropic
PV n = const = PV
1 1 = PV
n n
Process for Ideal Gas 2 2

n n −1 n−1
P V  T2  P2  n
V 
→ 2 = 1  , =  = 1
P1  V2  T1  P1   V2 

• Work 2 2
dV PV − PV mR (T2 − T1 )
1W2 = ∫ PdV = const ∫ = 2 2 1 1=
1 1
V n
1− n 1− n

• Values for n Isobaric process:

Isothermal Process:

Isentropic Process:
 Isochronic Process:
n = ∞, v = const

Chapter 9 – Second-Law Analysis for a Control Volume

Formule Unit
s

2nd Law Expressed as a

dSc.m. Q&
Change of Entropy = ∑ + S&gen
dt T

Entropy Balance Eq.

rate of change = + in − out + generation

dSC .V . &
Q
→ = ∑ m&i si − ∑ m&e se + ∑ C .V . +S&gen
dt T

where
SC .V . = ∫ ρ sdV = mc.v.s = m As A + m Bs B + ...

and
S&gen = ∫ ρ s&gen dV = S&gen .A + S&
gen .B + ...

Steady State Process

dSC .V . Q&C .V . &
dt
=0 → ∑ m&e se − ∑ m&i si = ∑ C .V . T
+ Sgen

• Continuity eq.
m&i = m&e = m& Q&C .V . &
⇒ m&( se − si ) = ∑ + Sgen
C .V . T
 • Adiabatic
se = si + sgen ≥ si
process

Transient Process
d Q&
( ms ) C .V . = ∑ m&i si − ∑ m&e se + ∑ C.V . + S&gen
dt T

Q&C .V .
t
→ ( m2 s2 − m1 s1 ) C .V . = ∑ mi si − ∑ me se + ∫ T
dt + 1 S&
2 gen
0

Reversible Steady State

Process
• If Process
Reversible & se = si
Adiabatic

e
he − hi = ∫ vdP
i

Vi 2 − Ve 2
w = ( hi − he ) + + g ( Zi − Ze )
2
e
Vi 2 − Ve 2
= − ∫ vdP + + g ( Zi − Ze )
i
2

• If Process is
1 Q
Reversible and m&( se − si ) = ∑
T C .V .
Q&C .V . = C .V .
T
Isothermal

or
Q&C .V .
e

T ( se − si ) = = q → T ( se − si ) = ( he − hi ) − ∫ vdP
m& i

• Incompressible  Bernoulli Eq.

Fluid V − Vi
2 2
v ( Pe − Pi ) + e
+ g ( Ze − Z i) = 0
2
 • Reversible e
Polytropic w = − ∫ vdP and Pv n = const = C n
Process i

for Ideal Gas

e e
dP
w = − ∫ vdP = −C ∫ 1
i i P n

n nR
=− ( Pe ve − Pv
i i) = − ( Te − Ti )
n −1 n −1

• Isothermal e e
dP Pe
Process (n=1) w = − ∫ vdP = −C ∫ = − Pv
i i ln
i i
P Pi

Principle of the
dSnet dS C.V . dS surr
Increase of Entropy = + = ∑ S&gen ≥ 0
dt dt dt

Efficiency

• Turbine Turbine work is out

wa hi − he
η= =
ws hi − hes

• Compressor Compressor work is in

(Pump) ws hi − hes
η= =
wa hi − he

• Cooled
Compressor wT
η=
w

• Nozzle Kinetic energy is out

1 V2
η= 2 2
e

1 V
2 es