State Equations

Reading Problems
3-6, 3-7, 4-3 → 4-5 3-59, 3-68, 3-80
6-6
7-3, 7-4, 7-7 → 7-10 7-38, 7-98, 7-143, 7-163

The Thermodynamics of State

IDEAL GAS

The defining equation for a ideal gas is

Pv
= constant = R
T

Knowing that v = V /m

PV
= constant = R
Tm

where R is a gas constant for a particular gas (as given in C&B Tables A-1 and A-2).

An Isentropic Process for an Ideal Gas

Given:

• constant specific heats over a wide range of temperature

• ds = 0
 
∂u
• du = cv dT ≡ cv =
∂T V
 
∂h
• dh = cp dT ≡ cp =
∂T P

1
Gibb’s equation can be written as

T ds = du + P dv = cv dT + P dv = 0 (1)

where ds = 0 because we have assumed an isentropic process.

The definition of enthalpy is

h = u + Pv

Taking the derivative yields

dh = du

+P dv +vdP
≡T ds

dh = T ds + vdP ⇒ T ds = 0 = dh − vdP

cp dT − vdP = 0 (2)

Equating Eqs. (1) and (2) through the dT term gives

dP cp dv
=− (3)
P cv v

Integrating (3) from its initial state to a final state

P1 v1k = P2 v2k = constant = P v k

where

cp
k=
cv

The product of P · v k remains constant for an ideal gas when:

• specific heats are constant

2
 • the gas undergoes an isentropic process → reversible + adiabatic

Combining this result with the ideal gas equation of state

 k−1  (k−1)/k
T2 v1 P2
= =
T1 v2 P1

The isentropic process is a special case of a more general process known as a polytropic process

where → P v n = constant and n is any number.

Special Cases

n=1 P v = RT = constant ⇒ isothermal process

n=0 P v 0 = constant = P ⇒ isobaric process (constant pressure)

n=k P v k = constant ⇒ isentropic process (k = cp /cv )

n=∞ P v ∞ = constant ⇒ isochoric process (constant volume)

Relative Pressure and Relative Specific Volume

• typically we assume specific heat to be constant with respect to temperature

• but when temperature swings are significant, this assumption can lead to inaccuracies, i.e.

T (K) cp (kJ/kg · K) % difference

300 1.0057
1000 1.1417 13.5
2500 1.688 67.8

• the relative pressure and relative volume tables (C&B Table A-17), provide an accurate
way of including the temperature effects on specific heat for ideal gases during isentropic
processes

• note: the specific heat ratio term given by k = cp /cv will also be influenced by temperature

3
 • Procedure:

– given T1 , P1 and P2 for an isentropic process

– determine Pr1 at T1 from Table A-17
– calculate Pr2 , where
 
P2 Pr2
=
P1 s=const Pr1
– read T2 from Table A-17 for the calculated value of Pr2

• use a similar procedure if volume is known instead of pressure, where

 
v2 vr2
=
v1 s=const vr1

In Summary
For an ideal gas with constant cp and cv

P v = RT

u2 − u1 = cv (T2 − T1 )

h2 − h1 = cp (T2 − T1 )

There are 3 forms of a change in entropy as a function of T & v, T & P , and P & v.

T2 v2
s2 − s1 = cv ln + R ln
T1 v1
T2 P2
= cp ln − R ln
T1 P1
v2 P2
= cp ln + cv ln
v1 P1

R = cp − cv

4
A General Formulation
Steady State, Steady Flow in a Flow Channel of Arbitrary Cross-section with Work and Heat
Transfer

dĖ = Ėf inal − Ėinitial

= Ėx+dx − Ėx

where

Ė = ṁ(e + P v)

(v ∗ )2
= ṁ(u + + gz + P v)
2

From the 1st law

rate of energy rate of rate of net rate of energy

= + +
storage work heat transf er leaving the system

dECV
= dẆ − dQ̇ − dĖ (1)
dt

5
 dECV
where = 0 for steady state.
dt
Equation (1) becomes


(v ∗ )2
0 = dẆ − dQ̇ − ṁ d u + P v + + gz (2)
2

From the 2nd law

⎧ ⎫
rate of ⎪
⎨ rate of rate of ⎬⎪ rate of
entropy = entropy − entropy + entropy
⎪
⎩ ⎪
⎭
storage inf low outf low production

dSCV dQ̇
= [ṁs]x − [ṁs]x+dx − + ṖS
dt TT ER

dSCV
where = 0 for steady state.
dt

dQ̇
0 = −ṁds − + ṖS
TT ER

or

dQ̇ = TT ER ṖS − TT ER ṁds (3)

Combining (2) and (3) through dQ̇

 
(v ∗ )2
TT ER ṖS − TT ER ṁds = dẆ − ṁ d u + P v + + gz (4)
2

Equation (4) can be used for any SS-SF process.

6
Special Cases
Reversible, SS-SF Process

Reversible implies ⇒ ṖS = 0

• frictionless process

• heat transfer is allowed but must be across ΔT → 0

• which means TT ER ≈ TCV = T

Equation 4 becomes

 
dẆ (v ∗ )2
= −T ds + du + d(P v) +d + d(gz) (5)
ṁ    2
=du +P dv + vdP
   
=T ds

Therefore

 
dẆ (v ∗ )2
= vdP + d + d(gz) (6)
ṁ 2

Integrating Eq. (6) between the inlet and the outlet

 out outout
Ẇ (v ∗ )2  

= vdP +  + gz  (7)
ṁ in 2 in 
    in 
ΔKE ΔP E

but ΔKE and ΔP E are usually negligible.

If ΔKE + ΔP E = 0

 out
Ẇ
= vdP (8)
ṁ in

Equation can be used for a reversible, SS-SF flow in a liquid or a gas.

7
If we keep in mind

ρliq >> ρgas ⇒ vliq << vgas

i.e. water @ 25 ◦ C ρ = 997 kg/m3 and air @ 25 ◦ C ρ = 1.18 kg/m3

Therefore
⎛ ⎞ ⎛ ⎞
Ẇ Ẇ
⎝ ⎠ << ⎝ ⎠
ṁ ṁ
liq gas

For example: the work required to operate a pump is much less that that required to operate a
compressor.

Incompressible Substance

This is a special case of Eq. (8) where v = constant = vin − vout.

From Equation (8)

Ẇ
= vin(Pout − Pin) (9)
ṁ

The work term represents the minimum work required to pump a liquid from Pin to Pout with
negligible ΔKE and ΔP E.

Incompressible Substance and dẆ = 0

From Eq. (6)

 
(v ∗ )2
vdP + d + d(gz) = 0 (10)
2

Therefore
   
P (v ∗ )2
d +d + d(gz) = 0
ρ 2

8
  
P (v ∗ )2
d + + gz =0 (11)
ρ 2

Integrating gives

P (v ∗ )2
+ + gz = constant (12)
ρ 2

Equation (12) is Bernoulli’s equation for frictionless flow with constant density. The constant is
Bernoulli’s constant, which remains constant along a streamline for steady, frictionless, incom-
pressible flow.

Isothermal Ideal Gas, Compression/Expansion

This is a special case of Eq. (8) for an ideal gas where P v = RT

P v = constant = (P v)in = (P v)out

 out  out
Ẇ dP
= vdP = (P v)in
ṁ in in P

Therefore

 
Ẇ Pout
= Pinvin ln (13)
ṁ Pin

Isentropic Ideal Gas, Compression/Expansion

Isentropic implies a reversible and adiabatic process where s = constant. With an ideal gas,
P v k = constant and (P v k )in = (P v k )out.

Equation (8) becomes

 out  out  1/k

Ẇ (P v k )in
= vdP = dP
ṁ in in P

9
   ⎡  ⎤
Ẇ k Pout (k−1)/k
= (P v)in ⎣ − 1⎦ = cp (Tout − Tin) (14)
ṁ k−1 Pin

The right side of Eq. (14) is based on the fact that ΔKE + ΔP E = 0 and dh = du + dP v
and du = 0. Which leads to h = vdP .

Note: for the same inlet state and pressure ratio

⎛ ⎞ ⎛ ⎞
Ẇ Ẇ
⇒⎝ ⎠ <⎝ ⎠
ṁ ṁ
rev.,isothermal rev.,adiabatic

10
Review of First and Second Law of Thermodynamics

Reading Problems
2-6, 4-1, 4-2 4-27, 4-40, 4-41
5-1 → 5-3
6-1, 6-2, 7-13

Definitions
SYSTEM:

• any specified collection of matter under study.

• all systems possess properties like mass, energy, entropy, volume, pressure, tempera-
ture, etc.

WORK & HEAT TRANSFER:

• thermodynamics deals with these properties of matter as a system interacts with its
surroundings through work and heat transfer
• work and heat transfer are NOT properties → they are the forms that energy takes to
cross the system boundary

1
First Law of Thermodynamics
Control Mass (Closed System)

CONSERVATION OF ENERGY:
• the energy content of an isolated system is constant

energy entering − energy leaving = change of energy within the system

Example: A Gas Compressor

Performing a 1st law energy balance:

⎧ ⎫ ⎧ ⎫
⎪ Initial ⎪   ⎪
⎨ ⎬ + Energy gain W1−2 ⎨ F inal ⎪
⎬
Energy = Energy
⎪
⎩ ⎭ −
⎪ Energy loss Q1−2 ⎪
⎩ ⎪
⎭
E1 E2

E1 + W1−2 − Q1−2 = E2

2
Control Volume Analysis (Open System)

CONSERVATION OF MASS:

⎧ ⎫ ⎧ ⎫ ⎧ ⎫
⎪
⎨ rate of increase ⎪
⎬ ⎪
⎨ net rate of ⎪
⎬ ⎪
⎨ net rate of ⎪
⎬
⎪
of mass within
⎪
= ⎪ mass f low ⎪
− ⎪ mass f low ⎪
⎩ ⎭ ⎩ ⎭ ⎩ ⎭
the CV IN OU T

d
(mCV ) = ṁIN − ṁOUT
dt

where:

mCV = ρ dV
V

ṁIN = (ρ v ∗ A)IN

ṁOUT = (ρ v ∗ A)OUT

with v ∗ = average velocity

3
CONSERVATION OF ENERGY:

The 1st law states:

ECV (t) + ΔQ + ΔWshaf t + (ΔEIN − ΔEOUT )+

(ΔWIN − ΔWOUT ) = ECV (t + Δt) (1)

where:

ΔEIN = eIN ΔmIN

ΔEOUT = eOUT ΔmOUT

ΔW = flow work
E (v ∗ )2
e = = u
 + + gz
m 2  
internal   potential
kinetic

4
Second Law of Thermodynamics
Fundamentals

1. Like mass and energy, every system has entropy.

Entropy is a measure of the degree of microscopic disorder and represents our uncertainty
about the microscopic state.

2. Unlike mass and energy, entropy can be produced but it can never be destroyed. That is, the
entropy of a system plus its surroundings (i.e. an isolated system) can never decrease (2nd
law).

Pm = m2 − m1 = 0 (conservation of mass)

PE = E2 − E1 = 0 (conservation of energy) → 1st law

PS = S2 − S1 ≥ 0 → 2nd law

The second law states:

(ΔS)system + (ΔS)surr. ≥ 0

where Δ ≡ f inal − initial

Example: A freezing process

5
3. Reference: In a prefect crystal of a pure substance at T = 0 K, the molecules are com-
pletely motionless and are stacked precisely in accordance with the crystal structure. Since
entropy is a measure of microscopic disorder, then in this case S = 0. That is, there is no
uncertainty about the microscopic state.

4. Relationship to Work: For a given system, an increase in the microscopic disorder (that is
an increase in entropy) results in a loss of ability to do useful work.

5. Heat: Energy transfer as heat takes place as work at the microscopic level but in a random,
disorganized way. This type of energy transfer carries with it some chaos and thus results in
entropy flow in or out of the system.

6. Work: Energy transfer by work is microscopically organized and therefore entropy-free.

Example: Slow adiabatic compression of a gas

A process 1 → 2 is said to be reversible if the reverse process 2 → 1 restores the system

to its original state without leaving any change in either the system or its surroundings.
→ idealization where S2 = S1 ⇒ PS = 0

T2 > T1 ⇒ increased microscopic disorder

V2 < V1 ⇒ reduced uncertainty about the whereabouts of molecules

   + Adiabatic
Reversible  P rocess ⇒ Isentropic
 
P rocess

PS =0 Q=0 S1 =S2

The 2nd law states:

PS = (ΔS)system + (ΔS)surr ≥ 0

6
 where:

>0 irreversible (real world)

=0 reversible (frictionless, perfectly elastic, inviscid fluid)

But does:

Isentropic P rocess ⇒ Reversible + Adiabatic

NOT ALWAYS - the entropy increase of a substance during a process as a result of irre-
versibilities may be offset by a decrease in entropy as a result of heat losses.

General Derivation of Gibb’s Equation

From a 1st law energy balance when KE and PE are neglected

Energy Input = Energy Output + Increase in Energy Storage

dQ = dW + dU
 (1)

amount dif f erential

We know that the differential form of entropy is

dQ
dS = (2) dW = P dV (3)
T

Combining Eqs. 1, 2 and 3

dU P dV du P dv
dS = + ⇒ ds = +
T T  T  T 
per unit mass

7
Second Law Analysis for a Control Mass

• control mass is uniformly at TT ER at all times

• control mass has a fixed size (V = constant)

From Gibb’s equation

0
TT ER dS = dU + P dV

From the 1st law

dU = dQ

Therefore for a reversible process

dQ
dS =
TT ER

We integrate to give

Q1−2
S2 − S1 =
TT ER

and for a non-reversible process

dQ
dS = + dPS
TT ER

We integrate to give

Q1−2
S2 − S1 = + PS1−2
TT ER

8
Second Law Analysis for a Control Volume

where:
FR - fluid reservoir
TER - thermal energy reservoir
MER - mechanical energy reservoir

9
For the isolated system

(ΔS)sys + (ΔS)sur = PS1−2 ≥ 0

QA
1−2 QB
1−2
ΔSCV − sA mA
1−2 + sB m1−2 −
B
+ = PS1−2
TTAER TTBER

or as a rate equation

  ⎛ ⎞ ⎛ ⎞
dS Q̇ Q̇
= ⎝sṁ + ⎠ − ⎝sṁ + ⎠ + ṖS
dt CV TT ER TT ER
IN OUT

This can be thought of as

accumulation = IN − OU T + generation

10
Availability

Reading Problems
8-1 → 8-8 8-29, 8-34, 8-50, 8-53, 8-63
8-71, 8-93, 8-103, 8-118, 8-137

Second Law Analysis of Systems

AVAILABILITY:

• the theoretical maximum amount of work that can be obtained from a system at a given
state P1 and T1 when interacting with a reference atmosphere at the constant pressure
and temperature P0 and T0 .
• describes the work potential of a given system.
• also referred to as “exergy”.

The following observations can be made about availability:

1. Availability is a property - since any quantity that is fixed when the state is fixed is a prop-
erty. For a system at state 1 and specified values of the atmosphere of T0 and P0 , the
maximum useful work that can be produced is fixed.

2. Availability is a composite property - since its value depends upon an external datum - the
temperature and pressure of the dead state.

3. Availability of a system is 0 at its dead state when T = T0 and P = P0 . It is not possible

for the system to interact with the reference atmosphere at the dead state. The system is said
to be in thermodynamic equilibrium with its surroundings.

4. Unless otherwise stated, assume the dead state to be:

P0 = 1 atm

T0 = 25◦ C

1
 5. The maximum work is obtained through a reversible process to the dead state.

REV
 ERSIBLE
 W ORK = U
 SEF U L
 W ORK + IRREV ERSIBILIT
 Y
Wrev Wusef ul I

Control Mass Analysis

• we know

Wrev = Wusef ul + I

but as shown in the figure, the actual work of the process is divided into two components

Wactual = Wusef ul + Wsur

• where Wsur is the part of the work done against the surroundings to displace the ambient
air

Wsur = P0 (V2 − V1 ) = −P0 (V1 − V2 )

2
 • this is unavoidable → this is not useful work. Nothing is gained by pushing the atmosphere
away.

To find Wactual , from the 1st law

E1 − Q − Wactual = E2 → Q = E1 − E2 − Wactual

From the 2nd law

Ps = ΔSsystem + ΔSsur ≥ 0
Q
= S2 − S1 +
T0

But from the 1st law balance we know

Q E1 − E2 − Wactual
=
T0 T0

and when we combine this with the 2nd law

E1 − E2 − Wactual
Ps = S2 − S1 +
T0

which leads to

Wactual = (E1 − E2 ) + T0 (S2 − S1 ) − T0 Ps

or by reversing the order of S2 and S1

Wactual = (E1 − E2 ) − T0 (S1 − S2 ) − T0 Ps

But we also know that

Wusef ul = Wactual − Wsur

3
therefore

Wusef ul = (E1 − E2 ) − T0 (S1 − S2 ) + P0 (V1 − V2 ) −T0 Ps

  
−Wsur

and

Wrev = Wusef ul + I

= Wactual − Wsur + I

where

I = T0 PS

Therefore

Wrev = (E1 − E2 ) − T0 (S1 − S2 ) + P0 (V1 − V2 )

In summary

Wactual = (E1 − E2 ) − T0 (S1 − S2 ) − T0 Ps

Wusef ul = (E1 − E2 ) − T0 (S1 − S2 ) + P0 (V1 − V2 ) − T0 Ps

X = Φ = Wrev = (E1 − E2 ) − T0 (S1 − S2 ) + P0 (V1 − V2 )

Define

X = Φ = CON T ROL M ASS AV AILABILIT Y

= Wrev (in going to the dead state)

= (E − E0 ) − T0 (S − S0 ) + P0 (V − V0 )

where the specific availability is defined as

Φ
φ=
m

4
What is the availability in going from one state to another?

The reversible work is

Wrev = (Φ1 − Φ0 ) − (Φ2 − Φ0 ) = Φ1 − Φ2

but we also know

Φ1 = (E1 − E0 ) − T0 (S1 − S0 ) + P0 (V1 − V0 )

Φ2 = (E2 − E0 ) − T0 (S2 − S0 ) + P0 (V2 − V0 )

Φ1 − Φ2 = (E1 − E2 ) − T0 (S1 − S2 ) + P0 (V1 − V2 )

The availability destroyed is

Xdes = I = Wrev − Wusef ul = T0 Ps = T0 Sgen

This can be referred to as: irreversibilities, availability destruction or loss of availability.

Control Volume Analysis

Consider a steady state, steady flow (SS-SF) process

From the 1st law

 
dEcv 0 (v ∗ )2 (v ∗ )2
 = −Ẇactual − Q̇ + ṁ(h + + gz) − ṁ(h + + gz) (1)
dt 2 in 2 out

From the 2nd law

⎛ ⎞ ⎛ ⎞
dScv 0 0
Q̇ Q̇
 = ⎝ṁs + ⎠ − ⎝ṁs + ⎠ + Ṗs (2)
dt TT ER T0
in out

5
Combining (1) and (2) through the Q̇ term, leads to the actual work output of the turbine, given as

     
(v ∗ )2 (v ∗ )2
Ẇactual = ṁ h + + gz − T0 s − ṁ h + + gz − T0 s − T0 ṖS
2 in 2 out

= ṁ [−T0 Δs + Δh + ΔKE + ΔP E] − (T0 Ṗs ) (3)

Ẇactual is the actual work output of the turbine.

The specific flow availability, ψ, is given as

 
(v ∗ )2 ∗ 0 2
(v
0 )
ψ = −T0 (s − s0 ) + (h − h0 ) + − + g(z − z0
0 ) (4)
2 2

For a steady state, steady flow process where we assume KE=PE=0

Ẇrev = (ṁψ)in − (ṁψ)out (5)

Ẋdes = I˙ = Ẇrev − Ẇactual = T0 Ṗs = T0 Ṡgen (6)

ψ = (h − h0 ) − T0 (s − s0 ) (7)

6
The General Exergy Equation

From the 1st law

dEcv
= Ẇin − Ẇout − Q̇0 + Q̇1 − Q̇2 + [ṁ(e + P v)]in − [ṁ(e + P v)]out (1)
dt

From the 2nd law

⎛ ⎞ ⎛ ⎞
dScv Q̇0 Q̇1 Q̇2
= ⎝ṁs − + ⎠ − ⎝ṁs + ⎠ + Ṗs (2)
dt T0 T1 T2
in out

Multiply (2) by T0 and subtract from (1) to eliminate Q0 , which leads to the generalized exergy
equation

d
(E − T0 S)CV = Ẇin − Ẇout + [ṁ(e + P v − T0 s)]in
dt
⎛ ⎞
T0 Q̇1
[ṁ(e + P v − T0 s)]out + ⎝Q̇1 − ⎠
T1
in
⎛ ⎞
T0 Q̇2
− ⎝Q̇2 − ⎠ − T0 ṖS (3)
T2
out

7
We can rewrite Eq. (3) in a generalized form by introducing the definitions of Φ and ψ.
  
dΦ dVCV T0
= P0 + Ẇ + ṁψ + Q̇ 1 −
dt dt TT ER in
  
T0
− Ẇ + ṁψ + Q̇ 1 − − I˙
TT ER out

where

I˙ = Ẋdes = T0 Ṗs

= exergy destruction rate

Φ = [(E − E0 ) + P0 (V − V0 ) − T0 (S − S0 )]

= non − f low exergy

1 
ψ = (h − h0 ) − T0 (s − s0 ) + (v ∗ )2 − (v0∗ )2 + g(z − z0 )
2
= f low exergy
 
dVCV
Ẇusef ul = (Ẇ − Ẇ ) − P0
 in  out dt
Ẇactual   
Wsur

Aside: The left side of the above equation is

dΦ dE + P0 dV − T0 dS
=
dt dt

but the left side of Eq. (3) does not contain the term P0 dV . Therefore, we must add a term P0 dV
to both the left and right side of the above equation in order to preserve a balance. Hence the term

dV
P0
dt

appears on the right side of the above equation to preserve this balance, while the left side is

dΦ (dE + P0 dV − T0 dS)
=
dt dt

8
Efficiency and Effectiveness

1. First law efficiency (thermal efficiency)

net work output Wnet

η= =
gross heat input Qin

Carnot cycle

QH − QL TL
η= =1−
QH TH

2. Second Law Efficiency (effectiveness)

net work output net work output

η2nd = =
maximum reversible work availability

Ẇ /ṁ
Turbine → η2nd =
ψe − ψi

ψe − ψi
Compressor → η2nd =
Ẇ /ṁ

Ẇ /ṁ
Heat Source → η2nd = 
T0
Q̇/ṁ 1 −
TT ER
3. Isentropic efficiency (process efficiency)

(a) adiabatic turbine efficiency

work of actual adiabatic expansion Wact
ηT = =
work of reversible adiabatic expansion WS

(b) adiabatic compressor efficiency

work of reversible adiabatic compression WS
ηC = =
work of actual adiabatic compression Wact

9
Carnot Cycle

Reading Problems
6-7, 6-8, 6-10, 9-2, 10-1

• an ideal theoretical cycle that is the most efficient conceivable

• based on a fully reversible heat engine - it does not include any of the irreversibilities asso-
ciated with friction, viscous flow, etc.

• in practice the thermal efficiency of real world heat engines are about half that of the ideal,
Carnot cycle

Process State Points Description

Pump 1→2 isentropic compression from TL → TH

to return vapour to a liquid state
Heat Supply 2→3 heat is supplied at constant
temperature and pressure
Work Output 3→4 the vapour expands isentropically
from the high pressure and temperature
to the low pressure
Condenser 4→1 the vapour which is wet at 4 has to be
cooled to state point 1

1
Cycle Efficiency

• defined as the net work output divided by the gross heat supplied

Wnet
η =
QH
QH − QL
=
QH
TL
= 1−
TH

From the figure the gross heat supplied is

QH = area(s1 → s4 → 3 → 2 → s1 ) = TH (s4 − s1 )

The net work output is

QH − QL = area(1 → 4 → 3 → 2) = (TH − TL )(s4 − s1 )

Therefore the Carnot efficiency is

(TH − TL )(s4 − s1 ) TL
η= =1−
TH (s4 − s1 ) TH

2
Practical Problems

• at state point 1 the steam is wet at TL and it is difficult to pump water/steam (two phase) to
state point 2

• the pump can be sized smaller if the fluid is 100% liquid water

• the pump is smaller, cheaper and more efficient

• can we devise a Carnot cycle to operate outside the wet vapour region

– between state points 2 and 3 the vapour must be isothermal and at different pressures -
this is difficult to achieve
– the high temperature and pressure at 2 and 3 present metallurgical limitations

The net effect is that the Carnot cycle is not feasible for steam power plants.

3
Rankine Cycle

Reading Problems
10-2 → 10-7 10-16, 10-34, 10-37, 10-44, 10-47, 10-59

Definitions
• working fluid is alternately vaporized and condensed as it recirculates in a closed cycle

• water is typically used as the working fluid because of its low cost and relatively large value
of enthalpy of vaporization

• the standard vapour cycle that excludes internal irreversibilities is called the Ideal Rankine
Cycle

• the condensation process is allowed to proceed to completion between

state points 4 → 1

– provides a saturated liquid at 1

• the water at state point 1 can be conveniently pumped to the boiler pressure at state point 2

• but the water is not at the saturation temperature corresponding to the boiler pressure

• heat must be added to change the water at 2 to saturated water at ‘a’

• when heat is added at non-constant temperature (between 2 − a), the cycle efficiency will
decrease

1
Analyze the Process

Assume steady flow, KE = P E = 0.

From a 1st law balance, we know

energy in = energy out

Device 1st Law Balance

Boiler h2 + qH = h3 ⇒ qH = h3 − h2 (in)

Turbine h3 = h4 + wT ⇒ wT = h3 − h4 (out)

Condenser h4 = h1 + qL ⇒ qL = h4 − h1 (out)

Pump h1 + wP = h2 ⇒ wP = h2 − h1 (in)

The net work output is given as

wT − wp = (h3 − h4 ) − (h2 − h1 )

= (h3 − h4 ) + (h1 − h2 )

The net heat supplied to the boiler is

qH = (h3 − h2 )

The Rankine efficiency is

net work output

ηR =
heat supplied to the boiler
(h3 − h4 ) + (h1 − h2 )
=
(h3 − h2 )

2
If we consider the fluid to be incompressible

(h2 − h1 ) = v(P2 − P1 )

Since the actual process is irreversible, an isentropic efficiency can be defined such that
actual work
Expansion process ⇒ Isentropic efficiency =
isentropic work

isentropic work
Compression process ⇒ Isentropic efficiency =
actual work
Both isentropic efficiencies will have a numerical value between 0 and 1.

Effects of Boiler and Condenser Pressure

We know the efficiency is proportional to

TL
η ∝1−
TH

The question is → how do we increase efficiency ⇒ TL ↓ and/or TH ↑.

1. INCREASED BOILER PRESSURE:

• an increase in boiler pressure results in a higher TH for the same TL , therefore η ↑.

• but 4 has a lower quality than 4
– wetter steam at the turbine exhaust

3
 – results in cavitation of the turbine blades
– η ↓ plus ↑ maintenance
• quality should be > 80% at the turbine exhaust

2. LOWER TL :

• we are generally limited by the T ER (lake, river, etc.)

eg. lake @ 15 ◦ C + ΔT
 =10 ◦ C = 25 ◦ C
resistance to HT

⇒ Psat = 3.2 kP a.
• this is why we have a condenser
– the pressure at the exit of the turbine can be less than atmospheric pressure
– the closed loop of the condenser allows us to use treated water on the cycle side
– but if the pressure is less that atmospheric pressure, air can leak into the condenser,
preventing condensation

3. INCREASED TH BY ADDING SUPERHEAT:

• the average temperature at which heat is supplied in the boiler can be increased by
superheating the steam
– dry saturated steam from the boiler is passed through a second bank of smaller
bore tubes within the boiler until the steam reaches the required temperature

The advantage is
Wnet ↑
η= overall ↑
QH ↑

The value of T H , the mean temperature at which heat is added, increases, while
TL remains constant. Therefore the efficiency increases.
– the quality of the turbine exhaust increases, hopefully where x > 0.9
– with sufficient superheating the turbine exhaust can fall in the superheated region.

4
Rankine Cycle with Reheat
• the wetness at the exhaust of the turbine should be no greater that 10% - this can result in
physical erosion of the turbine blades
• but high boiler pressures are required for high efficiency - tends to lead to a high wetness
ratio
• to improve the exhaust steam conditions, the steam can be reheated with the expansion car-
ried out in two steps

High Pressure Low Pressure

T Turbine Turbine
Q RH Steam
Generator WT
QH Q RH
QH

QL
Condenser

s Pump
WP

• the temperature of the steam entering the turbine is limited by metallurgical constraints
• modern boilers can handle up to 30 M P a and a maximum temperature of
Tmax ≈ 650 ◦ C.
• newer materials, such as ceramic blades can handle temperatures up to 750 ◦ C.

5
Rankine Cycle with Regeneration
• Carnot cycle has efficiency: η = 1 − TL /TH

– add QH at as high a TH as possible

– reject QL at as low a TL as possible

• the Rankine cycle can be used with a Feedwater Heater to heat the high pressure sub-cooled
water at the pump exit to the saturation temperature

– most of the heat addition (QH ) is done at high temperature

Feedwater Heaters

There are two different types of feedwater heaters

1. OPEN FWH: the streams mix → high temperature steam with low temperature water at
constant pressure

2. CLOSED FWH: a heat exchanger is used to transfer heat between the two streams but the
streams do not mix. The two streams can be maintained at different pressures.

6
1. OPEN FWH:

• working fluid passes isentropically through the turbine stages and pumps
• steam enters the first stage turbine at state 1 and expands to state 2 - where a fraction
of the total flow is bled off into an open feedwater heater at P2
• the rest of the steam expands into the second stage turbine at state point 3 - this portion
of the fluid is condensed and pumped as a saturated liquid to the FWH at P2
• a single mixed stream exists the FWH at state point 6

Analysis:

• we must determine the mass flow rates through each of the components.
By performing an mass balance over the turbine

ṁ6 + ṁ7 = ṁ5 (1)

If we normalize Eq. (1) with respect the total mass flow rate ṁ1
ṁ6 ṁ7
+ =1 (2)
ṁ5 ṁ5
Let the flow at state point 2 be
ṁ6
y=
ṁ5
Therefore
ṁ7
=1−y (3)
ṁ5
Assuming no heat loss at the FWH, establish an energy balance across the FWH

yh6 + (1 − y)h2 = 1 · h3

h3 − h2 ṁ6
y= =
h6 − h2 ṁ5

and
ṁ7
1−y =
ṁ5

7
2. CLOSED FWH:

• two variations exist

(a) pump the condensate back to the high pressure line

(b) – a steam trap is inserted in the condensed steam line that allows only liquid to
pass
– liquid is passed to a low pressure region such as the condenser or a low pres-
sure heater

• the incoming feedwater does not mix with the extracted steam
– both streams flow separately through the heater
– the two streams can have different pressures

8
Other Topics

“IDEAL” RANKINE CYCLE:

• too expensive to build

• requires multiple reheat and regeneration cycles
• approaches Carnot efficiency

TOPPING CYCLE (BINARY CYCLE):

• involves two Rankine cycles running in tandem with different working fluids such as
mercury and water
• why:
– typically a boiler will supply energy at 1300 − 1400 ◦ C
– but Tcritical for water is 374.14 ◦ C
∗ most energy is absorbed below this temperature
∗ high ΔT between the boiler source and the water leads to a major source of
irreversibilities
– Tcritical for mercury is about 1500 ◦ C
∗ no need for superheating
– combine the large enthalpy of evaporation of water at low temperatures with the
advantages of mercury at high temperatures
– in addition, the mercury dome leads to a high quality at the exit of the turbine

9
Refrigeration Cycle

Reading Problems
11-1 → 11-7, 11-9 11-11, 11-44, 11-47, 11-104

Definitions

• a refrigeration system removes thermal energy from a low-temperature region and transfers
heat to a high-temperature region.

• the 1st law of thermodynamics tells us that heat flow occurs from a hot source to a cooler
sink, therefore, energy in the form of work must be added to the process to get heat to flow
from a low temperature region to a hot temperature region.

• refrigeration cycles may be classified as

– vapour compression
– gas compression

• we will examine only the vapour compression systems

• refrigerators and heat pumps have a great deal in common. The primary difference is in the
manner in which heat is utilized.

– Refrigerator ↓C → H

  
takes heat f rom transf ers to

– Heat Pump C
 → H ↑
  
takes heat f rom transf ers to

• this is simply a change in view point

• the Carnot cycle can serve as the initial model of the ideal refrigeration cycle.

– operates as a reversed heat engine cycle - transfers a quantity of heat, QL , from a cold
source at temperature, TL

QL = TL (s3 − s2 )

QH = TH (s4 − s1 )

1
 Win = Qnet = QH − QL

= (TH − TL )(s3 − s2 )

The coefficient of performance (COP) is given by

benef it
COP =
cost

where the benefit for a refrigeration process is the cooling load given as QL . This is the net benefit,
i.e. heat is removed from the cold space. For a heat pump, the benefit is the heat added to the hot
space, i.e. QH .

QL TL
COPref rig = =
Win TH − TL

QH TH
COPheat pump = =
Win TH − TL

Note:

TH (TH − TL ) + TL TL
COPheat pump = = = +1
TH − TL TH − TL TH − TL
= COPref rig + 1

The “1” accounts for the sensible heat addition in going from TL to TH .

2
Vapour Compression Refrigeration Cycle

Room Air

QH
superheated
sat. liquid
Condenser vapour

compressor
Expansion
Valve h4 = h 3 gas

Evaporator
2 phase sat. vapour
QL

Food

Assumptions for Ideal VCRC

• irreversibilities within the evaporator, condenser and compressor are ignored

• no frictional pressure drops

• refrigerant flows at constant pressure through the two heat exchangers (evaporator and con-
denser)

• stray heat losses to the surroundings are ignored

• compression process is isentropic

3
Refrigeration Process

Process Description

1-2s: A reversible, adiabatic (isentropic) compression of the refrigerant.

The saturated vapour at state 1 is superheated to state 2.
⇒ wc = h2s − h1

2s-3: An internally, reversible, constant pressure heat rejection

in which the working substance is desuperheated and then condensed
to a saturated liquid at 3. During his process, the working substance
rejects most of its energy to the condenser cooling water.
⇒ qH = h2s − h3

3-4 An irreversible throttling process in which the temperature and

pressure decrease at constant enthalpy.
⇒ h3 = h4

4-1 An internally, reversible, constant pressure heat interaction

in which the working fluid is evaporated to a saturated vapour
at state point 1. The latent enthalpy necessary for evaporation
is supplied by the refrigerated space surrounding the evaporator.
The amount of heat transferred to the working fluid in the evaporator
is called the refrigeration load.
⇒ qL = h1 − h4

The thermal efficiency of the cycle can be calculated as

qevap h1 − h4
η= =
wcomp h2s − h1

4
Common Refrigerants
There are several fluorocarbon refrigerants that have been developed for use in VCRC.

R11

R12 CCl2 F2 dichlorofluoromethane

- used for refrigeration systems at higher
temperature levels
- typically, water chillers and air conditioning

R22 CHClF2 has less chlorine, a little better for the

environment than R12
- used for lower temperature applications

R134a CF H2 CF 3 tetrafluorethane - no chlorine

- went into production in 1991
- replacement for R12

R141b C2 H3 F Cl2 dichlorofluoroethane

Ammonia N H3 corrosive and toxic

- used in absorption systems

R744 CO2 behaves in the supercritical region

- low efficiency

R290 propane combustible

How to Choose a Refrigerant

Many factors need to be considered

• ozone depletion potential

• global warming potential
• combustibility
• thermal factors

Ozone Depletion Potential

• chlorinated and brominated refrigerants

• acts as a catalyst to destroy ozone molecules

5
 • reduces the natural shielding effect from incoming ultra violet B radiation

Global Warming Potential

• gases that absorb infrared energy

• gases with a high number of carbon-fluorine bonds
• generally have a long atmospheric lifetime

Combustibility

• all hydro-carbon fuels, such as propane

Thermal Factors

• the heat of vaporization of the refrigerant should be high. The higher hf g , the greater the
refrigerating effect per kg of fluid circulated

• the specific heat of the refrigerant should be low. The lower the specific heat, the less heat
it will pick up for a given change in temperature during the throttling or in flow through the
piping, and consequently the greater the refrigerating effect per kg of refrigerant

• the specific volume of the refrigerant should be low to minimize the work required per kg
of refrigerant circulated

• since evaporation and condenser temperatures are fixed by the temperatures of the surround-
ings - selection is based on operating pressures in the evaporator and the condenser

• selection is based on the suitability of the pressure-temperature relationship of the refrigerant

• other factors include:

– chemical stability
– toxicity
– cost
– environmental friendliness
– does not result in very low pressures in the evaporator (air leakage)
– does not result in very high pressures in the condenser (refrigerant leakage)

6
 Designation Chemical Ozone Depletion Global Warming
Formula Potential1 Potential2
Ozone Depleting & Global Warming Chemicals
CFC-11 CCl3 F 1 3,400
CFC-12 CCl2 F2 0.89 7,100
CFC-13 CClF3 13,000
CFC-113 C2 F3 Cl3 0.81 4,500
CFC-114 C2 F4 Cl2 0.69 7,000
CFC-115 C2 F5 Cl1 0.32 7,000
Halon-1211 CF2 ClBr 2.2-3.5
Halon-1301 CF3 Br 8-16 4,900
Halon-2402 C2 F4 Br2 5-6.2
carbon tetrachloride CCl4 1.13 1,300
methyl chloroform CH3 Ccl3 0.14
nitrous oxide N2 O 270
Ozone Depleting & Global Warming Chemicals - Class 2
HCFC-22 CHF2 Cl 0.048 1,600
HCFC-123 C2 HF3 Cl2 0.017 90
HCFC-124 C2 HF4 Cl 0.019 440
HCFC-125 C2 HF5 0.000 3,400
HCFC-141b C2 H3 F Cl2 0.090 580
HCFC-142b C2 H3 F2 Cl 0.054 1800
Global Warming, non-Ozone Depleting Chemicals
carbon dioxide CO2 0 1
methane CH4 0 11
HFC-125 CHF2 CF3 0 90
HFC-134a CF H2 CF3 0 1,000
HFC-152a CH3 CHF2 0 2,400
perfluorobutane C4 F10 0 5,500
perfluoropentane C5 F12 0 5,500
perfluorohexane C6 F14 0 5,100
perfluorotributylamine N (C4 F9 )3 0 4,300

1 - relative to R11
2 - relative to CO2

7
Cascade Refrigeration System

• combined cycle arrangements

• two or more vapour compression refrigeration cycles are combined
• used where a very wide range of temperature between TL and TH is required
• the condenser for the low temperature refrigerator is used as the evaporator for the high
temperature refrigerator

Advantages

• the refrigerants can be selected to have reasonable evaporator and condenser pressures in the
two or more temperature ranges

8
Absorption Refrigeration System
Differences between an absorption refrigeration system and a VCRC

VCRC Absorption RS
• vapour is compressed • the refrigerant is absorbed by
between the evaporator and an absorbent material to form a
the condenser liquid solution
• process is driven by work • heat is added to the process
to retrieve the refrigerant vapour
from the liquid solution
• process is driven by heat

Advantages

• since the working fluid is pumped as a liquid the specific volume is less than that of a gas (as
in the VCRC compressor), hence the work input is much less.

• there are considerable savings in power input because a pump is used instead of a compres-
sor.

• this is weighed off against the cost of extra hardware in an absorption system

Common Refrigerant/Absorber Combinations

Refrigerant Absorber

1. ammonia water

2. water lithium bromide

lithium chloride

9
Process

Room Air Source of

Heat

liquid
QH Q*H
ammonia
ammonia vapour only
Condenser Generator

weak ammonia cold

Expansion water solution
Valve regenerator

Evaporator Absorber
2 phase dry vapour
QL
Q*L
Food strong ammonia pump
cold water solution
sink

• ammonia circulates through the condenser, expansion valve and evaporator (same as in the
VCRC)
• the compressor is replaced by an absorber, pump, generator, regenerator and a valve
• in the absorber, ammonia vapour is absorbed by liquid water
– the process is exothermic (gives off heat)
– ammonia vapour is absorbed into the water at low T and P maintained by means of
Q∗L
– absorption is proportional to 1/T ⇒ the cooler the better
• the pump raises the solution to the pressure of the generator
• in the generator, ammonia is driven out of the solution by the addition of Q∗H ,
(endothermic reaction)
• ammonia vapour is passed back to the condenser
• a regenerator is used to recoup some of the energy from the weak ammonia water solution
passed back to the absorber. This energy is transferred to the solution pumped to the genera-
tor. This reduces the Q∗H required to vapourize the solution in the generator. It also reduces
the amount of Q∗L that needs to be removed from the solution in the absorber.

10
Internal Combustion Engines

Reading Problems
9-3 → 9-7 9-37, 9-41, 9-47, 9-51, 9-56

Definitions

1. spark ignition:

• a mixture of fuel and air is ignited by a spark plug

• applications requiring power to about 225 kW (300 HP)
• relatively light and low in cost

2. compression ignition engine:

• air is compressed to a high enough pressure and temperature that combustion occurs
when the fuel is injected
• applications where fuel economy and relatively large amounts of power are
required

The Gasoline Engine

1
 • conversion of chemical energy to mechanical energy
• can obtain very high temperatures due to the short duration of the power stroke

Air Standard Cycle

ASSUMPTIONS:
• air is an ideal gas with constant cp and cv
• no intake or exhaust processes
• the cycle is completed by heat transfer to the surroundings
• the internal combustion process is replaced by a heat transfer process from a TER
• all internal processes are reversible
• heat addition occurs instantaneously while the piston is at TDC

Definitions

Mean Effective Pressure (MEP): The theoretical constant pressure that, if it acted on the piston
during the power stroke would produce the same net work as actually developed in one
complete cycle.

net work for one cycle Wnet

M EP = =
displacement volume VBDC − VT DC

The mean effective pressure is an index that relates the work output of the engine to it size
(displacement volume).

2
Otto Cycle

• the theoretical model for the gasoline engine

• consists of four internally reversible processes

• heat is transferred to the working fluid at constant volume

The Otto cycle consists of four internally reversible processes in series

1 → 2 isentropic compression or air as the piston moves from BDC to TDC

2 → 3 constant volume heat addition to the fuel/air mixture from an external source while the
piston is at TDC (represents the ignition process and the subsequent burning of fuel)

3 → 4 isentropic expansion (power stroke)

4 → 1 constant volume heat rejection at BDC

3
The Otto cycle efficiency is given as

 k−1  1−k
T1 V2 V1
η =1− =1− =1−
T2 V1 V2

If we let

V1 V4
r= = = compression ratio
V2 V3

Then

ηOtto = 1 − r 1−k

Why not go to higher compression ratios?

• there is an increased tendency for the fuel to detonate as the compression ratio increases

• the pressure wave gives rise to engine knock

• can be reduced by adding tetraethyl lead to the fuel

• not good for the environment

4
Diesel Cycle

• an ideal cycle for the compression ignition engine (diesel engine)

• all steps in the cycle are reversible

• heat is transferred to the working fluid at constant pressure

• heat transfer must be just sufficient to maintain a constant pressure

If we let

V1 V4
r = = compression ratio =
V2 V2

V3
rv = = cutof f ratio → injection period
V2

then the diesel cycle efficiency is given as

  k 
1 1 r −1
ηDiesel = 1 − v
r k−1 k rv − 1

5
Where we note

  k 
1 1 r −1
ηDiesel = 1 − v
r k−1 k rv − 1
  
=1 in the Otto Cycle

Comparison of the Otto and the Diesel Cycle

• ηOtto > ηDiesel for the same compression ratio

• but a diesel engine can tolerate a higher ratio since only air is compressed in a diesel cycle
and spark knock is not an issue

• direct comparisons are difficult

Dual Cycle (Limited Pressure Cycle)

• this is a better representation of the combustion process in both the gasoline and the diesel
engines

• in a compression ignition engine, combustion occurs at TDC while the piston moves down
to maintain a constant pressure

6
Dual Cycle Efficiency

Given

V1
r = = compression ratio
V2
V4
rv = = cutof f ratio
V3
P3
rp = = pressure ratio
P2

rp rvk − 1
ηDual = 1 −
[(rp − 1) + krp (rv − 1)] r k−1

Note: if rp = 1 we get the diesel efficiency.

7
Stirling Cycle

8
 • reversible regenerator used as an energy storage device

• possible to recover all heat given up by the working fluid in the constant volume cooling
process

• all the heat received by the cycle is at TH and all heat rejected at TL

• ηStirling = 1 − TL /TH (Carnot efficiency)

With perfect regeneration

QH = TH (s2 − s1 )

QL = TL (s3 − s4 )

9
 Wnet QH − QL QL TL (s3 − s4 )
η= = =1− =1− (1)
QH QH QH TH (s2 − s1 )

From Gibb’s equation

T ds = du + P dv = cv dT + P dv

P dv Rdv
if T = constant ⇒ T ds = P dv ⇒ ds = =
T v
Integrating gives

   
v3 v2
s3 − s4 = R ln = R ln = s2 − s1
v4 v1

Therefore s3 − s4 = s2 − s1 , and Eq. 1 gives

TL
η =1− ⇒ Carnot ef f iciency
TH

10
Brayton Cycle

Reading Problems
9-8 → 9-10 9-78, 9-84, 9-108

Open Cycle Gas Turbine Engines

• after compression, air enters a combustion chamber into which fuel is injected

• the resulting products of combustion expand and drive the turbine

• combustion products are discharged to the atmosphere

• compressor power requirements vary from 40-80% of the power output of the turbine (re-
mainder is net power output), i.e. back work ratio = 0.4 → 0.8

• high power requirement is typical when gas is compressed because of the large specific
volume of gases in comparison to that of liquids

Idealized Air Standard Brayton Cycle

• closed loop
• constant pressure heat addition and rejection
• ideal gas with constant specific heats

1
Brayton Cycle Efficiency

The Brayton cycle efficiency can be written as

η = 1 − (rp )(1−k)/k

where we define the pressure ratio as:

P2 P3
rp = =
P1 P4

2
Maximum Pressure Ratio

Given that the maximum and minimum temperature can be prescribed for the Brayton cycle, a
change in the pressure ratio can result in a change in the work output from the cycle.

The maximum temperature in the cycle (T3 ) is limited by metallurgical conditions because the
turbine blades cannot sustain temperatures above 1300 K. Higher temperatures (up to 1600 K can
be obtained with ceramic turbine blades). The minimum temperature is set by the air temperature
at the inlet to the engine.

3
Brayton Cycle with Reheat

• T3 is limited due to metallurgical constraints

• excess air is extracted and fed into a second stage combustor and turbine
• turbine outlet temperature is increased with reheat (T6 > T4 ), therefore potential for regen-
eration is enhanced
• when reheat and regeneration are used together the thermal efficiency can increase signifi-
cantly

4
Compression with Intercooling

• the work required to compress in a steady flow device can be reduced by compressing in
stages

• cooling the gas reduces the specific volume and in turn the work required for compression

• by itself compression with intercooling does not provide a significant increase in the effi-
ciency of a gas turbine because the temperature at the combustor inlet would require addi-
tional heat transfer to achieve the desired turbine inlet temperature

• but the lower temperature at the compressor exit enhances the potential for regeneration i.e.
a larger ΔT across the heat exchanger

5
Brayton Cycle with Regeneration

• a regenerator (heat exchanger) is used to reduce the fuel consumption to provide the required
Q̇H

• the efficiency with a regenerator can be determined as:

Ẇnet Q̇L
η= = 1−
Q̇H Q̇H

6
 cp (T6 − T1 )
= 1− ⇒ (f or a real regenerator)
cp (T3 − T5 )

cp (T6 − T1 )
= 1− ⇒ (f or an ideal regenerator)
cp (T3 − T5 )

cp (T2 − T1 )
= 1−
cp (T3 − T4 )

and
 
Tmin
η =1− (rp )(k−1)/k
Tmax

• for a given Tmin/Tmax , the use of a regenerator above a certain rp will result in a reduction
of η

with an ideal
regenerator

without a
regenerator

better with a better without T1 / T3 = 0.2

regenerator a regenerator

T1 / T3 = 0.25

T1 / T3 = 0.3

r p, cr rp

7
Regenerator Effectiveness

Q̇reg,actual h5 − h2 h5 − h2 T5 − T2
= = = =
Q̇reg,ideal h5 − h2 h4 − h2 T4 − T2

Typical values of effectiveness are ≤ 0.7

Repeated intercooling, reheating and regeneration

 will provide
 a system that approximates the
TL
Ericsson Cycle which has Carnot efficiency η = 1 − .
TH

Brayton Cycle With Intercooling, Reheating and Regeneration

8
 T
Tmax
QH Q H, R

7s 9s
Q reg
Q reg
2s
4s

QL
Tmin
Q L, I

Compressor and Turbine Efficiencies

Isentropic Efficiencies

h2,s − h1 cp (T2,s − T1 )
(1) ηcomp = =
h2 − h1 cp (T2 − T1 )

h3 − h4 cp (T3 − T4 )
(2) ηturb = =
h3 − h4,s cp (T3 − T4,s )

Wnet QH − QL QL cp (T4 − T1 )
(3) ηcycle = = =1− =1−
QH QH QH cp (T3 − T2 )

Given the turbine and compressor efficiencies and the maximum (T3 ) and the minimum (T1 ) tem-
peratures in the process, find the cycle efficiency (ηcycle ).

(4) Calculate T2s from the isentropic relationship,

 (k−1)/k
T2,s P2
= .
T1 P1

Get T2 from (1).

(5) Do the same for T4 using (2) and the isentropic relationship.

(6) substitute T2 and T4 in (3) to find the cycle efficiency.

9
Jet Propulsion

Reading Problems
9-11 9-117, 9-121

Gas Turbines for Aircraft Propulsion

• gas turbines are well suited to aircraft propulsion because of their favorable power-to-weight
ratio
• the exhaust pressure of the turbine will be greater than that of the surroundings
• gases are expanded in the turbine to a pressure where the turbine work is just equal to the
compressor work plus some auxiliary power for pumps and generators i.e. the net work
output is zero
• since the gases leave at a high velocity, the change in momentum that the gas undergoes
provides a thrust to the aircraft
• typically operate at higher pressure ratios, often in the range of 10 to 25

Conservation of Momentum

where vi∗ is the velocity of the aircraft

d(M om)x,cv 
= (Ṁ om)x,in − (Ṁ om)x,out + Fx
dt

d
for steady flow ⇒ = 0 and
dt

1
 ṁivi∗ − ṁe ve∗ + FT + PiAi − Pe Ae = 0

Since the air-fuel mass ratio is high

ṁf uel << ṁi ⇒ ṁi ≈ ṁe

and

Pe ≈ Pi ≈ Patm

Therefore

FT = ṁe ve∗ − ṁivi∗ − Patm(Ai − Ae )

  
negligible

= ṁi(ve∗ − vi∗ )

FT thrust
Specific Impulse: I= = ve∗ − vi∗ =
ṁi mass

Propulsive Power: ẆT = FT vi∗ ≈ ṁi(ve∗ − vi∗ )vi∗

ẆT
Propulsive Efficiency: η=
Q̇in

Since the net work output is zero, we must define the propulsive efficiency as propulsive power
over the heat flow rate in the combustion process. This then becomes a measure of how efficiently
the energy released during the combustion process is converted to propulsive energy.

2
Turbojet Engine

Sections

• a-1: diffuser

– decelerates the incoming flow relative to the engine

– a pressure rise known as a ram effect occurs, v ∗ (↓), P (↑)

• 1-4: gas generator

– compressor, combustor and turbine

∗ 1-2: isentropic compression
∗ 2-3: constant pressure heat addition
∗ 3-4: isentropic expansion through the turbine during which work is developed
– turbine power just enough to drive the compressor
– air and fuel are mixed and burned in the combustion chamber at constant pressure
– PT >> Patm

• 4-5: nozzle

– isentropic expansion through the nozzle, air accelerates and the pressure deceases
– gases leave the turbine significantly higher in pressure than atmospheric pressure
– gases are expanded to produce a high velocity, ve∗ >> vi∗ results in a thrust
– v1∗ << va∗ v1∗ is negligible
– v4∗ << v5∗ v4∗ is negligible

3
Afterburner

• similar to a reheat device

• produces a higher temperature at the nozzle inlet, T5 > T4
• results in an increase in velocity

4
By performing a 1st law energy over the nozzle we can obtain an expression for the exit velocity
in terms of the entrance temperature to the nozzle.

⎧ ⎡ ⎤⎫
⎪
⎪ ⎪
⎪   
⎪
⎨ ⎢ ⎪
0
dE ⎢ (v4∗ )2 ⎥
⎥
⎬ (ve∗ )2
 +Ẇ
= Q̇ 0
 0
+ ⎪ṁ ⎢h4 + ⎥ − ṁ he +
dt ⎪
⎪
⎩
⎣ 2 ⎦⎪
  ⎪
⎪
⎭
2
→0

If we assume that the air velocity leaving the turbine is relatively small, the kinetic energy term at
4 can be assumed to go to zero and we get

#
ve∗ = 2(h4 − he )
#
= 2cp (T4 − Te )

#
• exit velocity proportional to ve∗ ∝ 2cp (T4 − Te )

• afterburner is used to increase T4 to T5

• similar to a reheat device

• produces a higher temperature at the nozzle inlet

5
Other Types of Engines

1. Turbo-Prop Engine

• gas turbine drives the compressor and the propeller

• most of the thrust is from the propeller
• works by accelerating large volumes of air to moderate velocities
• propellers are best suited for low speed (< 300 mph) flight
• new turbo-props are suitable for velocities up to 500 mph
• by-pass ratio of 100:1 or more
• by-pass ratio defined as:

mass flow bypassing the combustion chamber

bypass ratio =
mass flow through the combustion chamber

6
2. Turbo-Fan Engine (Ducted Turbo-Prop Engine)

• best choice for fuel economy and speed

• high speed exhaust gases are mixed with the lower speed air in the by-pass resulting in
a considerable noise reduction
• by-pass ratio can be adjusted
• by-pass provides thrust for takeoff
• the core provides thrust for cruising
• typically used for speeds up to 600 mph
• increasing the by-pass ratio results in increased thrust
• typical by-pass ratios are 5-6

7
3. Ramjet

• no moving parts
• compression is achieved by decelerating the high-speed incoming air in the diffuser
• aircraft must already be in flight at a high speed
• used in aircraft flying above Mach 1

4. Pulse Jet Engine

• similar to a ram jet but lets in a slug of air at a time and then closes a damper during
the combustion stage
• uses a shutter-type valve for damper control
• can be used effectively at low velocities
• used in German V1 missle
• the combustion firing rate was approximately 40 cycles/sec with a maximum flight
velocity of 600 mph

8
Non-Reacting Gas Mixtures

Reading Problems
13-1 → 13-3 13-52, 13-60
14-1 → 14-7 14-32, 14-35, 14-68, 14-71, 14-75
14-79, 14-103, 14-112

Introduction
• homogeneous gas mixtures are frequently treated as a single compound rather than many
individual constituents
• the individual properties of inert gases tend to be submerged, such that the gas behaves as a
single pure substance
• eg. - air consists of oxygen, nitrogen, argon and water vapour. But dry air can be treated as
a simple gas with a molar mass of 28.97 kg/kmole
• equations can be derived to express the properties of mixtures in terms of the properties of
their individual constituents
• it is assumed that each constituent is unaffected by the other constituents in the mixture

P-V-T Relationships for Ideal Gas Mixtures

Amagat Model (law of additive volumes)

• the volume of a mixture is the sum of the volumes that each constituent gas would occupy if
each were at the pressure, P and temperature, T , of the mixture

T, P T, P T, P

mA mB remove mC = mA + mB
nA nB → nC = nA + nB
VA VB partition VC = VA + VB

• the volume that ni moles of a component i would occupy at P and T is called the partial
volume, Vi
niRT
Vi =
P

1
The volume of the gas mixture is equal to the sum of the volumes each gas would occupy if it existed
at the mixture temperature and pressure.

j

V = Vi
i=1

Dalton Model (law of additive pressures)

• the pressure of a mixture of gases is the sum of the pressures of its components when each
alone occupies the volume of the mixture, V , at the temperature, T , of the mixture

V, T V, T V, T

mA , nA , P A + mB , nB , P B = mC = mA + mB
nC = nA + nB
PC = PA + PB

• for a mixture of ideal gases the pressure is the sum of the partial pressures of the individual
components

The pressure of a gas mixture is equal to the sum of the pressures each gas would exert if it existed
alone at T and V .

By combining the results of the Amagat and Dalton models i.e. (1) and (2), we obtain for ideal gas mixtures

Pi Vi ni
= =
P V n

Therefore, Amagat’s law and Dalton’s law are equivalent to each other if the gases and the mixture
are ideal gases.

2
Mixture Properties

Extensive properties such as U, H, cp , cv and S can be found by adding the contribution of each
component at the condition at which the component exists in the mixture.

  
U = Ui = m i ui = m Xiui = mu
 
= niui = n Yiui = nu

where u is the specific internal energy of the mixture per mole of the mixture.

$
u = Xi ui
$
h = Xi hi
$
cv = Xi cvi
$
cp = Xi cpi
$
s = Xi si

Changes in internal energy and enthalpy of mixtures

  T2
u2 − u1 = Xi(u2 − u1 )i = cv dT = cv (T2 − T1 )
T1

  T2
h2 − h1 = Xi(h2 − h1 )i = cp dT = cp (T2 − T1 )
T1

 T2 P2
s 2 − s1 = Xi(s2 − s1 )i = cp ln − R ln
T1 P1

These relationships can also be expressed on a per mole basis.

Entropy Change Due to Mixing of Ideal Gases

• when ideal gases are mixed, a change in entropy occurs as a result of the increase in disorder
in the systems

• if the initial temperature of all constituents are the same and the mixing process is adiabatic

3
 – temperature does not change
– but entropy does

 
PA PB
ΔS = − mA RA ln + mB RB ln + ···
P P
j
 Pi
= − miRi ln
i=1 P
j

= −R ni ln Yi
i=1

4
Psychrometrics
• studies involving mixtures of dry air and water vapour
• used in the design of air-conditioning systems, cooling towers and most processes involving
the control of vapour content in air
• for T ≤ 50◦ C (Psat ≤ 13 kP a) ⇒ h ≈ h(T )
– water vapour can be treated as an ideal gas

Definitions

Moist Air

• a mixture of dry air and water vapour where dry air is treated as if it were a pure component
mRT
• the overall mixture is given as ⇒ P =
V

Total Pressure

P = Pa + Pw
m a Ra T
Pa =
V
mw Rw T
Pw =
V

where Pa is the partial pressure of air and Pw is the partial pressure of water vapour. Typically
mw << ma .

Relative Humidity - φ

Pw (T ) vapour pressure at the prevailing T

φ= =
Psat(T ) saturation pressure at the prevailing T

If Pw = Psat(T ) the mixture is said to be saturated.

Specific Humidity (Humidity ratio) - ω

mw mass of water vapour

ω = =
ma mass or air

5
 M̃w nw M̃w (Pw V /RT )
= =
M̃a na M̃a (Pa V /RT )
⎛ ⎞ 
M̃w Pw
= ⎝ ⎠
M̃a Pa
 
Pw
= 0.622
Pa

In addition ω can be written as

     
Pw Pw φPsat
ω = 0.622 = 0.622 = 0.622
Pa P − Pw P − φPsat

which can be rearranged in terms of relative humidity

Pω Pω
φ= ⎛ ⎞ =
M̃w Psat(ω + 0.622)
Psat ⎝ω + ⎠
M̃a

Dry Bulb Temperature - the temperature measured by a thermometer placed in a mixture of air
and water vapour

Wet Bulb Temperature

6
 • thermometer surrounded by a saturated wick

• if air/water vapour mixture is not saturated, some water in the wick evaporates and diffuses
into the air → cooling the water in the wick

• as the temperature of the water drops, heat is transferred to the water from both the air and
the thermometer

• the steady state temperature is the wet-bulb temperature

Sling Psychrometer - a rotating set of thermometers one of which measures wet bulb temperature
and the other dry bulb temperature. TDB and TW B are sufficient to fix the state of the mixture.

The Psychrometric Chart

where the dry bulb temperature is the temperature measured by a thermometer place in the mixture
and the wet bulb temperature is the adiabatic saturation temperature.

7
An Adiabatic Saturator
How can we measure humidity?

• the adiabatic saturator is used to measure humidity

• two inlets, single exit device through which moist air passes
• air-water mixture of unknown humidity enters at a known pressure and temperature
• if air/water mixture is not saturated, (φ < 100%), some water from the pool will evaporate
• the energy required to evaporate the water comes from the moist air → mixture temperature
decreases
• for a sufficiently long duct, the moisture exits with φ3 = 1
• the temperature of the exiting mixture is called the adiabatic saturation temperature

Adiabatic Saturator Analysis

Conservation of Mass

ṁa,1 = ṁa,3 air (1)

ṁw,1 + ṁw,2 = ṁw,3 water (2)

Conservation of Energy

(ṁh)a,1 + (ṁh)w,1 + (ṁh)w,2 = (ṁh)a,3 + (ṁh)w,3 (3)

8
By definition

 
ṁw
ω1 = (4)
ṁa 1
 
ṁw
ω3 = (5)
ṁa 3

From (2) and (1)

⎛ ⎞
  ⎜ ⎟  
ṁw,2 ⎜ ṁw,3 ⎟ ṁw,1
⎜ ⎟
= ⎜ ⎟ − = ω3 − ω1
ṁa,1 ⎜ ṁa,1 ⎟ ṁa,1
⎝    ⎠
ṁa,3

mw2
Dividing (3) by ṁa,1 and noting ma1 = ma3 and = ω3 − ω1
ma1

ha,1 + ω1 hw,1 + (ω3 − ω1 ) hw,2 = ha,3 + ω3 hw,3 (6)

(ha,3 − ha,1 ) + ω3 (hw,3 − hw,2 )

ω1 =
(hw,1 − hw,2 )

9
If we assume:
i) air is an ideal gas and (ha,3 − ha,1 ) = cpa (T3 − T1 )

ii) (hw,3 − hw,2 ) = hg − hf = hf g (T3 )

iii) hw,1 ≈ hg (T1 )

iv) hw,2 = hf (T2 ) = hf (T3 )

then we can write ω1 as a function of T1 and T3 only

cpa (T3 − T1 ) + ω3 hf g (T3 )

ω1 =
hg (T1 ) − hf (T3 )

Aside: Since hf << hg very little is lost if the denominator is approximated as hf g (T1 )

During the adiabatic saturation process, the vapour pressure increases and the temperature de-
creases; so the adiabatic saturation temperature is higher than the dew point temperature and lower
than the dry bulb temperature. For the limiting case of a saturated mixture, the dry bulb, dew point
and adiabatic saturation temperature are the same.

Equation 6 can be written as

h∗1 + (ω3 − ω1 ) h,2 = h∗3

  
negligible

where

h∗ = ha + ω hw

Therefore h∗1 ≈ h∗3 (Twb ). The lines of wet bulb temperature and h∗ coincide on the psychromet-
ric chart. Since h∗3 is solely a function of Twb , lines of h∗1 are proportional to Twb .

10
Reacting Gas Mixtures

Reading Problems
15-1 → 15-7 15-21, 15-32, 15-51, 15-61, 15-74
15-83, 15-91, 15-93, 15-98

Introduction

• thermodynamic analysis of reactive mixtures is primarily an extension of the principles we

have learned thus far

• it is necessary to modify the methods used to calculate specific enthalpy, internal energy and
entropy

Definitions

Combustion Process:

• a fuel made up of hydrocarbons is said to have burned completely if:

– all the carbon present in the fuel is burned to carbon dioxide
– all the hydrogen is burned to water
• if the conditions are not fulfilled the combustion process is incomplete

Combustion Reactions:
reactants → products
or
fuel + oxidizer → products

• in all cases the mass is conserved

mass of products = mass of reactants

Fuels:

• fuel is simply a combustible substance

• hydrocarbon fuels exist as liquids, gases and solids
– liquids → gasoline - octane, C8 H18

1
 – gases → methane, CH4
– solids → coal

Combustion Air:
• oxygen is required in every combustion reaction
• in most combustion reactions air provides the needed oxygen
• dry air is considered to be

21% oxygen
on a molar basis
79% nitrogen
nN2 0.79
molar ratio = = = 3.76
nO2 0.21
1 mole of air can then be written as [0.21 O2 + 0.79 N2 ]
For convenience, we typically refer to air as [O2 + 3.76 N2 ] which is actually 4.76
moles of air.

Note: From the Amagat model, we know that a mixture at a known T and P (as is the
case with combustion reactions)
ni Vi
=
n V

Therefore, by expressing a mixture in terms of the number of moles we are also ex-
pressing it in terms of a volume fraction.
• nitrogen does not undergo a chemical reaction in combustion since it is inert

Air-Fuel Ratio:
mass of air moles of air × M̃air
=
mass of f uel moles of f uel × M̃f uel
⎛ ⎞
M̃air
¯ ⎝
AF = AF ⎠
M̃f uel

where:

AF - air fuel ratio on a mass basis

AF - air fuel ratio on a molar basis

M̃air = 28.97 kg/kmole

2
Theoretical or Stoichiometric Air:

• the minimum amount of air that supplies sufficient oxygen for complete combustion of
all carbon and hydrogen in the fuel - referred to as stoichiometric, 100% stoichiometric
or theoretical
• no free oxygen would appear in the products
• greater than stoichiometric leads to free oxygen in the products
• less than stoichiometric and C, CO, OH, H2 will appear in the products since there is
not enough oxygen to form water or carbon dioxide (the actual proportions will depend
on the temperature and the pressure)
• normally the amount of air supplied is given as a percentage of the theoretical value
i.e. 150% = 1.5 × the theoretical air
- referred to as 20% excess air, 120% stoichiometric

Equivalence Ratio:

• defined as
AFactual
equivalence ratio =
AFtheoretical
• if the equivalence ratio is:
– > 1 → lean mixture (excess air)
– < 1 → rich mixture (not enough air)

3
Conservation of Energy for Reacting Systems

Enthalpy of Formation

• previous calculations involving enthalpy were all based on differences and the reference used
to determine enthalpy did not matter

• when chemical reactions occur, reactants disappear and products are formed
→ differences cannot be calculated for all substances involved

• it is necessary to establish a common base to account for differences in composition

• the enthalpy datum for reacting systems is set to zero at standard temperature and pressure

– Tref = 25◦ C → 298 K

– Pref = 1 atm

• h = 0 assigned to elements in their most stable form i.e. O2 , N2 , C, etc.

• Enthalpy of Formation: the energy released or absorbed when a compound is formed from
its stable elements at STP

o
where hf is the enthalpy of formation.

Taking an energy balance over the combustion chamber shown above, we obtain

o o o o o
a hA + b hB + c hC + hf −→ hABC
  
generally=0

The left side of the equation is typically zero because h = 0 for elements in their stable
o
form. The sign of hf indicates the direction of heat flow; +ve is endothermic and -ve is
exothermic.

4
Effects of Non-Standard Temperature

o o
h(T, P ) = hf + (hT,P − hT =25 ◦C, P = 1 atm)
  
Δh at known temperatures

where

o
hf is the heat resulting from a chemical change at T = 25 ◦ C and P = 1 atm

Δh is the heat resulting from a change in temperature (sensible heat) with respect
to the reference temperature, Tref = 25 ◦ C

5
Enthalpy of Combustion
• while the enthalpy of formation is related to elemental reactants −→ resulting in a single
compound; the enthalpy of combustion is related to f uel + oxidizer as the reactants

• Enthalpy of Combustion: the difference between the enthalpy of the products and the en-
thalpy of the reactants where complete combustion occurs at a given temperature and pres-
sure
 
Q = (mh)P − (mh)R = HP (TP ) − HR (TR )
  
HRP

 
Q = (nh)P − (nh)R = H P (TP ) − H R (TR )
  
H RP

where

hc = HRP /kmole of f uel

with:

+ve Q ⇒ endothermic

−ve Q ⇒ exothermic

• when enthalpy of formation data are available for all products and reactants the above equa-
tion can be used

• otherwise a calorimeter must be used to measure the enthalpy of combustion

6
Heating Value
• the heating value of a fuel is a positive value equal to the magnitude of the enthalpy of
combustion when products are returned to the state of the reactants

• two values are used

– HHV: higher heating value - obtained when all the water formed by combustion is a
liquid at the reference temperature
– LHV: lower heating value - obtained when all the water formed by combustion is a
vapour as an ideal gas in the mixture of the products

• the HHV exceeds the LHV by the energy required to vaporize the liquid formed

(m · hf g )H2 O
HHV = LHV +
kmole of f uel
nH2 O
= LHV + (M̃ · hf g )H2 O ·
nf uel

where

hf g (25 ◦ C) = 2, 442.3 kJ/kg

M̃H2 O = 18.015 kg/kmole

Adiabatic Flame Temperature

• if the system is perfectly insulated it cannot dispose of the LHV and the LHV goes into
heating the products above the reference temperature

7
• under adiabatic conditions, the maximum temperature attained by the products when com-
bustion is complete is called the adiabatic flame or adiabatic combustion temperature

HP (Tad ) = HR (TR )

 o 0  o 0
nP (hf + h −h ) =
   P
nR (hf + h −h )
   R
P R
Δh Δh

We need to collect terms based on what we know or can readily calculate and what we do
not know, i.e. terms that are a function of Tad .

 
  o  o
nP (h)P = nR (h − h )R − − nP (h )P
P
   R P
sensible heat   
f unction of Tad sensible heat
f unction of TR or Tref

 o  o
+ nR (hf )R − nP (hf )P
R P
  
chemical heat
f unction of TR or Tref

Step 1: Calculate the right hand side based on known values of TR and Tref .

Step 2: Calculate the left hand side based on a guessed value of Tad .

Step 3: Repeat Step 2, until LHS = RHS.

8
Dew Point
• since water is formed when hydrocarbon fuels are burned, the mole fraction of water vapour
in the form of gaseous products can be significant

• if the gaseous products of combustion are cooled at constant mixture pressure the dew point
temperature is reached when water vapour begins to condense

• since corrosion of duct work, mufflers etc. can occur, the knowledge of dew point tempera-
ture is important

Evaluation of Entropy for Reacting Systems

The 2nd law entropy equation can be written as

S −S + Sgen = ΔSsystem
 in  out      
due to heat & mass transf er generation change in entropy

For a closed system, such as a combustion process, the entropy balance on the system can be
written as

 Qi
+ Sgen = SP − SR
Ti

• a common datum must be used to assign entropy values for each substance involved in the
reaction

• an entropy of 0 for pure crystalline substances is obtained at absolute zero

• the entropy relative to this datum is called absolute entropy

• absolute entropy at 1 atm and temperature T is denoted as so (T ) or so (T ) for a per unit

mass or per mole basis

• while h was only a function of temperature for ideal gases, we must account for the effects
of both T and P in entropy

9
• the entropy at any value of T and P can be calculated as
 
Pi
s(T, P ) = s (T ) −R ln
o
   Pref
tables

where

Pref = 1 atm

Pi = partial pressure of i th component

R = 8.31434 kJ/kmole · K

• the partial pressure Pi can also be written as

Pi = YiP

and
 
YiP
s(T, Pi) = soi (T ) − R ln
Pref

where P is the mixture pressure and Yi is the mole fraction of the i th component.

10