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Chapter 1: Basic Concepts

Introduction to Thermodynamics
Thermodynamic System and Control Volume
Properties, Processes and Cycles
Units
Specific Volume and Density
Pressure
Energy and Temperature
1

Control Mass and Control Volume

Control Mass:

Control Volume:

Encloses a fixed amount of mass

Mass can enter or leave

Control surface

Control surface

Notice volume may change

Complete system: Power Plant


Conversion of fuel energy into electricity and heat

Water
Loop

Heat
Loop

(Condenser)

Complete system: Refrigerator


Refrigerator pushes energy out of a cold space into a warmer space (room)
Refrigerant flows
in a loop through
4 devices

Properties, Processes and Cycles


Phases: Solid, Liquid and Vapor (gas)
State: a specific condition expressed by a unique set of property values
like P, T and density .
Two independent properties are needed to specify a state
Intensive properties are independent of mass (P, T, )
Extensive properties depend on mass (Mass, Volume, Energy)

Process: A change of a substance beginning at state 1 to a final state 2


through a continuous variation of the state.
Example: Heat a cup of cold water to be warm water
Example: Compress air in a cylinder to a smaller volume (bike pump)

Properties, Processes and Cycles, Continued

Process path or type: A specific succession of states is usually given a


name that relates to the condition under which this happens. This is given
by the way the device behaves as a process equation or device equation.
Example: The heating of water in a cup takes place at atmospheric
pressure so it is called an isobaric process, pressure is constant.
Example: Heating of air in a constant volume container is called an
isochoric process, volume is constant.
Example: Air is compressed in a piston cylinder while it is maintained
at a constant temperature called an isothermal process.
Example: Air is compressed in a well insulated piston cylinder so it
does not have any heating or cooling called an adiabatic process.
The type of process is often dictated by the device behavior and could
also be called a device equation.
6

Properties, Processes and Cycles, Continued

Cycle: A process path that ends in the initial state. It can be a complex
process or a combination of several simple processes.
Example: Water circulating in a steam power plant
Example: Refrigerant (like R-134a, R-410A or R-12) circulating in a
refrigerator or air-conditioner.
Example: Air going through 4 sequential processes in a piston cylinder
similar to what happens in a car engine. This is repeated in time.
Cycles do not (net) change the working substance which keeps looping in
space (flow) or in time. However during the cycle the outside world
exchanges energy with the working substance at different conditions
during the cycle so the net effect is an energy conversion process.

UNITS

SI or English:
SI: mass (kg), length (m), time (s), force (N)
F = ma has units

1 N = (1 kg) (1 m/s2) = 1 kg m/s2

English: mass (lbm), length (ft), time (s), force (lbf)


F = mg has units

1 lbf = (1 lbm) (32.174 ft/s2) = 32.174 lbm ft/s2

Mole: A fixed number of particles (No = 6.022*1023 particles per mol)


distinguish between gram mole (mol) and kilomole (kmol).
m=nM

where m is mass , n = number of moles, M is molecular mass

Units and Conversions: See Table A.1

Specific Volume and Density


Specific volume: Volume per unit mass (v)
v = V/m

limit for small volume

Density: Mass per unit volume ()


= m/V limit for small volume

Typical numbers SI:


Liquid water: v 0.001 m3/kg and 1000 kg/m3
Atmospheric air: v 1 m3/kg and 1 kg/m3
See Tables for a few
typical substances.
SI: A3, A4, A5
Eng.: F2, F3, F4

Pressure
Pressure is force per unit area (normal stress)

= lim

With uniform P, piston at rest (F = F)

Fext = P Acyl
Units for P
1 Pa = 1 N/m2
1 kPa = 1000 Pa = 1 kN/m2
1 bar = 105 Pa = 100 kPa = 0.1 MPa
1 atm = 101.325 kPa = 14.696 lbf/in2

10

Pressure
Study 1.1
A hydraulic lift
A hydraulic cylinder has a diameter of 7.5 cm. What should the
fluid pressure inside be to create a force of 6000 N on the rod if we
neglect the outside pressure?

Solution

____

_____

From the definition of pressure as force per unit area


F=PA

or

F
P=A

The cross sectional area is

A = r2 = D2/4 = 4 0.0752 m2 = 0.004418 m2


so the pressure becomes
P=

F
6000 N
=
= 1 358 080 Pa = 1358 kPa
A 0.004418 m2

11

Manometer/Barometer
Manometer
Force acting down on cross section at B:
Column mass:

m = AH

F = PBA = PoA + mg = PoA + AHg


PB = PA = Po + P = Po + gH
Pgauge = P = gH

Manometer

Barometer
The top pressure is near zero (perfect vacuum)
Column:

m = AHo held up by

F = (Patm Ptop) A = mg = AHog

Barometer

Patm = Ptop + P gHo


12

Manometer
Example:

Column height and pressure difference

Find P for a 10 m column of liquid water or air, assuming


densities of 1000 and 1 kg/m3 respectively, use g = 10 m/s2.

Solution

____

______

Pliq = gH = 1000 kg/m3 10 m/s2 10 m = 100 kPa

Manometer

Patm = gH = 1 kg/m3 10 m/s2 10 m = 0.1 kPa


We can neglect P in atmospheric air for most cases.

13

Energy and Temperature


Energy on the macroscale can be written as
E = Internal + Kinetic + Potential = U + KE + PE
2

= mu + mV + mgZ
velocity and elevation are for the center of mass.
The internal energy u has similar terms on the microscale

A diatomic molecule, O2, N2 .


2 modes of rotation ( x, z axis)
1 mode of vibration (in y axis)

u = uext molecule + utranslation + uint molecule


Term 1: potential energy from intermolecular forces fct. of distance
strong (solid, liquid) weak for a gas (distance is large)
Term 2: molecular kinetic energy
Term 3: depends on structure of molecule

A H2O molecule, 3 modes of vibration,


3 modes of rotation (not shown)

uint molecule = upotential + urotation + uvibration + uatoms


Each mode of energy possesses kT of energy in average, k is
Boltzmans constant. Translation always has 3 modes (x, y, z).
14

Temperature
Temperature is a measure of hotness which is a sensible level of average energy in
atoms and molecules and photons. Energy (frequency) has a distribution that is
characteristic for a single temperature. Recall the average energy per energy mode
(degree freedom) is kT. In practice we use a thermometer to measure T which rely on
some other property like v or , an ohmic resistance (thermistor) or a voltage from a bimetal junction (thermocouple) all sensitive to T.
Relative T (has offset):
Absolute T ( T 0):
Ice point at 1 atm:
Very cold:

Celcius
Kelvin

C
K

0.01 oC,
32 F
40 oC, 40 F

or
or

Fahrenheit F
Rankine
R

Steam point: 100 oC,


(at this point TC = TF)

212 F

TK = TC + 273.15
TR = TF + 459.67 = 1.8 TK

TC
-40
-17.8
0
10
20
25
30
37.8
50
70
100

TF
-40
0
32
50
68
77
86
100
122
158
212

Later we show the ideal gas temperature scale, chapter 2, and the thermodynamic
temperature scale, chapter 5, and prove they are the same as the absolute T above.

15

Thermocouples, thermistors

16

Chapter 2

Phase Boundaries and The P-v-T Surface


The Two Phase States
The Liquid and Solid States
The Superheated Vapor States
The Ideal gas States
Compressibility Factor
Equations Of State (EOS)
Computerized Tables

17

Phase Boundaries and The P-v-T Surface


Complete phase diagram (P, T) separates the solid (S),
the liquid (L) and the vapor (V) phases.
Sublimation line (S above, V below)
Fusion line (S left, L right)
Vaporization curve (L above, V below)
On each curve: P = Psat(T)
or T = Tsat(P)
One point on each curve is a pair (Psat, Tsat)
State a:
Superheated vapor (T > Tsat for same P)
Expanded vapor (P < Psat for same T)
State b:
Compressed liquid (P > Psat for same T)
Subcooled liquid (T < Tsat for same P)

Vaporization curve

Critical Point and Triple Point data

Water
CO2
O2
N2

Tc, oC
374
31
-118
-147

Pc, MPa
22
7.4
5.1
3.4

Ttp, oC
0.01
-56
-219
-210

Ptp, kPa
0.6113
520
0.15
12.5

18

Phase Boundaries and The P-v-T Surface


The phase diagram for water

The phase diagram for CO2

Notice the P axis must be log(P) to fit the large range.


19

The P-v-T surfaces


Show the (T, v) combinations following constant P processes for water
Small vs are liquid
Large vs are vapor (gas)
Liquid and vapor regions
are separated by a 2-phase
region of mixtures with a
combination of liquid and
vapor.

liquid
vapor

The borders are the


Saturated liquid line and
Saturated vapor line
They meet at critical point

20

The B Section Tables for Water


Saturated two-phase liquid + vapor region
Table B.1.1 Gives listing of
Tentry Psat, vf, vfg, vg, .
Table B.1.2 same but with
Pentry Tsat,
vf vfg vg
Psat as function of T

21

The Tables for Water


Table B.1.3 superheated vapor along a constant P curve: Tentry, v,
Table B.1.4 compressed liquid

TABLE B.1.3
Superheated
Vapor

Subheading P (Tsat)
22

The Tables for Water


The saturated solid-vapor table and the sublimation line

Table B.1.5 Gives listing of

Tentry Psat, vi, vig, vg, .

23

The Tables for Water


Example 2.1
Determine the phase for each of the following water states using table B.1 and indicate
the relative position in the P-v, T-v and P-T diagrams.
a. 120oC, 500 kPa
b. 120oC, 0.5 m3/kg

Solution

____

_____

a. Enter B.1.1: T = 120oC: Psat = 198.5 kPa < P = 500 kPa so compressed liquid.
Enter B.1.2: P = 500 kPa: Tsat = 151.86oC > T = 120oC

so subcooled liquid

b. Enter B.1.1: T = 120oC: vf = 0.00106 < v < vg = 0.891 86 m3/kg

24

The Two Phase States


Consider a mixture of some liquid in equilibrium
with some vapor. For the combination we can
write:
V = Vf + Vg = mf vf + mgvg
m = mf + mg
Average specific volume
mf
mg
v = V/m = m vf + m vg
v = (1 x) vf + x vg
Quality x mg / m (mass fraction: 0 x 1)
Defining vfg = vg vf we can also write
v = vf + x vfg
v is the mass fraction weighted average of vf and vg
x = mass fraction of vapor, 1 x = mass fraction of liquid
25

The Superheated Vapor States


Example 2.3
Determine the phase for each of the following states using the table in Appendix B and
indicate the relative position in the P-v, T-v and P-T diagrams.
a. Ammonia 30oC, 1000 kPa
b. R-134a 200 kPa, 0.125 m3/kg

Solution

____________________

_________

a. Enter B.2.1: T = 30oC: Psat = 1167 kPa since P < Psat it is superheated vapor.
If entry with 1000 kPa: Tsat 25oC and we see it is superheated about 5oC.

26

Ideal Gas Law

A different scaling can be used

Pv=RT
PV=mRT=nRT
Here n is the number of moles and M is the molecular mass.

n=m/M
From ideal gas law: 1 mol occupies same V at a given (P, T) regardless of which substance it is.
Compare a mass at state 1 with same mass at a state 2:

mR=

P2V2 P1V1
=
T2
T1

Differentiate the ideal gas law with time for constant state (P, T ) to get:

.
.
. _
P V = m R T = n RT

(2.1

27

Ideal Gas Law


Example 2.6

28

Ideal Gas Law


When do you have an ideal gas?
For very large v, so molecular distances are large (very small force between molecules)
To get a sense look at a T-v diagram for water.
If T is higher you can allow smaller vs and still have an ideal gas.

29

The Compressibility Factor


The deviation from the ideal gas law can be expressed by a factor Z so

P v = Z RT
For an ideal gas Z = 1 and for states approaching liquid Z becomes very small. For very high pressures Z can
actually be higher than 1. A chart for nitrogen gives a general shape of a compressibility chart.

30

Equations of State
The P-v-T surface is approximated in an equation of state. Several of these are extensions of the ideal gas law
as

P=

RT
a
2
v b v + cbv + db2

Here a and b are scaled to the critical properties

a = ao Pc x2 ; b = bo x ;

x = RTc/Pc

c and d are model constants shown in Tabel. D.1 including a correction with the accentric factor,

31

Work at a Moving Boundary of a Compressible Substance


Work from substance to piston
W = F dx = PA dx = P dV
2

=
P dV = area

1W2

To evaluate:

P = function of V
1W2

= Function(1, 2, path)

For example from figure


dV < 0

so

1W 2

is negative

Magnitudes:
1W2 A < 1W2 B < 1W2 C

32

Work at a Moving Boundary of a Compressible Substance


Example 3.4 continued
P = C1 + C2V;

C2 = ks /A2

2
1W2

=
P dV = area under the process curve
1

1
W
=
1 2 2 (P1 + P2)(V2 V1)
1
= 2 m (P1 + P2)(v2 v1)

33

Work in a Polytropic Process


Polytropic process definition:
PV n = constant = C

or

Pv n = constant

Indicated work ( n 1):


2

n
C V dV =
P dV =
1W2 =

C
2
(
V1 n )1
1n

C
1n
1n
(
V2
V1 )
1n
1
n 1n
n 1n
=
(
P2V2 V2
P1V1 V1 )
1n
1
=
(P V P1V1)
1n 2 2
=

Indicated work ( n = 1):


2

V2
2

P dV = C V dV = C ln V1 = P1V1 ln V
1W2 =

34

Work in a Polytropic Process


Example 3.6
An ideal gas in a piston cylinder starts out with 200 kPa, 0.04 m3. Let us look at 4
different possible processes and find the work for each case.

Solution __________________________________________________
a. Process: P = C, Heat the gas to V2 = 0.1 m3
2

1W2

=
P dV = P dV = P (V2 V1)
1

= 200 kPa (0.1 0.04) m3 = 12.0 kJ


b. Process: T = C, Heat the gas to V2 = 0.1 m3
Ideal gas: PV = m RT = C so polytropic with n = 1
2

V2
P dV = P1V1 ln V
1W2 =
1
1

= 200 kPa 0.04 m3 ln

0.1
= 7.33 kJ
0.04

To do the process the mass (load) on piston varies


35

Work in a Polytropic Process


Example 3.6 continued
c. Process: Polytropic with n = 1.3, Increase volume to V2 = 0.1 m3
1.3

P2 = P1 (V1 / V2) = 200 kPa (0.04 / 0.1)


1
W
=
1 2 1 n (P2V2 P1V1)

1.3

= 60.77 kPa

= 1 1.3 (60.77 0.1 200 0.04) kPa m3


= 6.41 kJ
d. Process: V = C, Cool the gas to P2 = 100 kPa
2
1W2

=
P dV = 0
1

Comment:
To do the process (c) the mass (load) on piston varies
To do the process (d) the piston is locked in place

36

The Internal Energy


Main characteristic:
u = uext molecule + utranslation + uint molecule
uint molecule = Potential + Rotation + Vibration + Atoms
uext molecule is sensitive to molecular distances and all parts are sensitive to T.
For liquid and solid phases this first part is significant (small distances) and it
diminishes for the vapor states going to zero for ideal gas states.
Information is in the B section tables for substances as fct(T, P).
For a two phase mixture of liquid and vapor
U = Uliq + Uvap = mliquf + mvapug
u = U/m = (mliq/m) uf + (mvap/m) ug
u = (1 x) uf + x ug
u = uf + x ufg

37

The Internal Energy


Example 3.8
Determine the missing property (P, T, v, x) for water at each of the following states:
a. T = 300oC, u = 2780 kJ/kg ;
b. P = 200 kPa, u = 2000 kJ/kg

Solution __________________________________________________
a) Table B.1.1 at 300oC: u > ug = 2563.0 kJ/kg, so superheated vapor,
x is undefined,
Table B.1.3 between 1600 and 1800 kPa at 300oC:
1600 kPa, 300oC: u = 2781.03 kJ/kg; v = 0.15862 m3/kg
1800 kPa, 300oC: u = 2776.83 kJ/kg; v = 0.14021 m3/kg
linear interpolation:
2780 2781.03
P = 1600 + 200
= 1600 + 200 0.24524
2776.83 2781.03
= 1648 kPa
v = 0.15862 + (0.14021 0.15862) 0.24524 = 0.1542 m3/kg

38

The Internal Energy


Example 3.8 continued
Determine the missing property (P, T, v, x) for water at each of the following states:
a. T = 300oC, u = 2780 kJ/kg ;
b. P = 200 kPa, u = 2000 kJ/kg

Solution __________________________________________________
b) Table B.1.2 at 2000 kPa:
uf = 906.4 < u < ug = 2600.3 kJ/kg two-phase
u = 2000 = uf + x uf g = 906.4 + x 1693.8
x = 0.6456
v = vf + x vfg = 0.001 177 + 0.6456 0.098 45
E

= 0.064 74 m3/kg

39

The Enthalpy
Example: The constant P process
Recall the work for a constant pressure process
1W2

P dV

= P dV = P (V2 V1)

Assume changes in kinetic and potential energies are zero, the


energy equation gives the heat transfer as
1Q2

= m (u2 u1) + 1W2 = m (u2 u1) + P (V2 V1)


= m (u2 u1) + P m (v2 v1)
= m [(u2 + P2v2) (u1 + P1v1)]

Definition of enthalpy
H U + PV ;

h u + Pv

Enthalpy has same units as u [kJ/kg], and for a two-phase state


h = (1 x) hf + x hg = hf + x hfg
as the mass fraction [1 x and x] averaged property (same as for v, u).
Comment: Any combination of thermodynamic properties is another
property. Enthalpy is used because it appears often.

40

The Enthalpy
Example 3.12
A piston cylinder has 0.1 m3 with 0.5 kg steam at 400 kPa. Heat is added to reach a final
temperature of 300oC while the pressure is constant. Find the heat transfer and work.

Solution ________________________________________
Control volume all the steam, a control mass.
Process:

P = C.

State 1 (P1, v1 = V1/m): From Table B.1.2 we get


v1 = V1/m = (0.1/0.5) m3/kg = 0.2 m3/kg = vf + x1 vfg
0.2 0.001084
= 0.4311
0.4614
h1 = hf + x1 hfg = 604.74 + 0.4311 2133.8 = 1524.7 kJ/kg

x1 = (v1 vf)/ vfg =

State 2 (P2, T2): B.2.2 gives


v2 = 0.6548 m3/kg,

h2 = 3066.8 kJ/kg

41

The Enthalpy
Example 3.12 continued
Work term from area in (P-v) diagram
1W2

= Pm (v2 v1) = 400 kPa 0.5 kg (0.6548 0.2) m3/kg = 91 kJ

Heat transfer from energy equation


1Q2 = m (u2 u1) + 1W2 = m [(u2 + P2v2) (u1 + P1v1)]
= m (h2 h1) = 0.5 kg (3066.8 1524.7) kJ/kg = 771.1 kJ

Comment: We could have found (u1, u2) and not used the enthalpies, same result.

42

The Specific Heats


Specific heats
Previous cases (KE = 0 and PE = 0 ) give for an incremental process per unit mass:
dv = 0

w = 0

so

q = du

dP = 0

w = P dv

so

q = dh

We want to express this in terms of a property we can measure: T. Due to the above
processes we define the specific heats as:
u
Cv = T ;
v

h
CP = T
P

Thermodynamic properties, a function of the state. They simplify to be fct(T) only, as an


approximation, in the single phase regions: solid, liquid and ideal gas.
du
Cv dT ;

dh
CP dT

No phase change

Then
du = Cv dT

and

u2 u1 = Cv dT Cv (T2 T1)

dh = CP dT

and

h2 h1 = CP dT CP (T2 T1)

where the last expression assumes constant specific heats.

43

The Specific Heats: Solids and Liquids


Specific heats for solids and liquids
Matter in these phases are dense and nearly incompressible so
v = constant and v is small
Then
dh = du + d(Pv) = du + P dv + v dP du + v dP
so
h2 h1 = u2 u1 + v dP = u2 u1 + v (P2 P1)
Cv (T2 T1) + v (P2 P1)
If pressures are moderate then the last term can be neglected thus changes in u and h are
the same and the two specific heats are the same.
C = Cv = CP are listed for some solids and liquids in Tables A.3, A.4, F.2 and F.3
Liquids in [kJ/kg-K]:
Solids in [kJ/kg-K]:

water (4.18)
ice (2.04)

fuels CxHy (2 - 2.5) metals (0.15 1)


granite (0.9)
metals (0.4 typ.)

If temperature varies significantly or great accuracy is required then a model for the
variation of C = Cv with temperature is required and integral must be done
u2 u1 = Cv dT
44

The Specific Heats: Ideal Gases


Specific heats for ideal gases
Large intermolecular distance gives small potential energy between molecules so only the
internal (like rotation, vibration) molecular energy terms for u are present.
u = uext molecule + utranslation + uint molecule utranslation + uint molecule = u(T)
Pv = RT
so
h = u + Pv = u + RT = h(T)
du
Cv0 = dT ;

Tables:

dh
CP0 = dT = Cv0 + R

u2 u1

Cv0 dT

Cv0 (T2 T1)

h2 h1

CP0 dT

CP0 (T2 T1)


A.5, F.4

A.7-9, F.5-6

A.6

Units for Cv0, CP0 and R: kJ/kg-K or Btu/lbm-R


The zero subscript indicates ideal gas, any gas when P 0 (v ) is an ideal gas.
45

The Specific Heat Function of Temperature

Specific heat with temperature


Monatomic gases Ar, He, ... cannot
rotate or vibrate so specific heat is
constant. Only translation active so
specific heat also low.
The complex molecules have more
modes of internal energies possible.
See Appendix C for more details.
Notice CP0/R is dimensionless

46

The Specific Heat Function of Temperature


Example 3.13
Calculate the change of enthalpy as oxygen is heated from 300 K to 1500 K. Assume
ideal gas behavior.

Solution ________________________________________
Table A.8:

h2 h1 = 1540.2 273.2 = 1267.0 kJ/kg

Table A.6:

h2 h1 =

CP0 dT = 1000 CP0 d


=1.5
1
1
1
= 1000 [0.88 2 0.0001 2 + 3 0.543 4 0.33 4 ] =0.3
= 1241.5 kJ/kg

Table A.5:

h2 h1 = CP0 (T2 T1) = 0.922 kJ/kg-K (1500 300) K = 1106.4 kJ/kg

The result goes from most accurate (A.8) to least accurate (A.5).
Notice how the slope of the cord is close to CP0(Tavg = 900 K)
1267 kJ/kg
slope = (h2 h1) / (T2 T1) = 1200 K = 1.056 kJ/kg-K
CP0 900 K = 0.88 0.0001 0.9 + 0.54 0.92 0.33 0.93
= 1.077 kJ/kg-K

47

The Entropy
Consider a cycle composed of two processes, A + B moving a substance between states 1
and 2. Assume both of these are reversible then
2

Q
=
0
=

T
1

1 Q
Q
T A +


2 T B

Compare this to a reversible cycle with path C + B


2 Q + 1 Q

Q
=
0
=
T C T B
T
1
2
Since the second integral is common we get by subtraction
2 Q = 2 Q = Fct(1,2)
T A
T C
1
1
Integral is the same for all reversible paths, define a state function:
Entropy S:

Q
dS T rev

or

q
ds T rev

[kJ/kg-K]

2 q
s2 s1 =
T rev
1
48

The Entropy
Entropy of a pure substance.

Entropy for water, T-s diagram

Entropy is tabulated together with other


properties as (T, P, v, u, h, s) in the B section
of appendix. Properties (u or h) and s are
zero at a reference point that depends on
the substance.
In the two-phase region s relates to the
saturated liquid-vapor values as (v, u, h)
s = (1 x)sf + x sg
= sf + x sfg

49

The Entropy
T-s diagram from CATT3 for water.
Showing P = 1.55 MPa & v = 0.13 m^3/kg
curves with the plot option

Enthalpy-Entropy for water,


h-s diagram, Mollier diagram

Aqua, red separated by P = Pcritical

50

The Entropy
Entropy changes in reversible processes.
In general
q
ds = T rev

and

qrev = T ds

Notice:
1. Change ds follows magnitude and sign of q
2. For a given q change ds is smaller for high T
3. For a reversible process we find heat transfer
2

qrev = T ds

1q2

=
T ds = area
1

These points are illustrated in the figures.

51

The Entropy
Entropy changes in reversible processes.
From the definition of the entropy there are two processes
for which we can evaluate the integral without further
developments.
Reversible adiabatic process:
q
ds = rev = 0
T

q = 0

T-S diagram

so

s = constant

2
1q2

=
T ds = area = 0
1

This is called an isentropic process.


Reversible isothermal process:
2
s2 s1 =

T = constant so

1q2
q
T rev = T

The two processes and the


area below the process curve
shows the heat transfer.

2
1q2

=
T ds = area = T (s2 s1)
1

52

The Carnot Cycle in a T-s diagram


Entropy changes in the Carnot Cycle.

Carnot Heat Engine


T-S diagram

The Carnot cycle consists of 2 adiabatic and 2 isothermal


processes so the cycle looks like a rectangle in a T-s
diagram as shown. Notice how the heat transfer is the area
below the process curve as in the heat engine
1q2

= TH (s2 s1) = qH

3q4

= TL (s4 s3) = qL

and
The two isentropic processes (rev. and adiabatic) give
s2 = s3

and

s4 = s 1

Carnot Heat Pump

so the entropy increase in 1-2 equals the decrease in the


3 4 process. The net work equals the net heat transfer so
the cycle efficiency is
wnet qH qL area 1-2-3-4-1
= q = q
= area 1-2-b-a-1
H
H
The reversed cycle is a refrigerator or heat pump and it has
opposite changes in entropy and all heat transfers.

53

The Entropy Change in Evaporation


Entropy changes in reversible processes.
Consider a constant pressure process of boiling
saturated liquid to saturated vapor from state 1 to state 2
in the diagram. From the energy equation
1q2

= u2 u1 + 1w2 = h2 h1 = hfg

Constant P process

The entropy change is


2 q
1q2 hfg

s2 s1 = sfg = T rev = T = T
1

relating the entropy of evaporation sfg to the enthalpy of


evaporation hfg. This is a consistency requirement for
the tables of thermodynamic properties.
hfg
sfg =
T

54

Entropy Change for a Solid or Liquid


For a solid or liquid we have the behavior for an incompressible substance:
v constant;

v also small;

du = C dT

du P
du
C
ds = T + T dv T = T dT
If specific heat is constant we can integrate
T2
2 C

s2 s1 = T dT = C ln T
1
1
Since v is constant u and s are functions of temperature only. Thus in an isentropic
process the temperature does not change, like pumping a liquid to higher pressure.
Example 6.3
Liquid water is heated from 20oC to 90oC. Find the change in entropy using constant
specific heat and by using the steam tables.

Solution _____________________________________________________
Table A.4:

T2
363.15
s2 s1 = C ln T = 4.18 kJ/kg-K ln 293.15 = 0.8951 kJ/kg-K
1

Table B.1.1:

s2 s1 = sf 90 sf 20 = 1.1925 0.2966 = 0.8959 kJ/kg-K

55

Entropy Change for an Ideal Gas


Now use the two Gibbs relations for an ideal gas
Ideal gas:

Pv = RT ;

du = Cv0 dT ;

dh = Cp0 dT

Gibbs:

RT
T ds = du + P dv = Cv0 dT + v dv
Cv0
R
ds = T dT + v dv
v2
2 Cv0
s2 s1 = T dT + R ln v
1
1

Gibbs:

(6.13)

RT
T ds = dh v dP = Cp0 dT
dP
P
Cp0
R
ds = T dT P dP
P2
2 Cp0
s2 s1 = T dT R ln P
1
1

(6.15)

Conclusions:
Ideal gas: u(T), h(T) but s(T, P) or s(T, v)
Entropy increases with T, increases with v, but decreases with P
Model for specific heat (recall Cp0 = Cv0 + R) needed to evaluate the integrals

56

Entropy Change for an Ideal Gas


Constant specific heat model:
Cp0 , Cv0 assumed constant and found in Table A.5, F.4
Integrals are done to give:
P2
2 Cp0
s2 s1 = T dT R ln P
1
1
v2
2 Cv0
s2 s1 = T dT + R ln v
1
1

T2
P2
s2 s1 = Cp0 ln T R ln P
1
1

(6.16)

T2
v2
s2 s1 = Cv0 ln T + R ln v
1
1

(6.17)

The expressions are alternatives and consistent. Use Cp0 = Cv0 + R and ideal gas law to
mathematically transform from one to the other equation.
Variable simple specific heat model:
Cp0(T) = Fct(T) polynomial, exponential or power functions

Cv0(T) = Cp0(T) RT

also a function of T only

Table A.6 shows an example of polynomials used for function Cp0(T).


57

Entropy Change using the Standard Entropy


Variable complex specific heat model:
Standard entropy tabulated:

Absolute entropy:

T Cp0
0

dT
+
s
ref
To T

(6.18)

P2
R ln
P1

(6.19)

s(T,

0
P0) = s T

s2

0
0
s1 = sT2 sT1

P
0
s(T, P) = sT R ln P

Function is shown for air in A.7, F.5 and other gases in A.8, F.6 with an offset to make
0

the standard entropy a certain value at T0. For other Tables sref = s(T0, P0) may be set to
zero. Normally we need a difference so any offset will cancel out.
0
0
T2 Cp0
0
T1 Cp0
0

Notice: sT2 sT1 =


dT
+
s

dT

s
ref
ref
To T
To T

T2 Cp0
To Cp0
2 Cp0
=
dT +
dT = T dT
To T
T1 T
1
58

Entropy Change Using Different Models


Example 6.4
Find the change in specific entropy of oxygen when state changes from 300 K, 200 kPa
to 1500 K, 150 kPa.

Solution _____________________________________________________
The most accurate result is using standard entropy from A.8 corrected for pressure as
s2

0
0
s1 = sT2 sT1

P2
150
R ln P = 8.0649 6.4168 0.2598 ln 200 = 1.7228 kJ/kg-K
1

The next best evaluation is using the equation from Table A.6 to get
P2
s2 s1 = CP0/T dT = CP0/ d R ln P
1
1

=1.5

= [0.88 ln 0.0001 + 2 0.542 3 0.33 3 ] =0.3 R ln

P2
P1

= 1.7058 kJ/kg-K
Constant specific heat evaluation becomes
T2
P2
1500
150
s2 s1 = Cp0 ln T R ln P = 0.922 ln 300 0.2598 ln 200 = 1.5586 kJ/kg-K
1
1
This last evaluation is too low since Cp0 is taken at 300 K and it increases with T so in
Example 3.13 we found the average should be like Cp0 = 1.06 kJ/kg-K.

59

Process Equation Using Entropy


Process: Isentropic, s = constant.
A simple reversible adiabatic compression or expansion is an isentropic process. From
the previous expressions for changes in s we can get relations between P, v and T. A set
of explicit relations are obtained using constant specific heat.
Constant specific heat model:
T2
P2
T2
v2
0 = s2 s1 = Cp0 ln T R ln P = Cv0 ln T + R ln v
1
1
1
1
First one gives:

ln (P2 / P1) = (Cp0/R) ln(T2 / T1) = ln[ (T2 / T1)Cp0 / R ]


Cp0 / R

P2 = P1 [T2 / T1]

Second one gives:

Cv0 / R

v2 = v1 [T1 / T2]

k/(k 1)

= P1 [T2 / T1]

k1

= v1 [T1 / T2]

With the ratio of specific heats k as


Cp0
Cp0
k
=
=
R Cp0 Cv0 k 1

and

Cp0
k=C
v0
60

Process Equation Using Entropy


The Isentropic Process continued
The relations can be extended with specific volume by the ideal gas law Pv = RT
P2 T2 k/(k1) v1 k
=
=
P1 T1
v2
T2 P2 (k1)/k v1 k1
=v
T1 = P1
2
These relations are known as the power relations and are valid for an isentropic process
in an ideal gas with constant specific heats. If one of the ratios is known in an isentropic
compression or expansion (typically the P or v ratio) the other ratios can be found.
The pressure to volume relation can be rewritten to recognize
P vk = constant
as a polytropic process with polytropic exponent n = k. The different processes are:

The polytropic processes:

P vn = constant

Isobaric:

n = 0, P = constant

Isentropic:

n = k, s = constant

Isothermal:

n = 1, T = constant

Isochoric:

n = , v = constant
61

Polytropic Process in P-v and T-s diagrams


The polytropic processes:

P vn = constant

Isobaric:

n = 0, P = constant

Isentropic:

n = k, s = constant

Isothermal:

n = 1, T = constant

Isochoric:

n = , v = constant

62