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Introduction to Thermodynamics
Thermodynamic System and Control Volume
Properties, Processes and Cycles
Units
Specific Volume and Density
Pressure
Energy and Temperature
1
Control Mass:
Control Volume:
Control surface
Control surface
Water
Loop
Heat
Loop
(Condenser)
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
Pressure
Pressure is force per unit area (normal stress)
= lim
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
____
_____
or
F
P=A
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
Manometer
Barometer
The top pressure is near zero (perfect vacuum)
Column:
m = AHo held up by
Barometer
Manometer
Example:
Solution
____
______
Manometer
13
= mu + mV + mgZ
velocity and elevation are for the center of mass.
The internal energy u has similar terms on the microscale
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
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
17
Vaporization curve
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
liquid
vapor
20
21
TABLE B.1.3
Superheated
Vapor
Subheading P (Tsat)
22
23
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
24
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
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
28
29
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
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
=
P dV = area
1W2
To evaluate:
P = function of V
1W2
= Function(1, 2, path)
so
1W 2
is negative
Magnitudes:
1W2 A < 1W2 B < 1W2 C
32
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
or
Pv n = constant
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
=
V2
2
P dV = C V dV = C ln V1 = P1V1 ln V
1W2 =
34
Solution __________________________________________________
a. Process: P = C, Heat the gas to V2 = 0.1 m3
2
1W2
=
P dV = P dV = P (V2 V1)
1
V2
P dV = P1V1 ln V
1W2 =
1
1
0.1
= 7.33 kJ
0.04
1.3
= 60.77 kPa
=
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
37
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
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)
Definition of enthalpy
H U + PV ;
h u + Pv
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.
h2 = 3066.8 kJ/kg
41
The Enthalpy
Example 3.12 continued
Work term from area in (P-v) diagram
1W2
Comment: We could have found (u1, u2) and not used the enthalpies, same result.
42
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
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)
43
water (4.18)
ice (2.04)
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
Tables:
dh
CP0 = dT = Cv0 + R
u2 u1
Cv0 dT
h2 h1
CP0 dT
A.7-9, F.5-6
A.6
46
Solution ________________________________________
Table A.8:
Table A.6:
h2 h1 =
Table A.5:
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
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.
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
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
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
T = constant so
1q2
q
T rev = T
2
1q2
=
T ds = area = T (s2 s1)
1
52
= TH (s2 s1) = qH
3q4
= TL (s4 s3) = qL
and
The two isentropic processes (rev. and adiabatic) give
s2 = s3
and
s4 = s 1
53
= u2 u1 + 1w2 = h2 h1 = hfg
Constant P process
s2 s1 = sfg = T rev = T = T
1
54
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:
55
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
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
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
dT
s
ref
ref
To T
To T
T2 Cp0
To Cp0
2 Cp0
=
dT +
dT = T dT
To T
T1 T
1
58
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
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
P2 = P1 [T2 / T1]
Cv0 / R
v2 = v1 [T1 / T2]
k/(k 1)
= P1 [T2 / T1]
k1
= v1 [T1 / T2]
and
Cp0
k=C
v0
60
P vn = constant
Isobaric:
n = 0, P = constant
Isentropic:
n = k, s = constant
Isothermal:
n = 1, T = constant
Isochoric:
n = , v = constant
61
P vn = constant
Isobaric:
n = 0, P = constant
Isentropic:
n = k, s = constant
Isothermal:
n = 1, T = constant
Isochoric:
n = , v = constant
62