Thermodynamic Properties August 26, 2010

Outline
Unit one – Properties of Pure
Substances • Extensive, E, m, intensive, T, P, , and
specific, e = E/m, variables
Larry Caretto •  = m/V = 1/v => density = 1/(sp. vol.)
Mechanical Engineering 370 • Look at P-v-T data for real substances
Thermodynamics • Ideal gases PV = nRuT = mRT
– Engineering gas constant: R = Ru / M
August 26, 2010 – With v = V/m, Pv = RT
• Use of V or v = V/m gives difference between
PV = mRT and Pv = RT
2

Thermodynamic Variables Thermodynamic System

• Extensive variables (volume, mass, • Basic unit of analysis defined by boundaries
energy) depend on size of system where all interactions occur
• State of system defined by properties
• Intensive variables (pressure,
temperature, density) do not • Interaction of system with surroundings
– Can interchange energy and mass
• Specific variables are ratio of an – Open/closed systems: Have/Do not have mass
extensive variable to mass (e.g. specific addition or removal
volume, v = V/m) • Open system called control volume
– Isolated system: constant energy and mass
• General notation, if E is an extensive – All interactions across boundaries
variable, e = E/m is specific variable
3 4

Thermodynamic State Ideal Gas Equations

• Two independent intensive properties • From chemistry: PV = nRuT
determine the state of a simple • Ru = Universal gas constant = 8.314
compressible system kJ/kmol·K = 8.314 kPa · m3/kmol·K =
• Once the state of a system is deter- 10.73 psia ·ft3/lbmol ·K
mined all other properties are known • Engineering gas constant, R = Ru/M
• Thermodynamic processes are a • Definition of mol, n = m / M PV = nR T
continuous series of states known as a • PV = (m/M)(MR)T = mRT
u

quasi-equilibrium process PV = mRT

• P(V/m) = Pv = RT
Pv = RT
5 6

ME 370 – Thermodynamics 1
Thermodynamic Properties August 26, 2010

Z = 1 is ideal gas
TR = T/Tcrit
Why Use Ideal Gas?
• Simple equations
• Real gas behavior close to ideal gas for
low pressure (or high temperature)
Figure 3-51 from Çengel,
• Want P low compared to Pc
Thermodynamics An Engineer
Approach, 2008 • Example calculation: find specific
volume of water at 1,000oC and 10 kPa
• Compare to property table value of v =
58.758 m3/kg for water (page 918)
PR = P/Pcrit 7 8

Finding R Ideal Gas Calculation

• Table A-1, page 908: for water, R =
1kJ = 1 kN·m = 1 (kN/m2)·m3 = 1 KPa·m3 0.4615 kJ/kg·K = 0.4615 kPa·m3/kg·K
0.4615 kPa  m 3
(1273.15 K )
RT kg  K 58.756 m 3
v  
P 10 kPa kg

• Error is only 0.0017% at this point

• Ideal gas often used for “permanent
gases” such as air
9 10

Ideal Gas Calculation II P-v-T for Real Substances

• A volume of 20 ft3 at a pressure of • Three phases: gas, liquid and solid
300 psia contains 20 lbm of Helium; • Look at gas and liquid
what is the temperature? • Thought experiment
• T = PV / (mR) – Add heat to a liquid at constant pressure;
• R = 2.6809 psia•ft3/lbm•R (page 958) measure T and v

300 psia 20 

– After a while vapor starts to form
PV ft 3 • Heat addition increases volume by converting
T   111.9 R  347.7 o F
mR 2.6809 psia  ft 3 liquid to gas while T is constant (at constant P)
(20 lbm ) – Finally have only gas that expands readily
lbm  R
• Ideal gas has v/T = const (at constant P)
11 12

ME 370 – Thermodynamics 2
Thermodynamic Properties August 26, 2010

Thought Experiment II Thought Experiment III

• Repeat experiment with difference in
variables
• Hold temperature constant
• Add heat and measure pressure, P, and
specific volume v
• States 2 to 4 are liquid vapor transition • Have same liquid-vapor transition
– Liquid and vapor have same properties (P, – P is constant if T is constant
vf = 1/f, vg = 1/g, and T) during transition; – Liquid and vapor properties constant in
only relative proportions change transition only relative proportions change
Figures 3-6 to 3-10 from Çengel, Thermodynamics An
Engineering Approach, 2008 13 14

Thought Experiment Results P-v Diagram for Water

1.E+08

• A constant temperature line on P-v

1.E+07 T = 50 C
– Looks like a hyperbola in the gas region
T = 100 C
Pressure (Pascals)

– Has constant pressure during the transition T = 200 C

from liquid to gas 1.E+06
T = 300 C
– Is nearly vertical in the liquid region Tcrit
1.E+05
• The points where the transition between Gas T = 500 C
Liquid
liquid and gas take place for different T = 1000
C
1.E+04
temperatures: saturation curve Sat
Mixed
• Results of “experiment” on next slide 1.E+03
15 0.0001 0.001 0.01 0.1 1 10 100 1000
Specific Volume (cubic meters per kilogram)

Critical P-v Diagram for Water Superheat P-v Diagram for Water
1.E+08
50,000

45,000
Sat
40,000 Sat
Pressure (Pascals)

T = 200 C 35,000 T = 50 C
Pressure (Pascals)

T = 300 C 30,000 T = 100 C

1.E+07 T = 200 C
Tcrit 25,000
T = 300 C
20,000
T = 500 C
Tcrit
15,000
T = 1000 T = 500 C
C 10,000
T = 1000
C
5,000
1.E+06
0.001 0.01 0.1 1 0
Specific Volume (cubic meters per kilogram) 0 50 100 150 200
Specific Volume (cubic meters per kilogram)

ME 370 – Thermodynamics 3
Thermodynamic Properties August 26, 2010

What We Have to Do Finding Properties

• Find all intensive thermodynamic • When we have a mixture of liquid and
properties when we are given only two gas T and P are not independent
intensive properties
• For a single phase (liquid or gas) T and
– Two independent, intensive properties
define state P are independent (can specify state)
• Here we will discuss only four intensive • In the mixed region we use vapor mass
properties, P, v, T, and fraction of vapor fraction, called quality, x
in mixed region called the quality, x mg v  vf v  v f • v and v are found
• Approach used here will be applied to x   f g
mg  m f v g  v f v fg from either T or P
finding other properties: internal energy,
enthalpy, and entropy 19 20

Quality Derived Saturation Properties

Sat
• Mixed region volume is sum of liquid Saturated liquid (f) and T = Tsat(P)
P = Psat(T)
and vapor volumes saturated vapor (g)
V mg mf mg m  mg properties can be found
V  mg v g  m f v f   vg  vf  vg  vf
m m m m m if P or T are known
P

• Use quality: x = mg/(mg + mf) = mg/m

v
V mg
 vg 
m  mg
v f  xvg  (1  x)v f  v f  xv g  v f  Use quality,
v  vf
m m m x
x, in mixed vg  v f
• Will apply this later to other properties region
vf v vg v  v f  xv g  v f 
21 22

Saturation Tables
• See steam tables, pp 914–923
• Saturation tables
– Table A-4 has T as lookup variable
– Table A-5 has P as lookup variable
– Same results in each table
• Other variables besides specific volume
• Use Table A-4, Page 915, T = 220oC
have saturated liquid (f) and gas (g)
• Find P = 2319.6 kPa, vf = 0.001190
• Example: what are P and v if T = 220oC m3/kg and vg = 0.086094 m3/kg
and x = 0.25?
23 24

ME 370 – Thermodynamics 4
Thermodynamic Properties August 26, 2010

What is v for x = 0.25? What if P and T are Given?

• Found from Table A-4 with lookup T • If these are independent properties then
– P = Psat(T = 220oC) = 2319.6 kPa they define a state
– vf(T = 220oC) = 0.001190 m3/kg • The “superheat” (gas) tables for water
– vg(T = 220oC) = 0.086094 m3/kg (Table A-6, pp 918 – 921) have a set of
v  vf tables for P with rows of data for v
x  v  v f  x(vg  v f )  (1  x)v f  xvg • Data are also given for other properties
vg  v f
v  (1  x)v f  xvg  (1  0.25)
0.001190 m3
 (0.25)
0.086094 m3 • Basic question: Given T and P, how do
kg kg we know if we have a liquid or a gas?
0.022416 m 3
v
kg 25 26

Finding State with Given T and P

Sat
Liquid when T = T1 < T2
T < Tsat(P) or T = T2 >T1
P > Psat(T) Psat(T1)
Psat(T2)
P

Gas when
T > Tsat(P) or
P < Psat(T)

vf v vg
27 28

General Rules
• When we are given T and P we have a
single phase. Is it gas or liquid?
– It is a gas if T > Tsat(P) or P < Psat(T)
– It is a liquid if T < Tsat(P) or P > Psat(T)
– “Superheat” tables have Tsat by P
– Can guess superheat and check
• Example: R134a at 0oC and P = 100 kPa, 400 kPa
• Guess superheat and find at 100 kPa and 0oC, v =
0.21630 m3/kg; at 400 kPa there is no 0oC entry
• Data from page 929
29 30

ME 370 – Thermodynamics 5
Thermodynamic Properties August 26, 2010

Results General Rules Continued

• v(0oC, 100 kPa) = 0.21630 m3/kg • The example did not find a 0oC entry at
• What is v(0oC, 100 kPa)? Page 929 400 kPa because this is a liquid
– The header 0.4 MPa (Tsat = 8.91oC confirms
that T = 0oC < Tsat = 8.91oC
• Approximation for compressed liquid:
v(T,P)  vf(T) Note it’s vf(T)
– To get answer for 400 kPa and 0oC look at
• Why are there no data at T = 0oC and P saturation table for T = 0oC, A-11, page 926
= 400 MPa (= 0.4 MPa)? – v(0oC,400 kPa)  vf(0oC) = 0.0007723 m3/kg
31 32

Two More Problems Review Last Problem

• What is the specific volume for refrigerant • What is the specific volume for refrigerant
134a (R-134a) when the pressure is 90 134a (R-134a) when the pressure is 90
psia and the temperature is 240oF psia and the temperature is 240oF
– R-134a tables in english units: pp. 976-979 – R-134a tables in english units: pp. 978-81
– Guess that this is gas and look in – What if we could not guess that this is gas or
“superheated” tables on page 979 made a wrong guess?
– v = 0.77796 ft3/lbm at given T and P • Use general rule that gas occurs when P <
Psat(T) or T > Tsat(P)
• What is P when T = 240oF and v = • For this problem T = 240oF > Tsat(90 psia) = 72.83oF
0.77796 ft3/lbm? • Also P = 90 psia < Psat(240oF) = 138.79 psia
90 psia 33 34

Find State Given v and (T or P) Given T-v(or P-v); Find P(or T)

Sat
Find vf and vg from T or P T = Tsat(P) • Determine state: find vf and vg from
P = Psat(T)
Liquid if v < vf saturation tables for given T (or P)
Gas if v > vg – If v > vg it is a gas; use superheat table
Otherwise mixed – If v < vf it is a liquid; see below
P

– If vf < v < vg it is in mixed region. Can find x

Liquid Gas • For liquid to use v  vf(T) we must be
Mixed given v-P: find T for which vf(T)= vgiven
• Compressed liquid tables for water
vf v vg
35 36

ME 370 – Thermodynamics 6
Thermodynamic Properties August 26, 2010

Interpolation Interpolation II
• Can use interpolation function on your • For a straight
calculator if you have one y line any two
y2 points on the line
• Basic idea is that you have a table with
can give slope
data pairs (x1, y1) and (x2, y2) Interpo-
• You want to find a value of y for some
lated y y2  y1 y  y1
y 
value of x between x1 and x2 x2  x1 x  x1
y1
• Simplest idea is to assume a straight y  y1 
line between x1 and x2 y2  y1
x1 x2 x x  x1 
37
x Want y for this x x2  x1 38

Interpolation III Example Problem

• Equation for a straight line between • For H2O at P = 2 MPa, what is T when
data pairs (x1, y1) and (x2, y2) is v(m3/kg) = (a) 0.00115, (b) 0.01, (c)0.2?
y2  y1 y  y1 y2  y1 • Table A-5, p 917 At 2000 kPa, vf =
y  y1  x  x1  or 
x2  x1 x  x1 x2  x1 0.001177 m3/kg, vg = 0.099587 m3/kg
– Thus (a) is liquid, (b) is mixed, (c) is gas
• Second form is easier to remember
• For compressed liquid state (a), correct
– It says that the slope between any point
T is one for which vf(T)= 0.00115 m3/kg
(x,y) and the point (x1, y1) is the same as
– Extract from Table A-4, next slide, shows
the slope between (x1, y1) and (x2, y2)
that this vf is between T = 195oC and T =
• First form used for computations 200oC
39 40

Data and Interpolation Example: (b) Mixed, (c) Gas

• We want to find T for v • (b) for mixed region, T = Tsat(2 Mpa) =
= 0.00115 m3/kg 212.38oC; can find quality
– Between 195oC and .01 m
3
 .001177 m
3

200oC v  vf kg kg
x   0.0896  8.96%
v g  v f .099587 m3  .001177 m
3
• For this interpolation x1 kg kg
= 0.001149 m3/kg, x2 = • (c) v = .2 m3/kg at P = 2 MPa found on p.
0.001157 m3/kg, y1 = 921 between T = 600oC and 700oC
195oC and y2 = 200oC
700o C  600 o C  .2 m3  .19962 m3   601.6o C
T  600 o C 
200 o C  195o C  .00115 m 3  .001149 m 3   195.6o C .22326 m
3
 .19962 m
3
 kg kg 
T  195 C 
o
kg kg
.001157 m
3
 .001149 m
3
 kg kg 
kg kg
41 42

ME 370 – Thermodynamics 7
Thermodynamic Properties August 26, 2010

Compressed Liquid Table More on Compressed Liquid

• Not a common table, use here to check • Check approximation that v(P,T)  vf(T)
approximation that v(P,T)  vf(T) for previous problem: v = 0.00115 m3/kg
• Table A-7, page 922, gives v(50 MPa, and P = 2 MPa
100oC) = 0.0010201 m3/kg • Do not have data for compressed liquid
• Table A-4, page 914, gives vf(100oC) = at 2 MPa in table on page 922
0.001043 m3/kg – First entry is at 5 MPa
• Error is about 2% even for a pressure • Have to use double interpolation and
difference of 49.9 MPa between the interpolation with saturation points
actual pressure and saturation pressure – Interpolate between Psat and 5 MPa
43 44

Interpolations Table
2 MPa Compressed liquid data
• We are looking for v = 0.00115 m3/kg
shown here
which is between 180oC and 200oC in
Looking for v = 0.00115
compressed liquid table at 5 MPa m3/kg at P = 2 MPa
• We have to find data at these No data for P < 5 M Pa
temperatures and 2 MPa Use saturated liquid data
– Because 5 MPa is the first table entry we for lower pressure
use saturation as the lower data point At 180oC, vf = 0.001127
vt(T) = v(T, Psat) m3/kg at P = 1.0021 MPa
At 200oC, vf = 0.001157
v(T ,5 MPa)  v f (T ) m3/kg at P = 1.5538 MPa
v(T , 2 MPa)  v f (T )  2 MPa  Psat (T ) Interpolate to get v at 2
5 MPa  Psat (T )
45 MPa at 180oC, 200oC 46

Interpolations II Interpolations III

• Apply formula for T = 180oC and 200oC • Now interpolate between results for two
v(180 C , 2 MPa)  .001127 m
o 3
 different T’s to find T at desired v
kg
200o C  180o C
.001125 m
3
 .001127 m
3
3 T  180o C 
kg kg
2 MPa  1.0021 MPa   .001126501 m .00115648 m 3 .001126501 m3

5 MPa  1.0021 MPa kg kg kg
 .00115 m3 .001126501 m 3 
3     195.7 o C
v( 200 C , 2 MPa)  .001157 m
o
  kg kg 
kg
• Previous result using v(T,P) ≈ vf(T) was
3 3
.001153 m  .001157 m 3
kg kg
2 MPa  1.5538 MPa   .00115648 m 195.6oC
5 MPa  1.5538 MPa kg
47 48

ME 370 – Thermodynamics 8