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Thermodynamics: ENG-214 Chapter 2 - Properties of Pure Substances

The document discusses properties of pure substances and phase changes, defining pure substances as having a fixed chemical composition and describing the solid, liquid, and gas phases. It explains that during phase changes, temperature remains constant while energy is required to overcome intermolecular forces, and explores pressure-temperature and pressure-volume diagrams for visualizing these relationships. Specific topics covered include vapor pressure curves, the impact of pressure on boiling point, and using property tables to determine temperature, pressure, and other intensive properties.

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114 views34 pages

Thermodynamics: ENG-214 Chapter 2 - Properties of Pure Substances

The document discusses properties of pure substances and phase changes, defining pure substances as having a fixed chemical composition and describing the solid, liquid, and gas phases. It explains that during phase changes, temperature remains constant while energy is required to overcome intermolecular forces, and explores pressure-temperature and pressure-volume diagrams for visualizing these relationships. Specific topics covered include vapor pressure curves, the impact of pressure on boiling point, and using property tables to determine temperature, pressure, and other intensive properties.

Uploaded by

Gregory MacLeod
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Thermodynamics

ENG-214
Chapter 2 – Properties of Pure Substances
Substance
(The physical construct, not the metaphysical or philosophical)

• Pure Substance - Fixed chemical composition


• Examples include
• Nitrogen (N2)
• Water (H2O)
• Air (mixture of N2, O2, Ar, etc.)
• Phase needs to be homogenous
Q: Is a water / oil mixture a pure substance? Why or Why Not?
• Multi-phase needs the same chemical composition
Phases
Q: Anyone know the phases of matter?
• Solid
• Liquid
• Gas
• Plasma (only applicable to wicked hot gasses!)
• Phase change merits particular attention
• Solid  Liquid
• Liquid  Vapor
• Solid  Vapor
Phase change – what happens?
• Energy goes into overcoming intermolecular forces
• Temperature remains constant as phase changes
• Can be seen in a T-v diagram
• Phase progression
• Subcooled (Compressed) Liquid
• Saturated Liquid
Phase change occurs (Liquid  Vapor)
• Saturated Vapor
• Superheated Vapor
• Is Pressure dependent
T-v Diagram for Water (H2O)
• Two types of heat
Sensible Heat
Phase is constant
Temperature Changes
Latent Heat
Phase changes
Temperature is Constant
• Heat of vaporization (liq-gas)
• Heat of fusion (liq->solid)
• Tsat is a function of pressure
T-v Diagram – Impact of Pressure

373.95
More on P dependence
• Recall degrees of freedom:
f = k - p +2
• When P is fixed, T is fixed since two phases are present
• Changes in Pressure (Psat)  Changes in Tsat
Examples:
• Boling Temperature vs. Elevation
• Pressure Cookers
• Vacuum Cooling (or vacuum freezing)

This interplay of Pressure, Temperature, Specific Volume and Phase


is Important and can be expressed graphically…
Vapor Pressure (Psat vs Tsat)
Putting it all together…
• Pure substances represent the simplest systems we can study
• State of the system is based on intensive properties, including:
• Temperature (T)
• Pressure (P)
• Specific Volume (v)
• Phase(s) present
• Can show the relation visually by graphing
• T vs. v
• P vs. v
• P vs. T
• P-v-T (3 dimensional plot)
T-v Diagram

Plots Temperature (T)


vs. Specific Volume (v)

Holding Pressure (P) constant


P-v Diagram

Plots pressure (P)


vs. Specific Volume (v)

Holding Temperature (T) constant


P-v Diagram – Including Solids
P-T Diagram
P-v-T Surface
P-v-T Surface - Water
Property Tables
• Tabulated data can be used to determine volume, temperature, etc.
vf = specific volume of saturated liquid
vg = specific volume of saturated gas
vfg = difference between vf and vg (vfg = vf– vg)

• See Table A-4/4E through A-8/8E & A-11/11E through A-13/13E

h (specific enthalpy) and u (Internal Energy) and s (entropy) values are given
for various P, T combinations… more about them a bit later.
Putting these property tables to good use….
• Determine the internal energy of water at 20 psia and 400 F

• A rigid tank has 50 kg of saturated liquid water at 90 C.


What is the pressure in the tank and the volume of the tank?

• Determine the temperature of water at P = 0.5 MPa and h = 2890 kJ/kg

• A piston-cylinder contains 2 ft3 of saturated water at 50 psia pressure.


Determine the temperature and mass of the vapor inside the cylinder
• A mass of 200 g of saturated liquid water is completely vaporized at a
constant pressure of 100 kPa. Determine the volume change.
Enthalpy (H)
H = U + PV
Where:
H = Enthalpy [BTU or kJ]
U = Internal Energy [BTU or kJ]
P = Pressure [psia or kPa]
V = Volume {ft3 or m3}

Note: Pressure (P) x Volume (V) gives units of Energy (BTU or kJ)

Can rewrite based on intensive properties…


h = u + Pv
Quality
• During vaporization you have two phases present. What are they?
• Quality (x) describes how wet (or dry) a vaporizing fluid is.
• Always given on a mass basis Can convert to a volumetric basis

mvapor vavg  v f
x x
mtotal v fg
Where: mtotal = mliqud + mvapor = mf + mg

Ranges from 1.0 [all (saturated) vapor] to 0.0 [all (saturated) liquid]

NOTE: The liquid PROPERTIES are the same… only the MASS of liquid changes
Quality and the P-v (or T-v) Diagram

An 80 L vessel has 4 kg of R-134a at 160 kPA. Determine the temperature,


quality and enthalpy as well as the volume occupied by the liquid phase.
Superheated Vapor
• Lower pressure
(P < Psat at a given T)
• Higher Temperature
(T > T sat at a given P)
• Higher specific volume
(v > vg at a given P or T)
• Higher internal energy
(u > ug at a given P or T)
• Higher enthalpies
( h > hg at a given P, T)
Compressed Liquid
• Higher pressure
(P > Psat at a given T)
• Lower Temperature
(T < T sat at a given P)
• Lower specific volume
(v < vg at a given P or T)
• Lower internal energy
(u < ug at a given P or T)
• Lower enthalpies
( h < hg at a given P, T)

KEEP IN MIND LIQUID PROPERTIES (v, H, u) DO NOT CHANGE MUCH WITH PRESSURE
Reference States
• u, h and s cannot be measured directly
• Relations deal with the CHANGE in u, h, s
• Need to set “reference state”
• Different for different compounds
Water  Sat. Liq at 0.01 C
R-134a  Sat. Liq. At -40 C

• Different tables from different books may have different values


• Thankfully since we are worried about CHANGE it’s not an issue
Tying it all together….
• Can determine missing properties… [Hint: fluid is water]

T, °C P, KPa U, kJ/kg X Phase(s)


200 0.6
125 1600
1000 2950
75 500
850 0
Equations of State
• Ideal Gas Law
PV = nRT
OR
R 
Pv  RT Where R u 
M 

What is the mass of air in a 4 m x 5 m x 6 m room at STP?

• Values for Ru [see back cover of text]


8.314 kJ/kmol·K
8.314 kPa·m3/kmol·K
0.08314 bar·m3/kmol·K
1.986 BTU/lbmol·R
10.73 psia·ft3/lbmol·R
Equations of State – Compressibility (Z)
• Modification to the
Ideal Gas Law
Pv=RT
becomes
Pv = ZRT

Z = compressibility factor
vactual
Z
videal

P T
PR  TR 
Pcr Tcr
Pseudo Specific Volume

vactual
vR 
RTcr Pcr

EXAMPLE 2-12
Equations of State
• Van Der Walls (Real Gas Law)

 a
 P  2  v  b   RT
 v 
27 RTcr2
a
64 Pcr
RTcr
b
8 Pcr
Equations of State

Beattie-Bridgeman
Benedict-Webb-Reubem
Strodbridge
Redlich Kwong (RK)
Soave Redlich Kwong (SRK)
Peng Robinson (PR)
Viral Equation of State

RT a T  b T  c T  d  T 
P  2  3  4  5  ...
v v v v v
Specific Heat
• Also called heat capacity  measures how much heat can be stored

• Energy required to raise the temperature of a unit mass of substance by one degree

• Large C = more energy (heat) needed to facilitate a temperature change

Cv   u
T v
 CP   h
T P

• Applies to single phases only (liquid or solid)
(since a phase change occurs with constant temperature)

• k = Cp/Cv (1.4 for air and diatomic gasses, 1.3 for steam)
Solids & Liquids… U, H and Cp
• Solids and liquids are considered incompressible
Cp = Cv = C
See Table A-3 for a listing of C for common liquids and solids
Consequences of this
Cv converts to an exact deferential
Enthalpy equation simplifies

And if constant pressure….. Or if constant temperature…..


Example 2-15
Vapor Pressure & Phase Equilibrium
Dalton's Law: Pt = SPi
For air / water system
Patm = Pair + PH2O

Relative Humidity… appropriate on a day like today

Evaporation
Boiling
Homework
2-1C, 2-4C, 2-6C, 2-11C, 2-17C, 2-23C, 2-31, 2-33E, 2-34, 2-44, 2-50,
2-51E, 2-52, 2-55E, 2-58, 2-63, 2-68, 2-70, 2-71E, 2-73E, 2-82, 2-83,
2-84E, 2-131, 2-132, 2-133, 2-134, 2-135, 2-136, 2-137, 2-138, 2-139,
2-140, 2-141

Also, read chapter 3

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