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Theory

Chapter 3: Properties of Pure Substances.


Part A: Pure Substances
A pure substance is known as a substance that completely filled with one type of
chemical composition where the material can be in any single type. Some example are pure H2
which shown in below figure 1.

Figure 1. H2 example
Part B: Phases of Pure Substance
Substances can be divided into three different phases (figure 2) such as:
- State A: Fixed position
- State B: Group together and move about each other
- State C: Random movement

Figure 2. Different state of pure substances


Part C: Phase-Change Processes of Pure Substances
Pure substances phase change can be categorized into 5 stages:
- Compressed Liquid (subcooled liquid): A substance that it is not about to vaporize.
- Saturated Liquid: A liquid that is above to vaporize.
- Saturated liquid-vapor mixture: The state at which the liquid and vapor phases coexist in
the equilibrium.
- Saturated vapor: A vapor that is about to condense.
- Superheated vapor: A vapor that is not about to condense
Below figure 3 shows five stages of phase change processes

Compressed Saturated Saturated liquid Saturated Superheated


liquid liquid vapor mixture vapor vapor
Figure 3. Stages of phase change processes

Heating process of water at constant pressure

Figure 4. T-v diagram


Based on figure 4 above, if the entire process between sate 1 and 5 is reversed by cooling
the water while maintaining the pressure at the same value, therefore the water will go back
to sate 1 retracting the same path with the amount of heat released that exactly matches the
amount of heat added during the heating process.
Part D: Saturation Temperature and Saturation Pressure
Definition:
Saturation temperature - The temperature at which a pure substance changes phase at a given
pressure.
Saturation pressure - The pressure at which a pure substance changes phase at a given
temperature.
Latent heat - The amount of energy absorbed or released during a phase-change process.
Latent heat of fusion - The amount of energy absorbed during melting. It is equivalent to the
amount of energy released during freezing.
Latent heat of vaporization - The amount of energy absorbed during vaporization and it is
equivalent to the energy released during condensation.
Latent heat of vaporization The amount of energy needed to vaporize a unit mass of saturated
liquid at a given temperature or pressure

Figure 5. Table of variation of standard atmospheric pressure and the boiling temperature of
water corresponding to altitude.
The magnitudes of the latent heats depend on the temperature or pressure at which the
phase change occurs. Therefore, according to table 1, the atmospheric pressure and the
temperature of water will decrease with elevation.
Part E: Property Diagram for Phase-Change Processes
Figures 6(a,b,c) - Sample of T-v diagram.
Based on figures 6(a,b,c) above, T-v diagram of constant-pressure phase-change
processes of a pure substance at various pressure. Beside that, there are several regions that we
can find from figure 6(a,b,c) above such as:
- Saturated Liquid Line
- Saturated Vapor Line
- Compressed Liquid Region
- Superheated Vapor Region
- Saturated Liquid Vapor Mixture region (Wet Region)
There is also a tripe point pressure and temperature where the substances are able to exist in
three phases when it reach equilibrium states. Besides that, based on figure 6c, there is a ciritical
point where it is a point at which the saturated liquid liquid and saturated vapor states are
identical. At low pressure which is below the triple-point value, the solids will evaporate without
melting first where the process can also be known as sublimation.
Part F: Property Tables
A table that present the property of substances in a convenient form which is in the result
of measurement and calculation. This is because most of the thermodyamics properties are
calculated by using their relation and measurable properties but it is too complex to be expressed
by simple equation so table will assist enginner in solving problems regaring thermodynamcs.
The properties for each substance were listed more than one table. Some example of substances
are supersaturated vapor, compressed liquid and saturated mixture regions. Besides that, a
combination property which known as Enthalpy,H are introduced and the formula are given
below:

Part G: Substances Properties


For both saturated liquid and saturated vapor states properties are listed under table A-4
and table A-5. Table A-4 are listed based on temperature while table A-5 are based on pressure.
Below table figure shows table A-4and table A-5:
Figure 7. Table A-4

Figure 8. Table A-5


From Table A-5, the Hfg decreases when pressure or temperature rises and eventually will
become zero at a critical point.
Next is saturated liquid-vapor mixture where it exists as part of liquid and part vapor
during the vaporization process. The proportion of liquid and vapor in the mixture are able to be
analyzed by using Quality X where it is the ratio of vapor mass to the mixture total mass and the
equation are given:

where
The properties of saturated liquid remain the same either it exists alone or in a mixture
with saturated vapor. The mixture also dependent on pressure and temperature. For convenience,
this two phases system can be treated as a homogenous mixture. Therefore, the average volume
of saturated liquid-vapor mixture is the sum of saturated vapor and saturated liquid. Below figure
show the derivation of formula using the condition of homogenous mixture.

Figure 9. Derivation of formula


From figure 9 formula, a general equation can be introduced

y = v, u, or h.
where
v= specific volume
u= internal energy
h= enthalpy
With the condition

The following is superheated vapor where it can be obtained by rising the temperature
above saturation temperature and maintaining the constant pressure. It is output of working
substance in steam engines. Superheated vapor exists at the region to the right of the saturated
vapor line and is above the critical point temperature and the temperature and pressure act as
independent variable. Characteristic of superheated vapor are:
T > Tsat (at a given P)
P < Psat (at a given T)
v > vg or h > hg or u > ug (at given either P or T)
At a specified P, superheated vapor exists a higher h than
the saturated vapor
Compressed liquid is a phase where there is no vapor and the liquid are not about to
vaporize. The characteristic of compressed liquid are:

T < Tsat (at a given P)


P > Psat (at a given T)
v < vf , h < hf , u < uf (at either given T or P)
Compressed liquid properties depend on
temperature much more strongly
Approximate compressed liquid behaviour
evaluated at the given TEMPERATURE
v=vf@t
h=hf@t
u=uf@t

Ideal gas is a hypothetical gas whose molecules occupy negligible space with no
interaction between each other. Below shows different types of ideal gas equation:
Ideal gas equation of state
Pv=RT
P = R(T/V)
R = Ru/M
While R is the gas constant 8.31447kJ/kmol K
M is the molar mass(kg/kmol), Ru is the universal gas
constant
Equation at two states at a fixed mass
P= pressure ,V= volume ,
Various expression of ideal gas equation
Real gases behave as an ideal gas at low densities

Real gases behave as an ideal gas at low densities

Compressibility factor, Z is a factor that accounts for the deviation of real gases from
ideal-gas behavior at a given temperature and pressure. The farther away Z is from unity, the
more the gas deviates from ideal-gas behavior. Gases behave as an ideal gas at low densities (i.e.,
low pressure, high temperature). Criteria for low pressure and high temperature is that the
pressure or temperature of a gas is high or low relative to its critical temperature or pressure. The
equation for Z are:
Part H: Other form of Equation of State

Several equations have been proposed to represent the P-v-T behavior of


substances accurately over a larger region with no limitations.

Van der Waals Equation of State

This model includes two effects not considered in the ideal-gas


model
- the intermolecular
Beattie-Bridgeman attraction forces
Equation of State
-the volume occupied by the molecules themselves

Benedict-Webb-Rubin Equation of State

Virial Equation of State

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