Thermodynamics Pure Substance: Lec. (3) Dr. Omar M. Ali

Lec. (3) Thermodynamics Dr. Omar M.
Ali
Pure substance
Pure substance: is one of homogenous and chemically stable. It can be
single phase which is present in more than one phase.
Phase: is the state of the substance such as solid, liquid or gas.
Boiling temperature: the temperature at which vaporization takes place
at a given pressure.
Freezing temperature: the temperature at which solidification takes
place at a given pressure fusion line (it is nearly straight) as the border
between the solid phase and the liquid phase.
Pure Substance States:

Consider a piston–cylinder device containing liquid water at the
following states that shown in figure below:
Lec. (3) Thermodynamics Dr. Omar M. Ali
State 1: 20C and 1 atm pressure, water exists in the liquid phase, and it
is called a compressed liquid, or a subcooled liquid
State 2: 100C and 1 atm pressure, saturated liquid state.
State 3: 100C and 1 atm pressure, Midway about the vaporization line,
the cylinder contains equal amounts of liquid and vapor.
State 4: 100C and 1 atm pressure, saturated vapor state.
A substance at states between 2 and 4 is referred to as a saturated liquid–
vapor mixture.
state 5: the temperature of the vapor is, let us say, 300C, superheated
vapor.
This constant-pressure phase-change process is illustrated on a T-v
diagram in Figure below.
The T-v Diagram

The phase-change process of water at 1 atm pressure was described in
detail on a T-v diagram in last figure. The same process may be plotted at
different pressures to develop the T-v diagram.
Saturation state: A state at which a phase change begins or ends.

The dome shaped region composed of the two-phase liquid–vapor states
is called the vapor dome.
Critical point: is defined as the point at which the saturated liquid and
saturated vapor states are identical.
The critical temperature, critical pressure, and critical specific volume of
a substance are Pcr = 22.06 MPa, Tcr = 373.95C, and vcr = 0.003106
m3/kg.
For helium, they are 0.23 MPa, -267.85°C, and 0.01444 m3/kg.
At pressures above the critical pressure, there is only one phase present.
Saturated liquid line: is a line formed by connecting saturated liquid

states in T-v diagram.
Saturated vapor line: is a line formed by connecting saturated vapor
states in T-v diagram.
Compressed liquid region: is a region in the left of the saturated liquid
line and contain all the compressed liquid states(single phase).
Superheated vapor region: is a region located to the right saturated
vapor line and contain all the superheated vapor states(single phase).
Liquid–vapor mixture region (wet region): is the region under the
dome and contain all the states that involve both phases in equilibrium.
The p-v diagram

The general shape of the P-v diagram of a pure substance is very much
like the T-v diagram, but the T = constant lines on this diagram have a
downward trend.
The p-T Diagram

This diagram is called the phase diagram since all three phases are
separated from each other by three lines.
Sublimation line: is the line separating the solid phase from the vapor
phase.
Vaporization line: is the line separating the liquid phase from the vapor
phase.
Melting line: is the line separating the solid phase from the liquid phase.
The triple line of the three-dimensional p–v–T surface projects onto a

point on the phase diagram called the triple point. The temperature of the
triple point of water is 273.16 K. The measured pressure at the triple
point of water is 0.6113 kPa.
Subcooled liquid: A liquid its temperature at a given pressure is lower
than the saturated temperature at that pressure.
Degree of subcool: the difference between the saturation temperature and
the actual temperature of the liquid at given pressure.
Superheated vapor: a gas its temperature at a given pressure is greater
than the saturated temperature at that pressure.
Degree of superheat: the difference between the actual temperature of a
given vapor and the saturation temperature of the vapor at given pressure.
The P-v-T Surface

In the p-v-T surface, T and v are independent variables (the base) and p
as the dependent variable (the height).
All the points on the surface represent equilibrium states. All states along
the path of a quasi-equilibrium process lie on the P-v-T surface since such
a process must pass through equilibrium states.
PROPERTY TABLES
For each substance, the thermodynamic properties are listed in more than
one table. In fact, a separate table is prepared for each region of interest
such as the superheated vapor, compressed liquid, and saturated (mixture)
regions.
Saturated Liquid and Saturated Vapor States
The subscript f is used to denote properties of a saturated liquid.
The subscript g to denote the properties of saturated vapor.
The subscript fg to denote the difference between the saturated vapor and
saturated liquid values of the same property. For example,
vf = specific volume of saturated liquid
vg = specific volume of saturated vapor
vfg = vg - vf
The quantity hfg is called the enthalpy of vaporization (or latent heat of
vaporization).
Gengel
Example: A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine
the pressure in the tank and the volume of the tank.
Example: A piston–cylinder device contains 2 ft3 of saturated water vapor at 50 psia

pressure. Determine the temperature and the mass of the vapor inside the cylinder.
Saturated Liquid–Vapor Mixture
During a vaporization process, a substance exists as part liquid and part

vapor. That is, it is a mixture of saturated liquid and saturated vapor.
Dryness fraction (quantity) (x): is defined as the ratio of the mass of

pure vapor (mg) present to the total mass of the mixture (mT).
x = 0 (saturated liquid state)
x = 1 (saturated vapor state)
0 < x <1 (mixture region)
Thermodynamic Properties of the mixture:
Specific Volume
Internal energy
Enthalpy
Entropy
Example: A rigid tank contains 10 kg of water at 90°C. If 8 kg of the water is in the

liquid form and the rest is in the vapor form, determine (a) the pressure in the tank and
(b) the volume of the tank.
Superheated Vapor
A substance exists as superheated vapor in the region to the right of the
saturated vapor line and at temperatures above the critical point
temperature.
Compared to saturated vapor, superheated vapor is characterized by
Lower pressures (p  psat at a given T)
Higher temperatures (T  Tsat at a given p)

Higher specific volumes (v  vg at a given p or T)
Higher internal energies (u  ug at a given p or T)
Higher enthalpies (h  hg at a given p or T)
Example: Determine the temperature of water at a state of P = 0.5 MPa and h = 2890
kJ/kg.
Compressed Liquid
A compressed liquid may be approximated as a saturated liquid at the
given temperature because the variation of properties of compressed
liquid with pressure is very mild.
The compressed liquid properties depend on temperature much more
strongly than they do on pressure. Thus,
y = yf @ T
Where y is v, u, or h of these three properties.
enthalpy h is most sensitive to variations in the pressure.
In general, a compressed liquid is characterized by
Higher pressures (p > psat at a given T)
Lower temperatures (T < Tsat at a given p)
Lower specific volumes (v < vf at a given p or T)
Lower internal energies (u < uf at a given p or T)
Lower enthalpies (h < hf at a given p or T)
Example: Determine the internal energy of compressed liquid water at 80°C and 5
MPa, using (a) data from the compressed liquid table and (b) saturated liquid data.
What is the error involved in the second case?
Reference State and Reference Values

We need to choose a convenient reference state and assign a value of zero
for a convenient property or properties at that state.
- For water, the state of saturated liquid at 0.01°C is taken as the

reference state, and the internal energy and entropy are assigned
zero values at that state.
- Sometimes different tables list different values for some properties
at the same state as a result of using a different reference state.
Example: Determine the missing properties and the phase descriptions in the
following table for water:
T, C p, kPa u, kJ/kg x Phase description
A 200 0.6
B 125 1600
C 1000 2950
D 75 500
E 850 0

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Lec. (3) Thermodynamics Dr. Omar M.

Pure Substance States:

The T-v Diagram

Saturation state: A state at which a phase change begins or ends.

Saturated liquid line: is a line formed by connecting saturated liquid

The p-v diagram

The p-T Diagram

The triple line of the three-dimensional p–v–T surface projects onto a

The P-v-T Surface

Example: A piston–cylinder device contains 2 ft3 of saturated water vapor at 50 psia

Saturated Liquid–Vapor Mixture

During a vaporization process, a substance exists as part liquid and part

Dryness fraction (quantity) (x): is defined as the ratio of the mass of

x = 0 (saturated liquid state)

x = 1 (saturated vapor state)

0 < x <1 (mixture region)

Thermodynamic Properties of the mixture:

Example: A rigid tank contains 10 kg of water at 90°C. If 8 kg of the water is in the

Higher temperatures (T  Tsat at a given p)

Reference State and Reference Values

- For water, the state of saturated liquid at 0.01°C is taken as the

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