Chapter 3 Volumetric Properties of Pure Fluids PDF
Chapter 3 Volumetric Properties of Pure Fluids PDF
Chapter 3 Volumetric Properties of Pure Fluids PDF
Equilibrium: the absence of change; all forces are in exact balance; the absence of driving force
The equilibrium state of a system is completely described by a fixed number of independent
variables (degrees of freedom). The other independent variables are specified using equations of state.
Example 2.5/p30
How many degrees of freedom have each of the following systems?
(a) Liquid water in equilibrium with its vapor
(b) Liquid water in equilibrium with a mixture of water vapor and nitrogen
(c) A liquid solution of alcohol in water in equilibrium with its vapor
Answer:
(a) F = 2 – π+ N = 2 – 2 + 1 = 1
(b) F = 2 – π + N = 2 – 2 + 2 = 2
(c) F = 2 – π + N = 2 – 2 + 2 = 2
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PV Diagram for a Pure Substance
• The isotherms
– the subcooled-liquid and the superheated-vapor regions
– isotherms in the subcooled-liquid regions are steep because liquid volumes change little
with large change in pressure
• The two-phase coexist regions
• The triple point is the horizontal line
• The critical point
Equations of State (EOS)
- An EOS relates pressure, molar or specific volume, and temperature for any pure homogeneous
fluid.
- empirical relationships that mathematically model the PVT behaviour of fluids
PVT equation of state is expressed analytically as: f(P,V,T) = 0
- equation may be solved for any one of the three quantities P, V, or T as a function of the other
two
for example: V = V(T,P) P = P(V,T) T = T(V,P)
Liquids
V V (T , P )
V V
dV
T
dT
P dP
P T
The partial derivatives in the equation have definite physical meanings and are related to two
properties, volume expansivity (β) and isothermal compressibility (κ)
1 V
V T P
1 V
V P T
β and κ can be assumed constant for liquids, at conditions not close to the critical point.
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The equation of state for liquids can then be written as:
dV
dT dP
V Values of and are found in many handbooks.
V
ln 2 T2 T1 P2 P1
V1
Example 3.1/p69
For liquid acetone at 20oC and 1 bar,
β = 1.487 x 10-3 oC-1 κ = 62 x 10-6 bar-1 V = 1.287 cm g-1
For acetone, find the
(a) value of ( ) at 20oC and 1 bar
(b) pressure generated by heating at constant V from 20oC and 1 bar to 30oC
(c) change in volume for a change from 20oC and 1 bar to 0oC and 10 bar.
Solution:
(a)
P P (V , T )
0 at constant volume
P P
dP
T
dT
V
dV
V T
dP P = (from EoS for liquids)
T
dT V
PV a bP cP 2
If b aB’, c aC’, etc., then
the parameters B’, C’, D’, etc. are virial coefficients, accounting of interactions between
molecules
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Ideal Gases
molecules on average are far apart
best at large V (low density)
occurs at low P and high T
intermolecular forces approach zero
no interactions between particles
2) PV Work
U U (T )
T2
U CV dT
T1
dH dU d ( PV ) dU RdT H T
T2
H C P dT
T1
Appen. C, p. 637, gives equations for ideal gas heat capacities as a function of temperature.
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Thermodynamic Processes
Isobaric (Constant-P) Process
Adiabatic Process
no heat flows in or out of the system
process occurs when the system is extremely well insulated or when the process
happens very quickly.
Qin 0
then U int Won,adiabatic n cV T
C
FoF P V const ; C
P
adiabatic coefficien t
V
T V 1 const
T P 1 const
Note: Special P-V-T relations are for an adiabatic and reversible process.
Polytropic Process
A polytropic process is a thermodynamic process that obeys the relation:
PVn = C
where P is pressure, V is volume, n is any real number (the polytropic index), and C is a constant.
For certain indices n, the process will be synonymous with other processes:
if n = 0, then PV0=P=const and it is an isobaric process (constant pressure)
if n = 1, then for an ideal gas PV= const and it is an isothermal process (constant temperature)
if n = γ = cp/cV, then for an ideal gas it is an adiabatic process (no heat transferred)
if n = ∞ , then it is an isochoric process (constant volume)
Example 3.2
Air is compressed from an initial condition of 1 bar and 25°C to a final state of 5 bar and 25 °C by
three different mechanically reversible processes in a closed system. (1) heating at constant volume
followed by cooling at constant pressure; (2) isothermal compression; (3) adiabatic compression
followed by cooling at constant volume. Assume air to be an ideal gas with the constant heat capacities,
CV = (5/2)R and CP = (7/2)R. Calculate the work required, heat transferred, and the changes in internal
energy and enthalpy of the air in each process.
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Example 3.3/ Example 3.4
An ideal gas undergoes the following sequence of mechanically reversible processes in a closed
system:
(1) From an initial state of 70°C and 1 bar, it is compressed adiabatically to 150 °C.
(2) It is then cooled from 150 to 70 °C at constant pressure.
(3) Finally, it is expanded isothermally to its original state.
Calculate W, Q, ΔU, and ΔH for each of the three processes and for the entire cycle. Take C V = (3/2)R and
CP = (5/2)R. If these processes are carried out irreversibly but so as to accomplish exactly the same
changes of state (i.e. the same changes in P, T, U, and H), then different values of Q and W result.
Calculate Q and W if each step is carried out with an efficiency of 80%.
Homework
1. An ideal gas initially at 184oC, 3.0 atm with a volume of 25 L undergoes expansion to a final pressure
of 1.4 atm. Determine the work done by the gas if the expansion is
(a) isothermal and reversible Ans. -5792 J
(b) isothermal and against a constant opposing pressure of 1.4 atm Ans. -4053 J
2. One g-mole of an ideal monoatomic gas, Cv = (3/2)R, has an initial pressure of 6 atm and a
temperature of 200oC. It expands to a final pressure of 2 atm. Calculate the work done by the gas on
expansion if the process is
(a) adiabatic and reversible Ans. -2098 J
(b) adiabatic and against a constant opposing pressure of 1.0 atm Ans. -982 J
Non-ideal Gases
Group activity: Compare the two equations truncated after the 2nd virial coefficient terms for
the problem in Example 3.7, p. 89. Ans.: V=3546 cm3/mol from 1st form, V=3488 from 2nd, a
1.7 % difference.
In 1873, Van der Waals developed an equation of state that qualitatively accounts for attractive
forces between molecules and an excluded volume due to the finite size of the molecules:
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RT a
P 2 (3.41)
V b V
Here, a and b are positive constants; when they are equal to zero, the ideal gas equation is
recovered.
This has been modified to make it better fit real gas behavior by many workers. For example,
Redlich and Kwong proposed the following equation of state in 1949:
RT a (T )
P
V b V V b
(3.47)
Note that a(T) is a constant, and is given by Eq. (3.45) found on p. 94 in the text.
These two-parameter equations of state are called cubic equations, because they are cubic in V.
Thus, there are three volumes corresponding to a given P and T. For saturated liquid and vapor,
the smallest root will be for the liquid, the largest for the vapor, and a third one will lie in
between (see Fig. 3.11, p. 92).
At the critical point, the P-V curve must obey the following relations:
P 2 P
0 (3.43) and (3.44)
V T V 2 T
The a and b parameters could also be fit to experimental PVT data for the fluid of interest. This
would give a better equation of state within the region of the experimental data, but would not
extrapolate well to other regions.
0.08664 RTc
b
Pc
Peng-Robinson equation of state
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RT a
P
V b V (V b) b(V b)
a a c (1 (1 Tr )) 2
0.45724 R 2Tc2
PR: ac
Pc
0.37464 1.54226 0.26992 2
0.07780 RTc
b
Pc
BPc
B o B1
RTc
V sat Vc Zc
1Tr
0 . 2857
(3.72)
* the same correction to Vsat can be made using isothermal compressibilities for specific
fluids
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