P-V-T behavior of pure substances

• P-V-T behaviour of fluid is the behaviour of fluid under • The graphical representations include P-T , P-V, T-S,
any imaginable conditions of pressure, temperature and P-H and H-S (Mollier}diagrams
volume (P-V-T).
• Pressure, volume and temperature are the building blocks of P-T Diagram
thermodynamics. These properties help us understand how
substances behave under different conditions. Knowing how • A typical P-T diagram showing the relationship
they interact is key to grasping the bigger picture of pure between pressure and temperature of a pure
substances substance is shown below
• The objective of a Pressure-Volume-Temperature (PVT) • The figure is called phase diagram which is a
study is to determine the physical and chemical fluid graphical representation of the physical states of a
characteristics to predict the fluid behaviour volume versus substance under different conditions of temperature
pressure and temperature changes and pressure.
• For a pure substance, the relations among pressure-volume-
• The simplest phase diagrams are pressure–
temperature (P-V-T) are expressed in the form of equations
(known as equation of state), diagrams/graphs (T-V, P-V and temperature diagrams of a single simple substance,
P-T) and property tables. such as water.
• The axes correspond to the pressure and temperature.

• .
.
• The phase diagram shows, in pressure–
temperature space, the lines of equilibrium or
phase boundaries between the three phases of
solid, liquid, and gas.
• As we cross the lines or curves on the phase
diagram, a phase change occurs.
• Measurements of the vapor pressure (the
pressure at which a liquid boils and is in
equilibrium with its own vapour) of a pure
substance, both as a solid and as a liquid, lead
to pressure-vs.-temperature curves such as
shown by lines 1-2 and 2-C in the Figure.
• The third line (2-3) gives the solid/liquid
equilibrium relationship. The three lines
display conditions of P and T at which two
phases may coexist, and are boundaries for the
single-phase regions.
• Line 1-2, the sublimation curve, separates the
solid and gas regions; line 2-3, the fusion
curve, separates the solid and liquid
• regions; line 2-C, the vaporization curwe, • In water, the critical point occurs at around Tc =
separates the liquid and gas regions 647.096 K (373.946 °C), pc = 22.064 MPa
• All three lines meet at the triple point, where the (217.75 atm) and Vc = 356 kg/m³.
three phases coexist in equilibrium • Homogeneous fluids are usually classified as
• The vaporization curve (phase boundary between liquids or gases. However, the distinction cannot
liquid and gas ) 2-C terminates at point C on the always be sharply drawn, because the two phases
phase diagram called the critical point. become indistinguishable at the critical point.
• The pressure and temperature corresponding to • This observation is different from ordinary
this point are known as the critical pressure PC and condition whereby the boundary between liquid
critical temperature TC respectively. These are the and gas is very clear. For example, consider a path
highest pressure and temperature at which a pure such as the one from A to B that lead from the
substance can exist in vapour-liquid equilibrium. liquid region to the gas region without crossing
the vapourization curve 2-C.
• At the critical point, the liquid and gas phases
• The transition from liquid to gas is gradual. On
become indistinguishable, because their properties
are the same. The fluid at this point is known as a the other hand, paths that cross the vapourization
supercritical fluid. curve will involve a vapourization or
condensation step, where an abrupt change from
• The coordinates of this point are the critical liquid to gas occurs.
pressure PC and the critical temperature Tc, the • A phase is generally considered a liquid if
highest pressure and highest temperature at which
vaporization results from pressure reduction at
a pure chemical species can exist in vapor/liquid
constant temperature.
• A phase is considered a gas if condensation PV Diagram
results from temperature reduction at • The P-T Diagram does not provide any
constant pressure. information about volume. It merely displays the
phase boundaries as a function of pressure and
• Since neither process occurs in the area temperature. On a pressure-volume (PV) diagram,
beyond the dashed lines, it is called the these boundaries become areas.
fluid region. • A PV diagram is a graphical way of representing
• The gas region is sometimes divided the relationship between the pressure and volume
of an ideal gas. It is a graph with pressure on the
into two parts, as indicated by the dotted y– axis and volume on the x-axis.
vertical line of Figure.
• A gas to the left of this line, which can • The P-V Diagram (Figure below) displays the
be condensed either by compression at regions (areas) where 2 phases of solid/liquid,
constant temperature or by cooling at solid/vapour, and liquid/vapour co-exist in
constant pressure, is called a vapor. equilibrium.
• • On the P-V Diagram, the triple point appears as a
The region everywhere to the right of horizontal line, where all 3 phases co-exist at a
this line, where T > Tc,, including the single temperature and pressure.
fluid region, is termed supercritical • Isotherms are lines of constant temperature and
these are superimposed on the P-V Diagram as
•.
PV diagrams for a pure substance. (a) Showing solid, liquid, and gas
regions. (b) Showing liquid, liquidlvapor, and vapor regions with isotherms
• Figure above shows the liquid, liquid/vapor, • The 2-phase liquid-vapour region lies under
and vapor regions of the P V diagram, with the curve BCD, whereas subcooled liquid and
four isotherms superimposed superheated vapour regions lie to the left and
• Point C is the critical point. VC is the critical right, respectively.
volume at this point. • Subcooled liquid exists at temperatures below
• The isotherm labelled T > TC does not cross a the boiling point for the given pressure.
phase boundary. T • Superheated vapour exists at temperatures
above the boiling point for the given pressure.
• The lines labelled T1 and T2 are isotherms for
subcritical temperatures, and they consist of 3 • Isotherms in the subcooled liquid region
segments. are very steep, because liquid volumes
• The horizontal segment of each isotherm change little with large changes in
represents all possible mixtures of liquid and pressure.
vapour in equilibrium, ranging from 100% • The horizontal segments of the isotherms
liquid at the left end (curve B-C) to 100% in the 2-phase region become
vapour at the right end (curve D-C). progressively shorter at higher
• Curve B-C represents saturated liquid at their temperatures, being ultimately reduced to
boiling points, and curve D-C represent a point at C, the critical point.
saturated vapours at their condensation points.
• The PV diagram is ued to calculate the Step 2. Determine if the gas is being
amount of workdone by the gas during compressed or is being expanded.
expansion or compression.
Step 3.. Report the work done as the area
• The area under the line drawn on a PV calculated in step 1, making it positive if the
diagram is an exact calculation of how much gas is contracting and negative if the gas is
work is done on the graph. expanding.
• When the gas expands, it expends energy to
do work on the environment.
Notes
• Because it lowers energy as it expands, the
work is represented with a negative number. When it comes to drawing basic PV diagram,
there are specific rules you must follow
• When the gas contracts, the environment
does work on the gas, adding internal energy (a) The y-axis represents the pressure, and the
to the gas which is represented with a x-axis represents the volume.
positive number for work. (b) Increasing pressure values follow a down-
• How to calculate Work done on a gas to-up direction, and increasing volume values
graphically follow left to right.
Step 1: Calculate the area under the line on a (c) An arrow indicates the direction of the
PV diagram process
 Examples on PV diagrams
Example 1
A gas expands from volume 1m3 to 2m3 at
constant atmospheric pressure.
(a) Calculate the work done by the gas.
(b) Represent the work done in PV diagram.
Solution.
(a) The pressure P = 1 atm = 101 KPa, Vf =2
m³and Vi = 1 m³.
From equation; W = = P,since P is constant,
it is taken out of the integral.
W = P(Vf - Vi ) = 101 × 103 ×(2-1) = 101
KJ.
(b) Since P is constant, PV diagram is a
straight line as shown in the figure. The area
is equal to the work done by the gas
Example 2 • We will calculate the area of the rectangle
The following PV diagram shows a gas PABQ.
taken from state A to state B. Calculate the • The area of a rectangle is the product of its
horizontal dimension (thee base) and its
work done on the gas during this event. vertical dimension (the height).
• The rectangle in this graph has a base of B rec =
2.5 x 10-3 m3 and a height of hrec = 0.6 x 106 Pa.
• The area of the rectangle is the product of the
base and the height.
• W = Brec hrec = (2.5 x 10-3 m3)(0.6 x 106 Pa) =
1500J

Step 2:
• Determine if the gas is being compressed or is
being expanded.
• The arrow is pointing to the right, indicating
Solution that the gas has expanded, it must give up
Step 1. Calculate the area under the line on some of its energy to exert a force on its
environment.
• Therefore, the work done on the gas is “negative”. .
(meaning the work was done by the gas)

Step 3:
• Report the work done as the area calculated in
Step 1, making it positive if the gas is
contracting, and negative if the gas is
expanding. Therefore, the work done on the gas
is W = -1500J

Example 3
• Calculate the work done on the gas sample
taken thro thermodynamic process from state A
to state B, as represented in Figure below

Solution
• Step 1: Calculate the area under the line on a
pressure-volume diagram
 • The rectangle has a base of B = 3 x 10-3 m3
• The area can be represented as a and a height of hrec = 1 x 106 Pa.
triangle and a rectangle as shown in • Therefore, the area of the rectangle is:
the figure below. Arec = B x hrec = (3 x 10-3 m3)(1 x 106 Pa)

= 3000 J
• The triangle has the same base as the
rectangle, which is B = 3 x 10-3 m3 and a
height of htri = 0.8 x 106 Pa.
• Since the area of a triangle is calculated as
of Atri = ½ (3 x 10-3 m3)(0.8 x 106 Pa)
= 1200J

• Therefore, the total area is

A = Arec + Atri = 3000 J + 1200 J = 4200 J
• To calculate the total area, we can Step 2:
calculate the area of the rectangle and • Determine if the gas is being compressed
• The arrow is pointing to the left, meaning
that the gas is being compressed by the
environment.

• Step 3: Report the work done as the area

calculated in Step 1, making it positive if the
gas is contracting, and negative if the gas is
expanding.

• Therefore, the work done on the gas during

this process is W = 4200 J
 The enthalpy-entropy graph (Mollier diagram
Mollier diagram is a graphical representation of a
functional relationship between enthalpy, entropy,
temperature, pressure and quality of steam.
• Mollier diagram is used commonly in the
design and analysis associated with power
plants, steam turbines, compressors, and
refrigeration systems
• The abscissa (horizontal or x-axis in a Cartesian
coordinate system) and ordinate (vertical or y-
axis in a Cartesian coordinate system) scales
represent entropy and enthalpy, respectively.
Therefore,
• Mollier diagram is also referred to as the
Enthalpy-Entropy Chart
• The constant pressure and constant temperature
lines in the Mollier diagram are referred to as
isobars and isotherms, respectively
• In addition, the graph includes lines • This relationship between Mollier diagram
representing constant steam quality, “x,” in and the psychrometric chart is apparent from
the bottom half of the diagram. the fact that both involve critical
• The bold line, spanning from left to right, in thermodynamic properties such as enthalpy,
the lower half of Mollier diagram is the temperature, sensible heat, latent heat
saturation line. and quality.
• The saturation line, labeled as x = 1, • A comparison of the Mollier diagram and
represents the set of points on Mollier the steam tables also reveals a marked
diagram where the steam is 100% vapor. similarity and equivalence between the two.
• All points above the saturation line are in • This equivalence between Mollier diagram
the superheated steam realm. and the steam tables is reinforced by the fact
• All points below the saturation line that both involve critical thermodynamic
represent a mixture of liquid and vapor properties of steam such as enthalpy,
phases entropy, temperature and pressure.
• A comparison of the Mollier diagram and Application of Mollier Diagram
the psychrometric chart reveals convincing • A common application of Mollier diagram
similarity between these two versatile and involves determination of an unknown
commonly applied thermodynamics tools. parameter among the key Mollier diagram
parameters such as, enthalpy, entropy, • Enthalpy Determination:
temperature pressure and quality. • To determine the enthalpy at point A, draw a
straight horizontal line from point A to the left till
it intersects with the diagonal enthalpy line. This
Example 1 horizontal line intersects the enthalpy line at an
(a) Determine if steam at 450°C and 1 bar is enthalpy value of, approximately, 3380 kJ/kg.
saturated or superheated. • Therefore, hA, or enthalpy at point A, is 3380
(b) Find the enthalpy and entropy of this steam kJ/kg.
• Entropy Determination: To determine the
entropy at point A, draw a straight vertical line
Solution: from point A to the bottom, until it intersects
• See the Mollier diagram in Figure below with the entropy line. The vertical line intersects
Identify the point of intersection of the 450°C the entropy line at, approximately, 8.7kJ/kg.°K.
line (or 450°C isotherm) and the constant • Therefore, sA, or entropy at point A, is
pressure line (or isobar) of 1 bar. This point of 8.7kJ/kg.°K
intersection of the two lines is labeled A. As
explained above, this region of the Mollier
diagram is the superheated steam region. Example 2
• Determine the amount of heat that must be
• Therefore, the steam at 450°C and 1 bar is
superheated.
• removed from a system, on per kg basis, in
order to reduce the temperature of steam
from 450°C, at 1 Atm. To 400°C, at 1
Atm.
• Solution:
• To determine the amount of heat that must
be removed from the steam in order to cool
the steam from 450°C, at 1 Atm. to 400°C,
at 1 Atm, we must assess the enthalpies at
those two points.
• The first point, at 450°C and 1 Atm, was
labeled as point A in Example 1.
• The enthalpy, hi at point A was determined
to be 3380 kJ/kg.
• The enthalpy, hf, at the second point,
referred to as point B, as shown on the
Mollier diagram in above in exanmple 1, is
• Therefore, the amount of heat that must be • hi = Enthalpy at 450°C and 1 Atm., as read
removed from the system in order to lower the from the Mollier Diagram
temperature from 450°C to 400°C, at 1 Atm, • = 3380 kJ/kg
would be:
• hf = Enthalpy at 400°C and 1 Atm., as read
• Δh = hi - hf
from the Mollier Diagram
• ∴ Δh = hi - hf = 3380 kJ/kg - 3280 kJ/kg =
• = 3280 kJ/kg
100 kJ/kg
• Then, using the Mollier Diagram, the
• In other words, 100 kJ of heat must be
removed from each kg of steam in order to amount of heat that must be removed from
cool it from 450°C, at 1 Atm. to 400°C, at 1 the system in order to lower the temperature
Atm. from 450°C to 400°C, at 1 Atm, would be:
Example 3 • Δh = hi - hf = 3380 kJ/kg - 3280 kJ/kg =
100 kJ/kg
• Prove the equivalence of the Mollier Diagram
and the Steam Tables by verifying the results
of Example 2 , through the use of Steam Tables • Now, lets determine the amount of heat to be
Solution: removed using the steam tables,
• The solution from Example 2.1, as restated • hi = Enthalpy at 450°C and 1 Atm
with the aid of Figure 3.1, is as follows: • = 3382.8 kJ/kg
• hf = Enthalpy at 400°C and 1 Atm.,
• = 3278.5 kJ/kg
So, using the Steam Tables, the amount of
heat that must be removed from the system
in order to lower the temperature from
450°C to 400°C, at 1 Atm, would be:
• Δh = hi - hf = 3382.8 kJ/kg - 3278.5
kJ/kg = 104.3 kJ/kg

• Therefore, for most practical purposes, the

Mollier Diagram and the Steam Tables are
equivalent insofar as thermodynamic
system analyses are concerned.
• The 4.3% difference between the two
approaches is due mainly to the small
amount of inaccuracy in reading of the
scale of the Mollier Diagram
Single-Phase Region
• For the regions of the diagram where a single
phase exists, Figure below implies a relation
connecting P, V, and T which may be
expressed by the functional equation:

• This means that an equation of state exists

relating pressure, molar or specific volume,
and temperature for any pure homogeneous
fluid in equilibrium states.
• The simplest equation of state is for an ideal
gas, PV = RT, a relation which has
approximate validity for the low pressure gas
region
• An equation of state may be solved for any
one of the three quantities P, V, or T as a
function of the other two.
• For example, if V is considered a function • Combination of Equations above provides
of T and P, then the equation
V = V(T, P),
and

• Both β and K are are zero. for

incompressible fluid
• The partial derivatives in this equation have • No real fluid is truly incompressible, but the
definite physical meanings, and are related idealization is useful, because it often
to two properties, commonly tabulated for provides a sufficiently realistic model of
liquids, and defined as follows liquid behavior for practical purposes.
• There is no PVT equation of state for an
incompressible fluid, because V is
independent of T and P.
• For small changes in T and P little error is
introduced if they are assumed constant.
• Integration of Eq. above then yields:
• Integration of Eq. above then yields: (b) The pressure generated when acetone is
heated at constant volume from 20°C and 1
bar to 30 °C
(c) The volume change when T and P go from
• This is a less restrictive approximation 20°C and 1 bar to 0°C and 10 bar.
than the assumption of an incompressible Solution  P 
fluid (a) The derivative  T Vis determined by
Example
 1.487 x 10 3 C application of Eq.  dT   dP 0 (contV )
For liquid acetone at 20°C
6
and 1 bar,
 62 x 10 bar to the case for which V is constant and
V 1.287 cm3 g  1 dV = 0 :
 dT   dP 0 (contV )

or  P   1.487 x 10 3
    6
24 bar  C
 T V  62 x10
 P 
For acetone, find :T V (b) If β and κ are assumed constant in the 10°C
(a) The value of at 20°C and 1 bar temperature interval, then for constant volume
the equation derived in (a) may be written (V=
  V2
0.9702
P  T (24)(10) 240 bar V1

and And

P2 P1  P 1  240 241bar V2 (0.9702)(1.287) 1.249 cm3 g  1

(c) Direct substitution into Eq. which gives

V V2  V1 1.249  1.287  0.038 cm3 g  1

gives

V2
In (1.487 x 10 3 )(  20)  (62 x 10 6 )(9)  0.0303
V1
• VlRlAL EQUATIONS OF STATE
• Figure below indicates the complexity of
the PVT behavior of a pure substance and
suggests the difficulty of its description by
an equation. However, for the gas region
alone relatively simple equations often
suffice
• Along a vapor-phase isotherm such as Tl
in Fig. b, V decreases as P increases. The
PV product for a gas or vapor should
therefore be much more nearly constant
than either of its members, and hence more
easily represented.
• For example, PV along an isotherm may
be expressed as a function of P by a power
series: 2 PV diagrams for a pure substance. (a) Showing
PV a  bP  cP  ....... solid, liquid, and gas regions. (b) Showing liquid,
If b aB ', c aC ', etc... liquidl/vapor, and vapor regions with isotherms
 PV a  aB ' P  aC ' P 2  .aD ' P 3 ......
. 2 3
PV  a (1  B ' P  C ' P  .D ' P
• In principle, the right side of Eq. above  ......)
is an
infinite series. • It is this property of gases that makes
• However, in practice a finite number of terms is
used. In fact, P VT data show that at low pressures
them valuable in thermometry, because
truncation after two terms usually provides the limiting values are used to establish a
satisfactory results. temperature scale which is independent
Ideal-Gas Temperatures; Universal Gas
of the gas used as thermometric fluid.
Constant
• In equation above; a, B', C', etc., are constants for • Make (P V)* directly proportional to T,
a given temperature and a given chemical species/ with R as the proportionality constant:
• However, parameters B', C', etc., in Eq. above are
species dependent and functions of
temperature, but parameter a is the same (PV)* =a = RT
function of temperature for all species.
• Therefore, Equation above becomes:
Two Forms of the Virial Equation
• A useful auxiliary thermodynamic
property is defined by the equation
 • Both of these equations are known as virial
expansions, and the parameters B', C', D',
• This dimensionless ratio is called the etc., and B, C, D, etc., are called virial
compressibility factor. coeficients.
• With this definition and with a = RT • Parameters B' and B are second virial
(Equation (PV)* =a = RT), then Equation coefficients; C' and C are third virial
PV a  aB ' P  aC ' P 2  .aD ' P 3 ...... coefficients; etc. For a given gas the virial
2 3
coefficients are functions of temperature
PV a (1  B ' P  C ' P  .D ' P  ......) only.
• THE IDEAL GAS
becomes
• Since the terms BIV, c/v2, etc., of the virial
Z (1  B ' P  C ' P 2  .D ' P3  ......) expansion above arise on account of
molecular interactions, the virial coefficients
An alternative expression for Z is also in B, C, etc., would be zero if no such
common use interactions existed. The virial expansion
would then reduce to:
 • If such forces did not exist, no energy would be required
• behavior of the gas. As the pressure of a real gas is reduced
to alter the average
at constant temperature, V increases
• intermolecular distance, and therefore no energy would be
• and the contributions of the terms B/ V , C/ v2, etc.,
required to bring about volume and
decrease. For a pressure approaching zero,
• pressure changes in a gas at constant temperature. We
• Z approaches unity, not because of any change in the virial
conclude that in the absence of molecular
coefficients, but because V becomes infinite. Thus in the
• interactions, the internal energy of a gas depends on
limit as the pressure approaches zero, the equation of state
temperature only.
assumes the
• These considerations
• same simple form as for the hypothetical case of B = C
= . . . = 0; i.e., • of the behavior of a hypothetical gas in which no
intermolecular forces exist and of a real gas
• in the limit as pressure approaches zero lead to the
definition of an ideal gas as one whose
• We know from the phase rule that the internal energy of a
• macroscopic behavior is characterized by:
real gas is a function of
• The equation of state:
• pressure as well as of temperature. This pressure
dependency is the result of forces between
• the molecules.
 For engineering purposes their use is practical
• An internal energy that is a function of temperature only
only where convergence is very rapid, that is,
where two or three terms suffice for
reasonably close approximations to the values
of the series.
• APPLICATION OF THE VlRlAL EQUATIONS: This is realized for gases and vapors at low to
moderate pressures.
• The two forms of the virial expansion given by above) are
infinite series.
• Figure below shows a compressibility-factor
graph for methane. Values of the
compressibility factor Z (as calculated from
P VT data for methane by the defining
equation Z = P V/ RT) are plotted vs.
• pressure for various constant temperatures.
• The resulting isotherms show graphically
• what the virial expansion in P is intended to represent
analytically. All isotherms originate
• at the value Z = 1 for P = 0. In addition the isotherms are
nearly straight lines at low pressures.
• Thus the tangent to an isotherm at P = 0 is a good
approximation of the isotherm from
• P -+ 0 to some finite pressure. Differentiation of Eq. (3.1
1) for a given temperature gives:

• From which

• Compressibility-factor graph for methane

• Thus the equation of the tangent line is • Equation
Z 1  B / P
• a result also given by truncating Eq.

•
• may also be truncated to two terms
• to two terms. A more common form of this equation for application at low pressures:
• results from the substitution B' = BIRT: •: PV B
Z
PV
1 
BP Z 1 
RT RT RT V
• When the virial equation is truncated to two
terms, Eq.
PV BP
Z 1 
RT RT
• is preferred
• This equation
• satisfactorily represents the P V T behavior of many • Example
vapors at subcritical temperatures up to a
• pressure of about 5 bar. At higher temperatures it is • Reported values for the virial
appropriate for gases over an increasing coefficients of isopropanol vapour at
• pressure range as the temperature increases. The second
virial coefficient B is substance dependent
200°C are:
• and a function of temperature. B= -388 cm3 mol-1
C =-26, 000 cm6 mol-2
• When the virial equation is truncated to three terms, the
appropriate form is: Calculate V and Z for isopropanol
vapour 200°C and 10 bar by
(a) The ideal-gas equation
(b) Equation PV BP
• This equation can be solved directly for pressure, but is
Z 1 
cubic in volume RT RT
• Solution CUBIC EQUATIONS OF STATE
• The absolute temperature is T= 473.15 K, and • If an equation of state is to represent the PVT
the appropriate value of the gas constant is behavior of both liquids and vapors, it must
R= 83.14 cm3 bar mol-1K-1 • encompass a wide range of temperatures and
pressures. Yet it must not be so complex as to
• present excessive numerical or analytical
(a) (i) By the ideal-gas equation, V=RT/P = difficulties in application. Polynomial equations
that
[(83.14)(473.15)]/10 = 3,934 cm3 mol-1
• are cubic in molar volume offer a compromise
(ii) Z=1 for an ideal gas between generality and simplicity that is suitable
• to many purposes. Cubic equations are in fact the
simplest equations capable of representing
(b) (i) Solving Equation PV BP • both liquid and vapor behavior
Z 1 
RT RT
for V, we find • The van der Waals Equation of State
• The first practical cubic equation of state was the
V = (RT/P) +B= 3,934 – 388 = 3,546 cm3 mol-1 van der Waals Equation of State given by
(ii)
PV V 3,546
Z   0.9014
RT RT / P 3,934
Here, a and b are positive constants; where a is associated
with the attractive force a /V2 between molecules in the Notes
fluid and b is associated with the repulsive force RT/(V-b) (1) For van der Waals equation, the constants
between molecules in the fluid.
27 R TC 2 2 RTC
when they are zero, the ideal-gas equation is recovered.
a b
• Given values of a and b for a particular fluid, one can
64 Pc 8Pc
calculate P as a function of V for various values of T.
• Since the introduction of the van der Waals equation, (2) For Redlich/Kwong equation, the constants
scores of cubic equations of state have been proposed. All and
are special cases of the equation:
• The Redlich/Kwong equation, is a modern development 0.42748R 2TC 2.5 0.08664 RTC
of cubic equations of state. This equation, like other cubic a b
equations o, has three volume roots, of which two may be Pc Pc
complex
• Theorem of Corresponding States;
• Redlich/Kwong equation is gvien by the following Acentric Factor
expression

• Experimental observation shows that

compressibility factors Z for different fluids
RT a exhibit similar behavior when correlated as a
P  1/ 2
V  b T V (V  b) function of reduced temperature T, and
and reducedpressure P,; by dejinition,
• Generalized Correlations for Gases • “All fluids, when compared at the same
• Equations of state which express Z as a reduced temperature and reduced
function of Tr and Pr are said to be pressure, have approximately the same
generalized, because of their general compressibility factor, and all deviate from
applicability to all gases. ideal-gas behavior to about the same
degree’
• Experimental observation shows that compressibility
factors Z for different fluids exhibit similar behavior when
correlated as a function of reduced temperature T, and
reducedpressure P,; by dejinition,
• Although this theorem is very nearly exact for the simple
Any equation of state can be put into this form, fluids (argon, krypton, and
thus providing a generalized correlation for the • xenon) systematic deviations are observed for more
properties of fluids. complex fluids.
Such correlation has the advantage of allowing • Appreciable improvement results from introduction of a
third corresponding-states parameter, characteristic of
the estimation of property values from very molecular structure; the most popular such parameter is
limited information. One needs only the critical the acentric factor w,
temperature and critical pressure of the fluid.
This is the basis for the two-parameter theorem
of corresponding states. This states that
• The acentric factor for a pure chemical • If the two-parameter theorem of
species is defined with reference to its vapor corresponding states were generally valid,
pressure. Since the logarithm of the vapor the slope S would be the same for all pure
pressure of a pure fluid is approximately fluids. This is observed not to be true;
linear in the reciprocal of absolute each fluid has its own characteristic value
temperature, of S, which could in principle serve as a
third corresponding-states parameter.
However, Pitzer noted that all vapor-
pressure data for the simple fluids (Ar, Kr,
• Xe) lie on the same line when plotted as
log P,Sat vs. 1/T, and that the line passes
through log PTt = -1.0 at T, = 0.7.
• The acentric factor is defined as this
• where PTt is the reduced vapor pressure, T, difference evaluated at T, = 0.7:
is the reduced temperature, and S is the
slope of a plot of log P,Sat vs. 1/T,. Note that
"log" denotes a logarithm to the base 10.
• Therefore w can be determined for any fluid from Tc, PC, • Pitzer Correlations for the Compressibility Factor
and a single vapor-pressure measurement made at T, = 0.7.
• The correlation for Z takes the form:
Values of w and the critical constants T,, PC, and V, for a
number of fluids are listed

• The definition of w makes its value zero for argon,

krypton, and xenon, and experimental
• where ZOand Z1' are functions of both Tr and P,. When w =
• data yield compressibility factors for all three fluids that 0, as is the case for the simple fluids,
are correlated by the same curves
• the second term disappears, and ZO becomes identical with
• when Z is represented as a function of T, and P,. This is the Z. Thus a generalized correlation
basic premise of the following
• for Z as a function of T, and P, based on data for just argon,
• three-parameter theorem of corresponding states: krypton, and xenon provides
• the relationship ZO = F’ O(T,, P,).
• All fluids having the same value of w, when • By itself, this represents a two-parameter
compared at the same Tr and Pr, have about the correspondingstates
same value of Z, and all deviate from ideal-gas
• correlation for Z.
• behavior to about the same degree.
• Equation
the simplest form of the virial
equation:
is a simple linear relation between Z and o for given values
of Tr and P,.
• Experimental data for Z for nonsimple fluids plotted vs. w
at constant Tr and Pr do indeed yield
• approximately straight lines, and their slopes provide Thus, Pitzer and coworkers proposed a
values for Z' from which the generalized second correlation, which yields values for
• function Z1 = F1(T,, P,) can be constructed BPc/RTc:

• The tabular nature of the generalized compressibility-

factor correlation is a disadvantage, but
• the complexity of the functions Z0 and Z1 precludes their
accurate representation by simpleequations. However, we Together, these two equations become
can give approximate analytical expression to these
functions for a limited range of pressures
• The basis for this is Eq.
• : PV BP
Z 1 
RT RT
• Comparison of this equation with Eq. • They are well represented by the following
equations:
0 1
Z Z  w Z
provides the following identifications:

Example
• Determine the molar volume of n-butane at
510 K and 25 bar by each of the following:
(a) The ideal-gas equation
• Second virial coefficients are functions of
temperature only, and similarly B0 and B1 (b) The generalized compressibility-factor
are functions of reduced temperature only. correlation
(c) The generalized virial-coefficient
correlation
• Solution • Interpolation in Tables for Z, then
provides
(a) By the ideal-gas equation,

RT (83.14)(510)  1 Z = 0.865 and Z1=0.038

0
3
V  1, 696.1 cm mol
P 25 Thus by equation
0 1
(b) Taking values of Tc and Pc from the
Z Z  w Z
Tables of Tc and Pc , we find with w = 0.200,
510 Z Z 0  w Z 1 0.865  (0.200)(0.038) 0.873
Tr  1.200
425.1
and
25 ZRT (0.873)(83.14)(510)
Pr  0.669 V  1, 480.7 cm3 mol  1
37.96 P 25
 • Then by Equation
(c) Values of B0 and B1 are given by Eqs

0.659
Z 1  ( 0.220) 0.879
1.200

B0 = - 0.232 and B1 = 0.059

By Eq. • From which we find

V = 1,489.1 cm3 mol-1
BPc
B 0  wB1  0.232  (0.200)(0.059)  0.220
RTc
a
Example
where n is the number of moles, m is the
• A mass of 500g of gaseous ammonia is mass of ammonia in the vessel if total volumr
contained in a 30,000cm3 vessel Vt, and M is the molar mass of ammonia.
immersed in a constant –temperature • Thus,
bath at 65°C. Calculate the pressure of
the gas by each of the following: 30, 000
V 1, 021.2 cm3 mol  1
500 /17.02
(a) The ideal-gas equation
(b) The Redlich/Kwong equation (a) By the ideal-gas equation,
(c) A generalized correlation
RT (83.14)(65  273.15)
P  27.53 bar
V 1, 021.2
Solution
The molar volume of ammonia in the
vessel is given by (b) For application of the Redlich/Kwong
Vt Vt equation,
V  0.42748R 2TCwe
2.5 first evaluate
b
a and
0.08664 RTCb
n m/M a
Pc Pc
 now gives
(0.42748)(83.14) 2 (405.7) 2.5
a
112.8 (83.14)(338.15) 8.684 x 107
P  1/ 2
23.84 bar
1, 021.2  25.9 (338.15) (1, 021.2  25.9)
8.684 x 107 bar cm6 K 1/ 2

(c) Since the reduced pressure is low (≈

and
0.2), we use the generalized virial
(0.08664)(83.14)(405.7) coefficient correlation.
b 25.91 cm 3
112.8 For a reduced temperature of
Tr=338.15/405.7 = 0.834, values of B0 and
Where values of Tc and Pc are from B1 as given by Eqs
the Tables.
Substitution of known values into Eq
RT a
P  1/ 2
V  b T V (V  b)
 and
are
B0= -0.482 and B1=-0.232  0.541RTc  (0.541)(83.14)(405.7)
B   161.8 cm3 mol  1
Pc 112.8
Substitute into Eq
Solving Eq below for P,
PV BP
Z 1 
RT RT
we obtain
with w = 0.253,
yields
RT (80.14)(338.15)
P  23.76 bar
V  B 1, 021.2 161.8
BPc
 0.482  (0.253)(  0.232)  0.541
RTc An iterative solution is not necessary,
because B is independent of pressure.
Compressibility Charts • In these expressions, R is the universal gas
• The p-v-T relation for a wide range of constant and pc and Tc denote the critical
common gases is often illustrated by the pressure and temperature, respectively.
generalized compressibility chart of Figure
below.
• To achieve greater accuracy, variables other
• The compressibility charts use the than Zc have been proposed as a third
compressibility factor as one of the parameter — for example, the acentric factor.
coordinates.
• Generalized compressibility data are also
• In this chart, the compressibility factor, Z, is available in tabular form.
plotted vs. the reduced pressure, PR, reduced
• The use of generalized data in any form
temperature, TR, and pseudoreduced specific
(graphical, tabular, or equation) allows p, v,
volume, V’R where
and T for gases to be evaluated simply and
with reasonable accuracy.
• When accuracy is an essential consideration,
and generalized compressibility data should not
be used as a substitute for p-v-T data for a
given substance as provided by computer
software, a table, or an equation of state.
Equations of State • These expressions are known as virial
expansions, and the coefficients … and B, C,
• Considering the isotherms of D … are called virial coefficients
compressibility chart, it is plausible that the
• Over 100 equations of state have been
variation of the compressibility factor might
developed in an attempt to portray accurately
be expressed as an equation, at least for the p-v-T behavior of substances and yet avoid
certain intervals of p and T. the complexities inherent in a full virial series.
• Two expressions can be written that enjoy a • Most are developed for gases, but some
theoretical basis. describe the p-v-T behavior of the liquid
• One gives the compressibility factor as an phase, at least qualitatively.
infinite series expansion in pressure, • Every equation of state is restricted to
particular states.
• The realm of applicability is often indicated
by giving an interval of pressure, or density,
where the equation can be expected to
and the other is a series in 1/v,
represent the p-v-T behavior faithfully. When
it is not stated, the realm of applicability often
may be approximated by expressing the
equation in terms of the
• compressibility factor Z and the
reduced properties, of the
compressibility factor Z and the
reduced properties, and
superimposing the result on a • Although the two-constant Redlich-Kwong equation
generalized compressibility chart performs better than some equations of state having
or comparing with compressibility several adjustable constants, two-constant equations
data from the literature. tend to be limited in accuracy as pressure (or density)
increases. Increased accuracy normally requires a
• Equations of state can be
greater number of adjustable constants.
classified by the number of
adjustable constants they involve. • For example, the Benedict-Webb-Rubin equation,
• The Redlich-Kwong equation is which involves eight adjustable constants, has been
considered by many to be the best successful in predicting the p-v-T behavior of light
of the two-constant equations of hydrocarbons.
state. It gives pressure as a • Benedict-Webb-Rubin equation is also explicit in
function of temperature and pressure,
specific volume and thus is
explicit in pressure:
• compressibility factor Z and the
reduced properties, of the
compressibility factor Z and the
reduced properties, and
superimposing the result on a • Although the two-constant Redlich-Kwong equation
generalized compressibility chart performs better than some equations of state having
or comparing with compressibility several adjustable constants, two-constant equations
data from the literature. tend to be limited in accuracy as pressure (or density)
increases. Increased accuracy normally requires a
• Equations of state can be
greater number of adjustable constants.
classified by the number of
adjustable constants they involve. • For example, the Benedict-Webb-Rubin equation,
• The Redlich-Kwong equation is which involves eight adjustable constants, has been
considered by many to be the best successful in predicting the p-v-T behavior of light
of the two-constant equations of hydrocarbons.
state. It gives pressure as a • Benedict-Webb-Rubin equation is also explicit in
function of temperature and pressure,
specific volume and thus is
explicit in pressure:
Generalized