CHEMICAL ENGINEERING

THERMODYNAMICS-I
UNIT-II

Mr. M. KOTESWARA RAO

Volumetric Properties of Pure Fluids
PVT BEHAVIOR OF PURE SUBSTANCES:
 Vaporization
 Condensation
 Melting
 Freezing
 Sublimation
 Desublimation
 Triple point
 Critical point
Volumetric Properties of Pure Fluids
PV Diagram:
Volumetric Properties of Pure Fluids
PT Diagram:
Single-Phase Region
❖ For the regions of the diagram where a single phase
exists, PV diagram (b) implies a relation connecting P,
V, and T which may be expressed by the functional
equation:
𝑓 𝑃, 𝑉, 𝑇 = 0
❖ 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
pressure gas region of PV diagram (b) .
❖ 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.
Single-Phase Region
❖ For example, if V is considered a function of T and P, then V =V(T, P), and
𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑P
𝜕𝑇 𝑃 𝜕𝑃 𝑇
❖ The partial derivatives in this equation have definite physical meanings, and are
related to two properties, commonly tabulated for liquids, and defined as follows:
1 𝜕𝑉
❖ Volume expansivity 𝛽 ≡
𝑉 𝜕𝑇 𝑃
1 𝜕𝑉
❖ Isothermal compressibility: K≡ −
𝑉 𝜕𝑃 𝑇
∴ 𝑑𝑉 = 𝛽𝑉𝑑𝑇 − 𝐾𝑉𝑑𝑃
𝑑𝑉
= 𝛽𝑑𝑇 − 𝐾𝑑𝑃
𝑉
❖ The isotherms for the liquid phase on the left side of of PV diagram (b) are very
𝜕𝑉 𝜕𝑉
steep and closely spaced. Thus both 𝑎𝑛𝑑 and hence both β and K are
𝜕𝑇 𝑃 𝜕𝑃 𝑇
small.
Single-Phase Region
❖ This characteristic behavior of liquids (outside the critical region) suggests an
idealization, commonly employed in fluid mechanics and known as the
incompressible fluid, for which both ,β and K are zero.
❖ There is no PVT equation of state for an incompressible fluid, because V is
independent of T and P.
❖ For liquids β is almost always positive (liquid water between 273.15 K (0°C) and
277.15 K (4°C) is an exception), and K is necessarily positive.
❖ At conditions not close to the critical point, β and K are weak functions of
temperature and pressure.
❖ Thus for small changes in T and P little error is introduced if they are assumed
𝑑𝑉
constant. Integration of Eq. = 𝛽𝑑𝑇 − 𝐾𝑑𝑃 then yields
𝑉
𝑉2
ln = 𝛽 𝑇2 − 𝑇1 − 𝐾(𝑃2 − 𝑃1 )
𝑉1
❖ Example 3.1:
❖ For acetone at 293K(20 °C) and 1 bar
𝛽 = 1.487 × 10−3 𝐾 −1 , 𝐾 = 62 × 10−6 𝑏𝑎𝑟 −1 , 𝑉 = 1.287 × 10−3 𝑚3 /𝑘𝑔
𝜕𝑃
Find (a) The value of .
𝜕𝑇 𝑉
(b) The pressure generated when acetone is heated at constant volume from 293K(20
°C) and 1 bar to 303K(30 °C) .
(c) The volume change when acetone is changed from 293K(20 °C) and 1 bar to
273K(0 °C) and 10 bar.
Data:
𝑇1 = 293𝐾(20 °𝐶)
𝛽 = 1.487 × 10−3 𝐾 −1
𝐾 = 62 × 10−6 𝑏𝑎𝑟 −1
𝑉 = 1.287 × 10−3 𝑚3 /𝑘𝑔
𝑇2 = 303𝐾(30 °𝐶)
𝑇3 = 273𝐾(0 °𝐶)
𝑃3 = 10 𝑏𝑎𝑟
❖ Solution:
1 𝜕𝑉
❖ 𝛽=
𝑉 𝜕𝑇 𝑃
1 𝜕𝑉
❖ 𝐾 =−
𝑉 𝜕𝑃 𝑇
❖ 𝑑𝑉/𝑉 = 𝛽𝑑𝑇 − 𝑘𝑑𝑃
❖ 𝐴𝑡 𝑐𝑜𝑛𝑠𝑡. 𝑣𝑜𝑙𝑢𝑚𝑒 𝛽𝑑𝑇 − 𝑘𝑑𝑃 = 0
𝜕𝑃 𝛽
❖ = = (1.487 × 10−3 )/(62 × 10−6 ) = 24 𝑏𝑎𝑟/𝐾
𝜕𝑇 𝑉 𝑘
❖ If β and k are assumed to be constant 10K temp. interval, then the at const. volume
𝛽
❖ ∆𝑃 = ∆𝑇 = 24 × 10 = 240 𝑏𝑎𝑟
𝑘
❖ 𝑃2 = 𝑃1 + ∆𝑃 = 1 + 240 = 241𝑏𝑎𝑟
❖ ln(𝑉2 /𝑉1 ) = 𝛽(𝑇2 − 𝑇1 ) − 𝐾(𝑃2 − 𝑃1 )
❖ = 1.487 × 10−3 (273 − 293) − 62 × 10−6 (10 − 1) = −0.0303
❖ 𝑉2 /𝑉1 = exp(−0.0303) = 0.9702
❖ 𝑉2 = 1.287 × 10−3 × 0.9702 = 1.249 × 10−3 𝑚3 / 𝑘𝑔
❖ ∆𝑉 = 𝑉2 − 𝑉1 = (1.249 − 1.287) × 10−3 = −0.038 × 10−3 𝑚3 / 𝑘𝑔
❖ 3.1:Express the volume expansivity and the isothermal compressibility as functions
of density ρ and its partial derivatives. For water at 323.15 K (50°C) and 1 bar, 𝐾 =
44.18 × 10−6 𝑏𝑎𝑟 −1 . To what pressure must water be compressed at 323.15 K
(50°C) to change its density by 1 %? Assume that K is independent of P.
Data: ❖ Solution: ❖ 𝜌2 = 1.1𝜌1
𝑇1 = 323𝐾 50 °𝐶 1 𝜕𝑉 1 𝜕𝑉
❖ 𝛽= ,K=− ❖ ∆𝑃 =
1
ln
1.1𝜌1
𝑃 = 1 𝑏𝑎𝑟 𝑉 𝜕𝑇 𝑃 𝑉 𝜕𝑃 𝑇 44.18×10−6 𝜌1
𝐾 = 44.18 × 10−6 𝑏𝑎𝑟 −1 1 1
❖ We know 𝑉 = ⇒ 𝜕𝑉 = − 2 𝜕𝜌 = 225.2 𝑏𝑎𝑟
𝑃2 =? 𝜌 𝜌
1 𝜕𝑉 1 𝜕𝜌 1 𝜕𝜌 𝑃2 = 𝑃1 + ∆𝑃
❖ ∴𝛽= =𝜌 − 2 =−
𝑉 𝜕𝑇 𝑃 𝜌 𝜕𝑇 P ρ 𝜕𝑇 𝑃 𝑃2 = 1 + 225.2
1 𝜕𝑉 1 𝜕𝜌 1 𝜕𝜌
❖ 𝐾=− = −𝜌 − 2 = = 226.2 𝑏𝑎𝑟
𝑉 𝜕𝑃 𝑇 𝜌 𝜕𝑃 𝑇 ρ 𝜕𝑃 𝑇
1 𝑑𝜌
❖ At constant temperature 𝐾 =
𝜌 𝑑𝑃
𝑑𝜌
❖ = 𝐾𝑑𝑝 integrate both sides
𝜌
𝜌 1 𝜌
❖ ln 2 = 𝐾 𝑃2 − 𝑃1 = 𝐾∆𝑃 ⇒ ∆𝑃 = ln 2
𝜌1 𝐾 𝜌1
VIRIAL EQUATIONS OF STATE
❖ Along a vapor-phase isotherm such as in Fig. 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:
𝑃𝑉 = 𝑎 + 𝑏𝑃 + 𝐶𝑃2 + ⋯
❖ 𝑖𝑓 𝑏 ≡ 𝑎𝐵′ . 𝑐 ≡ 𝑎𝐶 ′ , 𝑒𝑡𝑐 𝑡ℎ𝑒𝑛
𝑃𝑉 = 𝑎(1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷 ′ 𝑃3 + ⋯
❖ Where a, 𝐵′ , 𝐶 ′ , etc are constants for a given
temperature and a given chemical species.
❖ In principle, the right side of Eq. is an infinite series.
❖ However, in practice a finite number of terms is used.
❖ In fact, PVT data show that at low pressures truncation
after two terms usually provides satisfactory results.
❖ Ideal-Gas Temperatures; Universal Gas
Constant:
❖ Parameters B', C', etc., in above Eq. are species
dependent and functions of temperature, but
parameter a is the same function of temperature for
all species.
❖ This is shown experimentally by measurements of
volumetric data as a function of P for various gases at
constant temperature.
❖ Figure, for example, is a plot of PV vs. P for four
gases at the triple-point temperature of water. The
limiting value of PV as P is the same for all of the
gases. In this limit (denoted by the asterisk), Eq. (3.6)
becomes:
𝑃𝑉 ∗ = 𝑎 = 𝑓 𝑇
❖ Make (PV)* directly proportional to T, with R as the
proportionality constant: 𝑃𝑉 ∗ = 𝑎 = 𝑅𝑇
❖ Assign the value 273.16 K to the temperature of the triple point of water (denoted
by subscript t):
𝑃𝑉 ∗𝑡 = 𝑅 ×273.16K
Division of above two eq.s gives
𝑃𝑉 ∗ 𝑇/𝐾
∗ =
𝑃𝑉 𝑡 273.16 𝐾
𝑇 𝑃𝑉 ∗
= 273.16 ×
𝐾 𝑃𝑉 ∗𝑡
❖ Above Equation establishes the Kelvin temperature scale throughout the temperature
range for which values of (P V)* are experimentally accessible.
❖ The state of a gas at the limiting condition where P deserves some discussion. The
molecules making up a gas become more and more widely separated as pressure is
decreased, and the volume of the molecules themselves becomes a smaller and
smaller fraction of the total volume occupied by the gas.
❖ the forces of attraction between molecules become ever smaller because of the
increasing distances between them
❖ In the limit, as the pressure approaches zero, the molecules are separated by infinite
distances.
❖ Their volumes become negligible compared with the total volume of the gas, and the
intermolecular forces approach zero.
❖ At these conditions all gases are said to be ideal, and the temperature scale established
by above Eq. is known as the ideal-gas temperature scale.
❖ The proportionality constant R is called the universal gas constant. Its numerical value
is determined by means of Eq. 𝑃𝑉 ∗𝑡 = 𝑅 × 273.16𝐾 from experimental PVT data:
𝑃𝑉 ∗𝑡
𝑅=
273.16K
❖ Since PVT data cannot in fact be taken at zero pressure, data taken at finite pressures
are extrapolated to the zero-pressure state.
❖ Determined as indicated by Fig., the accepted value of 𝑃𝑉 ∗𝑡 is 22.7118 m3 bar kmol-1
leading to the following value of R:
22.7115 𝑚3 𝑏𝑎𝑟𝑘𝑚𝑜𝑙 −1
𝑅= = 0.0831447𝑚3 𝑏𝑎𝑟𝑘𝑚𝑜𝑙 −1 𝐾 −1
273.16𝐾
Two Forms of the Virial Equation:
❖ A useful auxiliary thermodynamic property is by the equation:
𝑃𝑉
𝑍≡
𝑅𝑇
❖ This dimensionless ratio is called the compressibility factor. With this definition and
with a = RT virial equation 𝑃𝑉 = 𝑎(1 + 𝐵′ 𝑃 + 𝑐 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯) becomes
𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯
An alternative expression for Z is also in common use
𝐵 𝐶 𝐷
𝑍 =1+ + 2+ 3+⋯
𝑉 𝑉 𝑉
❖ Both of these equations are known as virial expansions, and the parameters B', C', D',
etc., and B, C, D, etc., are called virial coefficients.
❖ Parameters B' and B are second virial coefficients; C' and C are third virial coefficients;
etc. For a given gas the virial coefficients are functions of temperature only.
❖ The two sets of coefficients in Eqs. (3.11) and (3.12) are related as follows:
2 3
𝐵 𝐶 − 𝐵 𝐷 − 3𝐵𝐶 + 2𝐵
𝐵′ = , 𝐶′ = , 𝐷 ′ = , 𝑒𝑡𝑐
𝑅𝑇 𝑅𝑇 2 𝑅𝑇 3
𝑍 = 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷 ′ 𝑃3 + ⋯
𝑃𝑉 𝐵 𝐶 𝐷
𝑧= =1+ + 2+ 3+⋯
𝑅𝑇 𝑉 𝑉 𝑉
𝑅𝑇 𝐵 𝐶 𝐷 1 𝐵 𝐶 𝐷
𝑃= 1 + + 2 + 3 + ⋯ = 𝑅𝑇 + + + +⋯
𝑉 𝑉 𝑉 𝑉 𝑉 𝑉2 𝑉3 𝑉4
2
′
1 𝐵 𝐶 𝐷 ′
1 𝐵 𝐶 𝐷
𝑍 =1+𝐵 𝑅𝑇 + + + +⋯ +𝐶 𝑅𝑇 + + + +⋯ +
𝑉 𝑉2 𝑉3 𝑉4 𝑉 𝑉2 𝑉3 𝑉4
3
1 𝐵 𝐶 𝐷
𝐷′ 𝑅𝑇 + 2+ 3+ 4+⋯ +⋯
𝑉 𝑉 𝑉 𝑉
𝐵′ 𝑅𝑇 𝐵𝐵′ 𝑅𝑇 𝐶𝐵′ 𝑅𝑇 𝐷𝐵′ 𝑅𝑇 𝐶 ′ 𝑅2 𝑇 2 𝐵2 𝐶 ′ 𝑅2 𝑇 2 2𝐵𝐶 ′ 𝑅2 𝑇 2
𝑍 =1+ + 2
+ 3
+ 4
+⋯+ 2
+ 4
+ 3
+⋯
𝑉 𝑉 𝑉 𝑉 𝑉 𝑉 V
′
DR T3 3 ′ 3
3BD R T 3
+ +
V3 𝑉4
𝐵 𝐶 𝐷
Compare coefficients of above equation with coefficients of eq. 𝑧 = 1 + + + +⋯
𝑉 𝑉2 𝑉3
 𝐵′ 𝑅𝑇 𝐵𝐵′ 𝑅𝑇 𝐶𝐵′ 𝑅𝑇 𝐷𝐵′ 𝑅𝑇 𝐶 ′ 𝑅2 𝑇 2 𝐵2 𝐶 ′ 𝑅2 𝑇 2 2𝐵𝐶 ′ 𝑅2 𝑇 2
𝑍 =1+ + 2
+ 3
+ 4
+ ⋯+ 2
+ 4
+ 3
+⋯
𝑉 𝑉 𝑉 𝑉 𝑉 𝑉 V
D′ R3 T 3 3B𝐷′ 𝑅3 𝑇 3
+ 3
+
V 𝑉4
𝐵 𝐶 𝐷
𝑧 =1+ + 2+ 3+⋯
𝑉 𝑉 𝑉
➢ 𝐵 = 𝐵 ′ 𝑅𝑇

➢ 𝐶 = 𝐵𝐵′ 𝑅𝑇 + 𝐶 ′ 𝑅2 𝑇 2 = 𝐵2 + 𝐶 ′ 𝑅2 𝑇 2
′ 𝐶−𝐵2
➢ 𝐶 =
𝑅2 𝑇 2
𝐶−𝐵2 2 2
➢ 𝐷= 𝐵′ 𝐶𝑅𝑇 + 𝐷′ 𝑅3 𝑇 3 + 2𝐵𝐶 ′ 𝑅2 𝑇 2 = 𝐵𝐶 + 𝐷′ 𝑅3 𝑇 3 + 2𝐵 2 2 𝑅 𝑇
𝑅 𝑇
➢ 𝐷 = 𝐵𝐶 + 𝐷′ 𝑅3 𝑇 3 + 2𝐵𝐶 − 2𝐵3
𝐷−3𝐵𝐶+2𝐵3
➢ 𝐷′ =
𝑅3 𝑇 3
 𝐵 𝐶 𝐷
IDEAL GAS: 𝑧 =1+ + + +⋯
𝑉 𝑉2 𝑉3
𝐵=𝐶=𝐷=0⇒𝑍=1
∴ 𝑃𝑉 = 𝑅𝑇
❖ At constant temperature If pressure approaches zero volume increases
𝐵 𝐶 𝐷
, , , 𝑒𝑡𝑐 𝑏𝑒𝑐𝑜𝑚𝑒𝑠 𝑧𝑒𝑟𝑜
𝑉 𝑉2 𝑉3
❖ 𝑍 = 1, ∴ 𝑃𝑉 = 𝑅𝑇
❖ From the phase rule that the internal energy of a real gas is a function of pressure as well
as of temperature.
❖ This pressure dependency is the result of forces between the molecules. If such forces did
not exist, no energy would be required to alter the average intermolecular distance, and
therefore no energy would be required to bring about volume and pressure changes in a
gas at constant temperature.
❖ We conclude that in the absence of molecular interactions, the internal energy of a gas
depends on temperature only.
❖ These considerations 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 macroscopic behavior is characterized by: 𝑈 = 𝑈(𝑇)
Implied Property Relations for an ideal gas:
❖ Heat capacity at constant volume, for an ideal gas to the conclusion that is a
function of temperature only:
𝜕𝑈 𝑑𝑈
𝐶𝑉 ≡ = = 𝐶𝑉 𝑇
𝜕𝑇 𝑉 𝑑𝑇
❖ equation for enthalpy, applied to an ideal gas, leads to the conclusion that H also is a
function of temperature only:
𝐻 ≡ 𝑈 + 𝑃𝑉 = 𝑈 𝑇 + 𝑅𝑇
❖ The heat capacity at constant pressure is a function of temperature only:
𝜕𝐻 𝑑𝐻
𝐶𝑃 ≡ = = 𝐶𝑃 𝑇
𝜕𝑇 𝑃 𝑑𝑇
❖ A useful relation between and for an ideal gas comes from differentiation of above
equation
𝑑𝐻 𝑑𝑈
𝐶𝑃 = = + 𝑅 = 𝐶𝑉 + 𝑅 ⇒ 𝐶𝑃 − 𝐶𝑉 = 𝑅
𝑑𝑇 𝑑𝑇
❖ For any change of state of an ideal gas 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
∆𝑈 = න 𝐶𝑉 𝑑𝑇

𝑑𝐻 = 𝐶𝑃 𝑑𝑇

∆𝐻 = න 𝐶𝑃 𝑑𝑇

Equations for Process Calculations: Ideal Gases:

❖ For an ideal gas in any mechanically reversible closed-system process, for a unit mass
or a mole 𝑑𝑈 = 𝑑𝑄 + 𝑑𝑊
𝐶𝑉 𝑑𝑇 = 𝑑𝑄 + 𝑑𝑊
❖ The work for a mechanically reversible closed-system for one mole or a unit mass:
𝑑𝑊 = −𝑃𝑑𝑉
𝐶𝑉 𝑑𝑇 = 𝑑𝑄 − 𝑃𝑑𝑉
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉
❖ The two preceding equations for an ideal gas undergoing a reversible process in a
closed system take several forms through elimination of one of the variables P, V , or
T
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉
❖ Thus, with 𝑃 = 𝑅𝑇/𝑉 they become:
𝑅𝑇
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉
𝑉
𝑑𝑉
𝑑𝑊 = −𝑅𝑇
𝑉
𝑅 𝑅𝑇
❖ Alternatively let, 𝑉 = 𝑅𝑇/𝑃 → 𝑑𝑉 = 𝑑𝑇 − 𝑑𝑃
𝑃 𝑃2
𝑅 𝑅𝑇
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑃 𝑑𝑇 − 2 𝑑𝑃
𝑃 𝑃
𝑅𝑇
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑅𝑑𝑇 − 𝑑𝑃
𝑃
𝑅𝑇
𝑑𝑄 = 𝐶𝑃 𝑑𝑇 − 𝑑𝑃
𝑃
𝑅 𝑅𝑇 𝑑𝑃
𝑑𝑊 = −𝑃𝑑𝑉 = −𝑃 𝑑𝑇 − 2 𝑑𝑃 = −𝑅𝑑𝑇 + 𝑅𝑇
𝑃 𝑃 𝑃
 𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉
1
❖ Finally let, T = PV/R → 𝑑𝑇 = (𝑃𝑑𝑉 + 𝑉𝑑𝑃)
𝑅
𝐶𝑉
𝑑𝑄 =
(𝑃𝑑𝑉 + 𝑉𝑑𝑃) + 𝑃𝑑𝑉
𝑅
𝐶𝑉 𝐶𝑉
𝑑𝑄 = 𝑃𝑑𝑉 + 𝑉𝑑𝑃 + 𝑃𝑑𝑉
𝑅 𝑅
𝐶𝑉 𝐶𝑉 𝐶𝑉 + 𝑅 𝐶𝑉
𝑑𝑄 = 𝑃 + 1 𝑑𝑉 + 𝑉𝑑𝑃 = 𝑃 𝑑𝑉 + 𝑉𝑑𝑃
𝑅 𝑅 𝑅 𝑅
𝐶𝑃 𝐶𝑉
𝑑𝑄 = 𝑃𝑑𝑉 + 𝑉𝑑𝑃
𝑅 𝑅
The work is simply 𝑑𝑊 = −𝑃𝑑𝑉
The above equations are valid for the restrictions
❖ The equations are valid for ideal gases.
❖ The process is mechanically reversible.
❖ The system is closed.
ISOTHERMAL PROCESS(Const. Temp): (dT=0)
∆𝑈 = 𝐶𝑉 𝑑𝑇 = 0, ∆𝐻 = 𝐶𝑃 𝑑𝑇 = 0
𝑑𝑄 = −𝑑𝑊 → 𝑄 = −𝑊
𝑅𝑇 𝑅𝑇
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉 = 𝑑𝑉
𝑉 𝑉
𝑉2 𝑅𝑇/𝑃2 𝑃1 𝑃2
𝑄 = 𝑅𝑇 𝑙𝑛 = 𝑅𝑇 𝑙𝑛 = 𝑅𝑇 𝑙𝑛 = −𝑅𝑇 𝑙𝑛
𝑉1 𝑅𝑇/𝑃1 𝑃2 𝑃1
𝑉2 𝑃2
𝑊 = −𝑅𝑇 𝑙𝑛 = 𝑅𝑇 𝑙𝑛
𝑉1 𝑃1
ISOBARIC PROCESS(Const. pressure): (dP=0)
∆𝑼 = න 𝐶𝑉 𝑑𝑇 , ∆𝑯 = න 𝐶𝑃 𝑑𝑇

𝑅𝑇
𝑑𝑄 = 𝐶𝑃 𝑑𝑇 − 𝑑𝑃 = 𝐶𝑃 𝑑𝑇 ⟹ 𝑄 = න 𝐶𝑃 𝑑𝑇 = ∆𝐻
𝑃
𝑑𝑃
𝑑𝑊 = −𝑅𝑑𝑇 + 𝑅𝑇 = −𝑅𝑑𝑇
𝑃
𝑊 = −𝑅(𝑇2 − 𝑇1 )
ISOCHORIC PROCESS(Const. volume): (dV=0)
∆𝑼 = න 𝐶𝑉 𝑑𝑇 , ∆𝑯 = න 𝐶𝑃 𝑑𝑇

∆𝑈 = 𝑄 + 𝑊
𝑊 = −𝑃𝑑𝑉 = 0

𝑄 = ∆𝑈 = න 𝐶𝑉 𝑑𝑇

Adiabatic Process: Constant Heat Capacities: (dQ=0)

An adiabatic process is one for which there is no heat transfer between the system and
its surroundings; that is, dQ=0.
𝑅𝑇
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉 = 0
𝑉
𝑅𝑇
𝑑𝑄 = 𝐶𝑃 𝑑𝑇 − 𝑑𝑃 = 0
𝑃
𝐶𝑃 𝐶𝑉
𝑑𝑄 = 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 0
𝑅 𝑅
 𝑅𝑇
𝑑𝑄 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉 = 0
𝑉
𝑑𝑇 𝑅 𝑑𝑉
=−
𝑇 𝐶𝑉 𝑉
𝑅
𝑇2 𝑅 𝑉2 𝑉1 𝐶𝑉
Integrate both sides 𝑙𝑛 = − 𝑙𝑛 = ln
𝑇1 𝐶𝑉 𝑉1 𝑉2
𝑅 𝐶𝑃 −𝐶𝑉
𝐶𝑉 𝐶𝑉 𝜸−𝟏 𝐶𝑃
𝑇2 𝑉1 𝑉1 𝑻𝟐 𝑽𝟏 =𝛾
= = ⟹ = 𝐶𝑉
𝑇1 𝑉2 𝑉2 𝑻𝟏 𝑽𝟐
𝑅𝑇
𝑑𝑄 = 𝐶𝑃 𝑑𝑇 − 𝑑𝑃 = 0
𝑃
𝑑𝑇 𝑅 𝑑𝑃
=
𝑇 𝐶𝑃 𝑃
𝑅
𝑇2 𝑅 𝑃2 𝑃2
Integrate both sides
𝐶𝑃
𝑙𝑛 = 𝑙𝑛 = 𝑙𝑛
𝑇1 𝐶𝑃 𝑃1 𝑃1
 𝑅 𝐶𝑃 −𝐶𝑉 𝐶𝑃 /𝐶𝑉 −1
𝑇2 𝑃2 𝐶𝑃 𝑃2 𝐶𝑃 𝑃2 𝐶𝑃 /𝐶𝑉
⟹ = = =
𝑇1 𝑃1 𝑃1 𝑃1
𝜸−𝟏
𝑻𝟐 𝑷𝟐 𝜸
=
𝑻𝟏 𝑷𝟏
𝐶𝑃 𝐶𝑉
𝑑𝑄 = 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 0
𝑅 𝑅
𝐶𝑃 𝐶𝑉
𝑃𝑑𝑉 = − 𝑉𝑑𝑃
𝑅 𝑅
𝐶𝑃 𝑑𝑉 𝑑𝑃
=−
𝐶𝑉 𝑉 𝑃
𝑃2 𝑉2 𝑉2 𝛾
Integrate both sides −𝑙𝑛 = 𝛾 𝑙𝑛 = 𝑙𝑛
𝑃1 𝑉1 𝑉1
𝜸
𝑷𝟏 𝑽𝟐
=
𝑷𝟐 𝑽𝟏
 𝜸−𝟏
𝑻𝟐 𝑽𝟏
= ⟹ 𝑻𝑽𝜸−𝟏 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑻𝟏 𝑽𝟐

𝜸−𝟏 𝟏−𝜸
𝑻𝟐 𝑷𝟐 𝜸 𝑷𝟏 𝜸 𝟏−𝜸
= = ⟹ 𝑻𝑷 𝜸 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑻𝟏 𝑷𝟏 𝑷𝟐

𝜸
𝑷𝟏 𝑽𝟐
= ⟹ 𝑷𝑽𝜸 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑷𝟐 𝑽𝟏
The work of an adiabatic process may be obtained from the relation:
𝑑𝑊 = 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
If 𝐶𝑉 is constant, integrate 𝑊 = ∆𝑈 = 𝐶𝑉 ∆𝑇
𝐶𝑃 𝐶𝑉 + 𝑅 𝑅
𝛾= = =1+
𝐶𝑉 𝐶𝑉 𝐶𝑉
𝑅 𝑅
𝛾−1= ⟹ 𝐶𝑉 =
𝐶𝑉 𝛾−1
 𝑊 = 𝐶𝑉 ∆𝑇
𝑅
𝑊= ∆𝑇
𝛾−1
For ideal gas 𝑃1 𝑉1 = 𝑅𝑇1 𝑎𝑛𝑑 𝑃2 𝑉2 = 𝑅𝑇2
𝑅𝑇2 − 𝑅𝑇1 𝑃2 𝑉2 − 𝑃1 𝑉1
𝑊= =
𝛾−1 𝛾−1 𝜸
𝑷𝟏 𝑽𝟐
𝑃1 𝑉1 𝑃2 𝑉2 =
𝑊= −1 𝑷𝟐 𝑽𝟏
𝛾 − 1 𝑃1 𝑉1
1 𝛾−1
−𝛾 𝛾
𝑃1 𝑉1 𝑃2 𝑃2 𝑃1 𝑉1 𝑃2
= −1 = −1
𝛾 − 1 𝑃1 𝑃1 𝛾−1 𝑃1
𝛾−1
𝑅𝑇1 𝑃2 𝛾
= −1
𝛾−1 𝑃1
POLYTROPIC PROCESS:
Since polytropic means "turning many ways: polytropic process suggests a model of
some versatility. With δ a constant, it is defined as a process for which
𝑃𝑉 𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇𝑉 𝛿−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
1−𝛿
𝑇𝑃 𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝛿−1
𝑅𝑇1 𝑃2 𝛿
𝑊= −1
𝛿−1 𝑃1
Moreover, for constant heat capacities, the first law solved for Q yields:
∆𝑈 = 𝑄 + 𝑊 ⟹ 𝑄 = 𝐶𝑉 ∆𝑇 − W
𝛾−1 𝛿−1
𝑅𝑇1 𝑃2 𝛾 𝑅𝑇1 𝑃2 𝛿
𝑄= −1 − −1
𝛾−1 𝑃1 𝛿−1 𝑃1
 𝛿−1 𝛿−1
1 1 𝑃2 𝛿 𝛿 − 𝛾 𝑅𝑇1 𝑃2 𝛿
𝑄 = 𝑅𝑇1 − −1 = −1
𝛾−1 𝛿−1 𝑃1 𝛾−1 𝛿−1 𝑃1

𝑃𝑉 𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇𝑉 𝛿−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
1−𝛿
𝑇𝑃 𝛿 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Isobaric process: δ = 0.
Isothermal process: δ=1
Adiabatic process: 𝛿 = 𝛾
𝑑𝑉 𝑉
Isochoric process: = ; for constant V, 𝛿 = ±∞
𝑑𝑃 𝑃𝛿
Irreversible Process:
❖ The equations have been derived for mechanically reversible system
processes for ideal gases.
❖ However, those equations which relate changes in state functions only
are valid for ideal gases regardless of the process.
❖ They apply equally to reversible and irreversible processes in both closed
and open systems, because changes in state functions depend only on the
initial and final states of the system.
❖ On the other hand, an equation for Q or W is specific to the process
considered in its derivation.
❖ The work of an irreversible process is calculated by a two-step procedure.
❖ First, W is determined for a mechanically reversible process that
accomplishes the same change of state as the actual irreversible process.
❖ Second, this result is multiplied or divided by an efficiency to give the
actual work.
❖ If the process produces work, the absolute value for the reversible process
is too large and must be multiplied by an efficiency.
❖ If the process requires work, the value for the reversible process is too
small and must be divided by an efficiency.
❖ Example 3.2: Air is compressed from an initial condition of 1 bar and 298K (25°C) to
a final state of 5 bar and 298K (25°C) by three different mechanically reversible
processes in a closed system:
A. Heating at constant volume followed by cooling at constant pressure.
B. Isothermal compression
C. Adiabatic compression followed by cooling at constant volume.
Assume air to be an ideal gas with the const. heat capacities, CV=(5/2)R and CP=(7/2)R.
Calculate the work required, heat transferred, and the change in internal energy an
enthalpy of the air for each process.
𝐽
Data: CV=(5/2)R= 5/2 × 8.314 = 20.785
𝑚𝑜𝑙 𝐾
𝑃1 = 1 𝑏𝑎𝑟, 𝑇1 = 298K (25°C) 𝐽
𝑃2 = 5 𝑏𝑎𝑟, 𝑇2 = 298K (25°C) CP=(7/2)R=7/2 × 8.314 = 29.099
𝑚𝑜𝑙 𝐾
CV=(5/2)R 𝑅𝑇1 8.314 × 298 3
CP=(7/2)R 𝑉1 = = = 0.02477 𝑚
𝑃1 105
R=8.314 J/(mol K) 𝑅𝑇2 8.314 × 298 3
𝑉2 = = = 0.004955 𝑚
𝑃2 5 × 105
❖ Initial and final temperatures are same
∆𝑈 = ∆𝐻 = 0
A. Heating at constant volume followed by cooling at constant pressure.
𝑇′ 𝑃2 𝑃2 𝑇1 5×298
Heating at constant volume = → 𝑇′ = = = 1490𝐾
𝑇1 𝑃1 𝑃1 1

𝑄1 = ∆𝑈1 = 𝐶𝑉 ∆𝑇 = 20.785 × 1490 − 298 = 24775.72 𝐽

∆𝐻1 = ∆𝑈1 + ∆ 𝑃𝑉 = ∆𝑈 + 𝑃∆ 𝑉 + 𝑉∆ 𝑃
∆𝐻1 = 24775.72 + 0.02477 5 − 1 × 105 = 34683.72
𝑊=0
cooling at constant pressure. 𝑄2 = ∆𝐻2 = 𝐶𝑃 ∆𝑇 = 29.099 × 298 − 1490 = −34686 𝐽
∆𝐻2 = ∆𝑈2 + ∆ 𝑃𝑉 = ∆𝑈 + 𝑃∆ 𝑉 + 𝑉∆ 𝑃
∆𝑈2 = ∆𝐻2 − 𝑃∆ 𝑉 = −34686 − 5 × 105 0.004955 − 0.02477 = −24778.5 𝐽
𝑊2 = ∆𝑈2 − 𝑄2 = −24778.5 + 34686 = 9907.5 𝐽
Overall heat transferred 𝑄 = 𝑄1 + 𝑄2 = 24775.72 − 34686 = −9910.2 𝐽
Overall Work 𝑊 = 𝑊1 + 𝑊2 = 0 + 9907.5 = 9907.5 𝐽
Overall ∆𝑈 = ∆𝑈1 + ∆𝑈2 = 24775.72 − 24778.5 = −2.78 ≅ 0
Overall ∆𝐻 = ∆𝐻1 + ∆𝐻2 = 34683.72 − 34686 = −2.28 ≅ 0
B. Isothermal compression:
𝑃1 1
𝑄 = −𝑊 = 𝑅𝑇 ln = 8.314 × 298 × ln = −3987.5 𝐽
𝑃2 5
∆𝑈 = ∆𝐻 = 0
C. Adiabatic compression followed by cooling at constant volume.
𝑇2 𝑉1 𝛾−1 𝑉1 𝛾−1 𝑪𝑷 𝟐𝟗. 𝟎𝟗𝟗
= ⟹ 𝑇2 = 𝑇1 𝜸= =
𝑪𝑽 𝟐𝟎𝟎𝟕𝟖𝟓
𝑇1 𝑉2 𝑉2
0.4 = 𝟏. 𝟒
0.02477
𝑇2 = 298 = 567.24𝐾
0.004955
𝛾 𝛾
𝑃2 𝑉1 𝑉1
= ⟹ 𝑃2 = 𝑃1
𝑃1 𝑉2 𝑉2
1.4
0.02477
𝑃2 = 1 × = 9.515 𝑏𝑎𝑟
0.004955
For this step Q1=0, 𝑊1 = ∆𝑈 = 𝐶𝑉 ∆𝑇 = 20.785 × 567.24 − 298 = 5596.15 𝐽
 ∆𝐻1 = 𝐶𝑃 ∆𝑇 = 29.099 × 567.24 − 298 = 7384.61 𝐽
Cooling at constant volume. W=0
𝑄2 = ∆𝑈2 = 𝐶𝑉 ∆𝑇 = 20.785 × 298 − 567.24 = −5596.15 𝐽
∆𝐻2 = 𝐶𝑃 ∆𝑇 = 29.099 × 298 − 567.24 = −7384.61 𝐽
Overall heat transferred 𝑄 = 𝑄1 + 𝑄2 = 0 − 5596.15 = −5596.15
Overall Work 𝑊 = 𝑊1 + 𝑊2 = 5596.15 + 0 = 5596.15𝐽
Overall ∆𝑈 = ∆𝑈1 + ∆𝑈2 = 5596.15 − 5596.15 = 0
Overall ∆𝐻 = ∆𝐻1 + ∆𝐻2 = 7384.61 − 7384.61 = 0
 POINT P1 P’ P2 T1 T’ T2 V1 V’ V2

Const. V 1 5 298 1490 0.02477 0.0247

Const. P 5 5 1490 298 0.0247 0.004955

Isotherm
1 - 5 298 - 298 0.02477 - 0.004955
al

Adiabatic 1 9.515 298 567.24 0.02477 0.004955

Const. V 9.515 5 567.24 298 0.004955 0.004955

❖ Exercise 3.9: An ideal gas initially at 600 K and 10 bar undergoes a four-step
mechanically reversible cycle in a closed system. In step 12, pressure decreases
isothermally to 3 bar; in step 23, pressure decreases at constant volume to 2 bar; in
step 34, volume decreases at constant pressure; and in step 41, the gas returns
adiabatically to its initial state.
(a) Sketch the cycle on a PV diagram.
(b) Determine (where unknown) both T and P for states 1, 2, 3, and 4.
(c) Calculate Q, W, ∆U, and ∆H for each step of the cycle.
Data: CV=(5/2)R and CP=(7/2)R.
Data: 𝐽
CV=(5/2)R= 5/2 × 8.314 = 20.785
𝑃1 = 10 𝑏𝑎𝑟, 𝑇1 = 600 K, 𝑉1 =? 𝑚𝑜𝑙 𝐾
𝑃2 = 3 𝑏𝑎𝑟, 𝑇2 = 𝑇1 , 𝑉2 =? 𝐽
CP=(7/2)R=7/2 × 8.314 = 29.099
𝑃3 = 2 𝑏𝑎𝑟, 𝑇3 =?, 𝑉3 = 𝑉2 𝑚𝑜𝑙 𝐾
𝑃4 = 𝑃3 , 𝑇4 =?, 𝑉4 =? 𝑅𝑇1 8.314 × 600 3
𝑉1 = = = 0.00499 𝑚
CV=(5/2)R 𝑃1 10 × 105
CP=(7/2)R 𝑅𝑇2 8.314 × 600 3
𝑉2 = = = 0.0166𝑚
R=8.314 J/(mol K) 𝑃2 3 × 105
 Data:
𝑅𝑇2 8.314 × 298 𝑃1 = 10 𝑏𝑎𝑟, 𝑇1 = 600 K, 𝑉1 =?
𝑉2 = = = 0.004955 𝑚 3
𝑃2 5 × 105 𝑃2 = 3 𝑏𝑎𝑟, 𝑇2 = 𝑇1 , 𝑉2 =?
𝑃3 = 2 𝑏𝑎𝑟, 𝑇3 =?, 𝑉3 = 𝑉2
Step41 Adiabatic process: 𝑃4 = 𝑃3 , 𝑇4 =?, 𝑉4 =?
𝛾−1 𝛾−1 CV=(5/2)R
𝑇4 𝑃4 𝛾 𝑃4 𝛾
= ⟹ 𝑇4 = 𝑇1 CP=(7/2)R
𝑇1 𝑃1 𝑃1
1.4−1 R=8.314 J/(mol K)
2 1.4
𝑇4 = 600 × = 378.831𝐾
10
𝑅𝑇4 8.314 × 378.831 3
𝑉4 = = = 0.01575 𝑚
𝑃4 2 × 105
STEP12 ISOTHERMAL PROCESS: ∆𝑈12 = ∆𝐻12 = 0
𝑃2
𝑊12 = −𝑄12 = 𝑅𝑇1 𝑙𝑛
𝑃1
𝑊12 = −𝑄12 = 8.314 × 600 × 𝑙𝑛 3/10 = 6005.89𝐽/𝑚𝑜𝑙
𝑄12 = −6005.89𝐽/𝑚𝑜𝑙
STEP23 CONST. VOL. PROCESS: Data:
𝑑𝑉 = 0 ⟹ 𝑊 = 0 𝑃1 = 10 𝑏𝑎𝑟, 𝑇1 = 600 K, 𝑉1 = 0.00499 𝑚3
𝑃2 = 3 𝑏𝑎𝑟, 𝑇2 = 𝑇1 , 𝑉2 = 0.0166𝑚3
𝑄23 = ∆𝑈23 = 𝐶𝑉 ∆𝑇 = 𝐶𝑉 (𝑇3 − 𝑇2 )
𝑃3 = 2 𝑏𝑎𝑟 𝑇3 = 400𝐾, 𝑉3 = 𝑉2
5
𝑄23 = ∆𝑈23 = × 8.314 × 400 − 600 𝑃4 = 𝑃3 , 𝑇4 = 378.831𝐾 𝑉4 = 0.01575 𝑚3
2
𝑄23 = ∆𝑈23 = 4157𝐽/𝑚𝑜𝑙
∆𝐻23 = 𝐶𝑃 ∆𝑇 = 𝐶𝑃 (𝑇3 − 𝑇2 )
7 STEP41 ADIABATIC PROCESS:
∆𝐻23 = 𝐶𝑃 ∆𝑇 = × 8.314 × 400 − 600 𝑊41 = ∆𝑈41 = 𝐶𝑉 ∆𝑇 = 𝐶𝑉 (𝑇1 − 𝑇4 )
2
∆𝐻23 = −5819.8𝐽/𝑚𝑜𝑙 𝑊41 = ∆𝑈41 = 5/2 × 8.314(600 − 378.831)
𝑊41 = ∆𝑈41 = 4596.99𝐽/𝑚𝑜𝑙
STEP34 CONST. PRESSURE PROCESS: ∆𝐻41 = 𝐶𝑃 ∆𝑇 = 𝐶𝑃 (𝑇1 − 𝑇4 )
𝑄34 = ∆𝐻34 = 𝐶𝑃 ∆𝑇 = 𝐶𝑃 (𝑇4 − 𝑇3 ) 7
𝑄34 = ∆𝐻34 = 7/2 × 8.314 × 378.831 − 400 ∆𝐻41 = 𝐶𝑃 ∆𝑇 = × 8.314 600 − 378.831
2
𝑄34 = ∆𝐻34 = −616J/mol ∆𝐻41 = 6435.79𝐽/𝑚𝑜𝑙
∆𝑈34 = 𝐶𝑉 ∆𝑇 = 𝐶𝑉 (𝑇4 − 𝑇3 )
∆𝑈34 = 5/2 × 8.314 × (378.831 − 400)
∆𝑈34 = −440J/mol
𝑊34 = ∆𝑈34 − 𝑄34 = −440 + 616 = 170𝐽/𝑚𝑜𝑙
Point Pressure Temperature Volume
1
1 10bar 600K 0.00499m3
P 2
2 3bar 600K 0.0166m3
3 2bar 400K 0.0166m3 4 3

4 2bar 378.831 0.01575m3 V

STEP ∆𝑼, 𝐉/𝐦𝐨𝐥 ∆𝐇, 𝐉/𝐦𝐨𝐥 𝐐, 𝐉/𝐦𝐨𝐥 𝐖, 𝐉/𝐦𝐨𝐥

12 0 0 6005.89 -6005.89
23 -4157 -5819.8 -4157 0
34 -440 -616 -616 176
41 4596.99 6435.79 0 4596.99
Overall 0 0 1232.89 -1232.9
APPLICATION OF THE VIRIAL EQUATIONS:
❖ The two forms of the expansion given by Eqs. are infinite series.
𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯
𝐵 𝐶 𝐷
𝑍 =1+ + 2+ 3+⋯
𝑉 𝑉 𝑉
❖ For engineering purposes their use is practical only where convergence is
very rapid, that is, where two or three terms suffice for reasonably close
approximations to the values of the series.
❖ This is realized for gases and vapors at low to moderate pressures.
❖ 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. 𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯ for a given temperature gives:
𝜕𝑍
❖ = 𝐵′ + 2𝐶 ′ 𝑃 + 3𝐷′ 𝑃2 + ⋯
𝜕𝑃 𝑇

𝜕𝑍
❖ = 𝐵′
𝜕𝑃 𝑇;𝑃=0

❖ Thus the equation of the tangent line is

❖ 𝑍 = 1 + 𝐵′ 𝑃
❖ A more common form of this equation results from
𝐵
the substitution B =
′
𝑅𝑇
𝑃𝑉 𝐵𝑃 𝑃𝑉 𝐵
❖ 𝑍= =1+ , 𝑍= =1+
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑉
❖ This equation satisfactorily represents the PV T behavior of many vapors at subcritical
temperatures up to a pressure of about 5 bar.
❖ For pressures above the range of applicability of above Eq. but below the critical
pressure, the virial equation truncated to three terms often provides excellent results.
In this case the expansion in 1/V , is far superior to expression in P.
❖ Thus when the virial equation is truncated to three terms, the appropriate form is:
𝑃𝑉 𝐵 𝐶
𝑍= =1+ + 2
𝑅𝑇 𝑉 𝑉
❖ This equation can be solved directly for pressure, but is cubic in volume. Solution for
V is easily done by an iterative scheme with a calculator.
❖ Values of C, like those of depend on the gas and on temperature. However, much
less is known about third virial coefficients than about second virial coefficients,
though data for a number of gases are found in the literature.
❖ Example 3.7: Repoted values for the virial coefficients of isopropanol vapor at 473 K
are 𝐵 = −0.388 𝑚3 /𝑘𝑚𝑜𝑙 , 𝐶 = −26 × 10−3 𝑚6 / 𝑘𝑚𝑜𝑙 2 calcilate V and Z for
isopropanol at 473 K and 10 bar by
a) The ideal gas equation
b) Equation truncated to two terms in pressure
c) Equation truncated to three terms in volume
a) For ideal gas
Data: 𝑅𝑇 83.14 × 10−3 × 473
𝑃 = 10 𝑏𝑎𝑟, 𝑉= = = 3.934 𝑚3 /𝑘𝑚𝑜𝑙
𝑃 10
𝑇 = 473 K, 𝑍 = 1 𝑓𝑜𝑟 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠
𝐵 = −0.388 𝑚3 /𝑘𝑚𝑜𝑙
𝐶 = −26 × 10−3 𝑚6 / 𝑘𝑚𝑜𝑙 2 b) Equation truncated to two terms in pressure
𝑃𝑉 𝐵𝑃 𝑅𝑇
𝑉 =? 𝑍= =1 + →𝑉 = +𝐵
𝑅𝑇 𝑅𝑇 𝑃
𝑍 =? 𝑉 = 3.943 − 0.388 = 3.546 𝑚3 /𝑘𝑚𝑜𝑙
𝑅 = 83.14 × 10−3 𝑚3 𝑏𝑎𝑟/(𝑘𝑚𝑜𝑙 𝐾) 𝑃𝑉 10 × 3.546
𝑍= = −3
= 0.9014
𝑅𝑇 83.14 × 10 × 473
C) Equation truncated to three terms in volume
𝑃𝑉 𝐵 𝐶
𝑍= =1+ + 2
𝑅𝑇 𝑉 𝑉
𝑅𝑇 𝐵 𝐶
𝑉𝑖+1 = 1+ + 2
𝑃 𝑉𝑖 𝑉𝑖
𝑅𝑇 𝑅𝑇 𝐵 𝐶
𝑖 = 0, 𝑉0 = (𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑣𝑜𝑙𝑢𝑚𝑒) 𝑉1 = 1 + + 2
𝑃 𝑃 𝑉0 𝑉0
𝑅𝑇 𝐵 𝐶
i 𝑽𝒊 𝑉𝑖+1 = 1+ + 2
𝑃 𝑉𝑖 𝑉𝑖
0.388 26 × 10−3
0 𝑉0 = 3.934 𝑉1 = 3.934 1 − − 2
= 3.538 𝑚3 /𝑘𝑚𝑜𝑙
3.934 3.934
0.388 26 × 10−3
1 𝑉1 = 3.538 𝑉2 = 3.934 1 − − 2
= 3.493 𝑚3 /𝑘𝑚𝑜𝑙
3.538 3.538
0.388 26 × 10−3
2 𝑉2 = 3.493 𝑉3 = 3.934 1 − − 2
= 3.489 𝑚3 /𝑘𝑚𝑜𝑙
3.493 3.493
0.388 26 × 10−3
3 𝑉3 = 3.489 𝑉4 = 3.934 1 − − 2
= 3.488 𝑚3 /𝑘𝑚𝑜𝑙
3.489 3.489
0.388 26 × 10−3
4 𝑉4 = 3.488 𝑉4 = 3.934 1 − − = 3.488 𝑚3 /𝑘𝑚𝑜𝑙
𝑃𝑉 10 × 3.488 3.488 3.488 2

𝑍= =
𝑅𝑇 83.14 × 10−3 × 473
CUBIC EQUATIONS OF STATE:
❖ If an equation of state is to represent the PVT behavior of both liquids
and vapors, it must encompass a wide range of temperatures and
pressures.
❖ Yet it must not be so complex as to present excessive numerical or
analytical difficulties in application.
❖ Polynomial equations that are cubic in molar volume offer a compromise
between generality and simplicity that is suitable to many purposes.
❖ Cubic equations are in fact the simplest equations capable of representing
both liquid and vapor behavior.
The van der Waals Equation of State:
❖ The first practical cubic equation of state was
proposed by J. D. van der in 1873:
𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉
❖ Here, a and b are positive constants; when
they are zero, the ideal-gas equation is
recovered.
❖ Given values of a and b for a particular fluid,
one can calculate P as a function of V for
various values of T.
❖ The smallest root is a liquid or "liquid-like"
volume, and the largest is a vapor or "vapor-
like" volume. The third root, lying between the
other values, is of no significance.
A Generic Cubic Equation of State:
𝑅𝑇 𝜃 𝑉−𝜂
𝑃= −
𝑉−𝑏 𝑉 − 𝑏 𝑉 2 + 𝑘𝑉 + 𝜆
❖ Where 𝑏, 𝜃, 𝑘, 𝜆 𝑎𝑛𝑑 𝜂 are parameters which are depends on temperature and
composition.
❖ It reduces to Van der waals equation when 𝜃 = 𝑎, 𝜂 = 𝑏 𝑎𝑛𝑑 𝑘 = 𝜆 = 0
❖ An important class of cubic equations results from the preceding equation with
the assignments
𝜂 = 𝑏 𝜃 = 𝑎 𝑇 𝑘 = 𝜖 + 𝜎 𝑏 𝜆 = 𝜖𝜎𝑏 2
❖ It is thus transformed into an expression general enough to serve as a generic
cubic equation of state, which reduces to all others of interest here upon
assignment of appropriate parameters:
𝑅𝑇 𝑎 𝑇
𝑃= −
𝑉−𝑏 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
❖ For a given equation, 𝜖 and 𝜎 are pure numbers, the same for all substances,
whereas parameters a(T) and b are substance dependent.
Determination of Equation-of-State Parameters:
❖ The constants in an equation of state for a particular substance may be
evaluated by a fit to available PVT data.
❖ For cubic equations of state, however, suitable estimates are usually found from
values for the critical constants and Since the critical isotherm exhibits a
horizontal inflection at the critical point, we may impose the mathematical
conditions:
𝜕𝑃 𝜕2𝑃
=0 2
=0 𝑎𝑡 𝑃 = 𝑃𝐶 , 𝑇 = 𝑇𝐶 & 𝑉 = 𝑉𝐶
𝜕𝑉 𝑇;𝑐𝑟 𝜕𝑉 𝑇;𝑐𝑟
❖ These three equations contain five constants: 𝑃𝐶 , 𝑉𝐶 , 𝑇𝐶 , 𝑎 𝑇𝐶 𝑎𝑛𝑑 𝑏.
❖ Of the several ways to treat these equations, the most suitable is elimination of
V𝐶 to yield expressions relating 𝑎(𝑇𝐶 ) and b to 𝑃𝐶 and 𝑉𝐶 . The reason is that
𝑃𝐶 and 𝑉𝐶 are usually more accurately known than 𝑉𝐶 .
Determination of Equation-of-State Parameters:
❖ An equivalent, but more straightforward, procedure is illustrated for the van
der Waals equation. Since 𝑉 = 𝑉𝐶 for each of the three roots at the critical
point
𝑉 − 𝑉𝐶 3 =0
𝑉 3 − 3𝑉 2 𝑉𝐶 + 3𝑉𝑉𝐶2 − 𝑉𝐶3 = 0
𝑎𝑡 𝑃 = 𝑃𝐶 , 𝑇 = 𝑇𝐶 & 𝑉 = 𝑉𝐶 Vander waals equation
𝑅𝑇𝐶 𝑎 𝑅𝑇𝑉 2 − 𝑎 𝑉𝐶 − 𝑏
𝑃𝐶 = − 2 → 𝑃𝐶 =
𝑉−𝑏 𝑉 𝑉 − 𝑏 𝑉2
𝑅𝑇 𝑉 2 𝑎 𝑉−𝑏
2 𝐶
𝑉−𝑏 𝑉 = −
𝑃𝐶 𝑃𝐶
2
3 2
𝑅𝑇𝐶 𝑉 𝑎𝑉 ab
𝑉 − 𝑏𝑉 − + − =0
𝑃𝐶 PC PC
 𝑅𝑇𝐶 𝑎 3
𝑎𝑏
3𝑉𝐶 = 𝑏 + , 3𝑉𝐶2 = , 𝑉𝐶 =
𝑃𝐶 𝑃𝐶 𝑃𝐶
3 3
2
𝑃 𝑉
𝐶 𝐶 𝑃 𝑉
𝐶 𝐶 1
𝑎 = 3𝑃𝐶 𝑉𝐶 𝑏= = 2 = 𝑉𝐶
𝑎 3𝑃𝐶 𝑉𝐶 3
𝑅𝑇𝐶 1 𝑅𝑇𝐶 1 𝑅𝑇𝐶 8 𝑅𝑇𝐶
3𝑉𝐶 = 𝑏 + = 𝑉𝐶 + → 3𝑉𝐶 − 𝑉𝐶 = → 𝑉𝐶 =
𝑃𝐶 3 𝑃𝐶 3 𝑃𝐶 3 𝑃𝐶
𝟑 𝑹𝑻𝑪
𝑽𝑪 =
𝟖 𝑷𝑪
2 𝟐 𝑻𝟐
3 𝑅𝑇𝐶 𝟐𝟕 𝑹 𝑪
𝑎 = 3𝑃𝐶 𝑉𝐶2 = 3𝑃𝐶 →𝒂=
8 𝑃𝐶 𝟔𝟒 𝑷𝑪
1 1 3 𝑅𝑇𝐶 𝟏 𝑹𝑻𝑪
𝑏 = 𝑉𝐶 = →𝒃=
3 3 8 𝑃𝐶 𝟖 𝑷𝑪
𝑃𝐶 𝑉𝐶 𝑃𝐶 3 𝑅𝑇𝐶 𝟑
𝑍𝐶 = = → 𝒁𝑪 =
𝑅𝑇𝐶 𝑅𝑇𝐶 8 𝑃𝐶 𝟖
 𝑅𝑇 𝑎 𝑇
❖ Generic Cubic equation: 𝑃 = −
𝑉−𝑏 𝑉+𝜖𝑏 𝑉+𝜎𝑏
❖ An analogous procedure may be applied to the generic cubic, Eq. yielding expressions
for parameters 𝑎(𝑇𝐶 ) and b. For the former
𝑅2 𝑇𝐶2
𝑎 𝑇𝐶 = 𝜓
𝑃𝐶
❖ This result may be extended to temperatures other than the critical by introduction of
a dimen- sionless function that becomes unity at the critical temperature. Thus
𝛼(𝑇𝑟 )𝑅2 𝑇𝐶2
𝑎 𝑇 = 𝜓
𝑃𝐶
❖ Function is an empirical expression, specific to a particular equation of state.
Parameter b is given by:
𝑅𝑇𝐶
𝑏=Ω
𝑃𝐶
❖ In these equations Ω and 𝜓 are pure numbers, independent of substance and
determined for a particular equation of state from the values assigned to 𝜖 and a.
❖ The modern development of cubic equations of state was initiated in 1949 by
publication of the Redlich/Kwong (RK) equation:
1
𝑅𝑇 𝑎 𝑇 −
𝑃= − 𝛼 𝑇𝑟 = 𝑇𝑟 2
𝑉−𝑏 𝑉 𝑉+𝑏
Eqn of
State 𝜶(𝑻𝒓 ) 𝝈 𝝐 𝛀 𝝍 𝒁𝑪
Vdw 1 0 0 1/8 27/64 3/8
−1/2
RK 𝑇𝑟 1 0 0.05664 0.42748 1/3
SRK 𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 + 1 0 0.08664 0.42748 1/3
PR 𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 ++
1+ 2 1− 2 0.0778 0.45724 0.30740
1 2
 𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 + = 1 + 0.48 + 1.574𝜔 − 0.176𝜔2 1 − 𝑇𝑟 2

1 2

 𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 ++ = 1 + 0.37464 + 2.5426𝜔 − 0.26992𝜔2 2

1 − 𝑇𝑟
Theorem of Corresponding States; Acentric Factor:
❖ Experimental observation shows that compressibility factors Z for different
fluids exhibit similar behavior when correlated as a function of reduced
temperature 𝑇𝑟 and reduced pressure 𝑃𝑟 by definition
𝑇 𝑃
𝑇𝑟 ≡ , 𝑃𝑟 ≡
𝑇𝐶 𝑃𝐶
This is the basis for the two-parameter theorem of corresponding states:
“All fluids, when compared at the same reduced temperature and reduced
pressure, have approximately the same compressibility factor, and all deviate
from ideal-gas behavior to about the same degree.”
Although this theorem is very nearly exact for the simple fluids (argon, krypton,
and xenon) systematic deviations are observed for more complex fluids.
Appreciable improvement results from introduction of a third corresponding-
states parameter, characteristic of molecular structure; the most popular such
parameter is the acentric factor 𝜔 introduced by K. S. Pitzer and coworkers.
The acentric factor for a pure chemical species is defined with reference to its
vapor pressure. Since the logarithm of the vapor pressure of a pure fluid is
approximately linear in the reciprocal of absolute temperature,

𝑑 log 𝑃𝑟𝑠𝑎𝑡
=𝑆
1
𝑑
𝑇𝑟
where 𝑃𝑟𝑠𝑎𝑡 is the reduced vapor pressure,
𝑇𝑟 is the reduced temperature,
1
and S is the slope of a plot of log 𝑃𝑟𝑠𝑎𝑡 𝑣𝑠
𝑇𝑟
If the two-parameter theorem of corresponding states were generally valid, the
slope S would be the same for all pure fluids.
This is observed not to be true; each fluid has its own characteristic value 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
1
Xe) lie on the same line when plotted as log 𝑃𝑟𝑠𝑎𝑡 𝑣𝑠
𝑇𝑟
and that the line passes
through log 𝑃𝑟𝑠𝑎𝑡 = −1.0 𝑎𝑛𝑑 𝑇𝑟 = 0.7.
This is illustrated in Fig Data for other
fluids define other lines whose locations can be
fixed in relation to the line for the simple fluids (SF)
by the difference: log 𝑃𝑟𝑠𝑎𝑡 𝑆𝐹 − log(𝑃𝑟𝑠𝑎𝑡 )
❖ The acentric factor is as this difference evaluated at 𝑇𝑟 = 0.7
𝜔 ≡ −1.0 − log 𝑃𝑟𝑠𝑎𝑡 Tr =0.7
❖ Therefore 𝜔 can be determined for any fluid from 𝑇𝐶 , 𝑃𝐶 and a single vapor-
pressure measurement made at 𝑇𝑟 = 0.7. Values of 𝜔 and the critical constants
and for a number of fluids are listed in App. B.
❖ The definition of 𝜔 makes its value zero for argon, krypton, and xenon, and
experimental data yield compressibility factors for all three fluids that are
correlated by the same curves when Z is represented as a function of 𝑇𝑟 and
𝑃𝑟 . This is the basic premise of the following three-parameter theorem of
corresponding states:
❖ “All fluids having the same value of 𝜔 when compared at the same 𝑇𝑟 and 𝑃𝑟 ,
have about the same value of Z, and all deviate from ideal-gas behavior to
about the same degree.”
Vapor & Vapor-Like Roots of the Generic Cubic Equation of State:
❖ Although one may solve explicitly for its three roots, the generic cubic
equation of state, is in practice far more commonly solved by iterative
procedures.
❖ Convergence problems are most likely avoided when the equation is
rearranged to a form suited to the solution for a particular root.
❖ For the largest root, i.e a vapor or vapor-like volume, generic cubic equation of
state is multiplied through by (𝑉 − 𝑏)/𝑃 It can then be written:
𝑅𝑇 𝑎 𝑇 𝑅𝑇 𝑎 𝑇 (𝑉 − 𝑏)
𝑃= − →𝑉−𝑏 = −
𝑉−𝑏 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏 𝑃 𝑃 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
𝑅𝑇 𝑎 𝑇 (𝑉 − 𝑏)
𝑉= +𝑏−
𝑃 𝑃 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
Vapor & Vapor-Like Roots of the Generic Cubic Equation of State:
❖ Solution for V may be by trial, iteration, or with the solve routine of a
software package.
❖ An initial estimate for V is the ideal-gas value RT/P.
❖ For iteration, this value is substituted on the right side of Eq.
❖ The resulting value of V on the left is then returned to the right side, and the
process continues until the change in V is suitably small.
❖ Convergence problems are most likely avoided when the equation is
rearranged to a form suited to the solution for a particular root.
❖ An equation for equivalent to above eqn. is obtained through the substitution
V = ZRT/P.
Vapor & Vapor-Like Roots of the Generic Cubic Equation of State:
In addition, the definition of two dimensionless quantities leads to
simplification.
𝑏𝑃 𝑎 𝑇
𝛽= 𝑞=
𝑅𝑇 𝑏𝑅𝑇
(𝑍 − 𝛽)
𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑃𝑟 Ψ 𝛼 𝑇𝑟
𝛽=Ω 𝑞=
𝑇𝑟 Ω𝑇𝑅
Iterative solution of above Eq. starts with the value Z = 1 substituted on the right
side. The calculated value of Z is returned to the right side and the process
continues to convergence.
The final value of Z yields the volume root through V = Z RT/P.
Liquid & Liquid-Like Roots of the Generic Cubic Equation of State:
𝑅𝑇 𝑎 𝑇 (𝑉 − 𝑏)
𝑉= +𝑏−
𝑃 𝑃 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
𝑉𝑃 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏 = 𝑅𝑇 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏 + 𝑏𝑃 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏 − 𝑎(𝑇)(𝑉 − 𝑏)
𝑎 𝑇 𝑉 − 𝑏 = 𝑅𝑇 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏 + 𝑏𝑃 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏 − 𝑉𝑃 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
𝑅𝑇 + 𝑏𝑃 − 𝑉𝑃
𝑉 − 𝑏 = 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
𝑎 𝑇
𝑅𝑇 + 𝑏𝑃 − 𝑉𝑃
𝑉 = 𝑏 + 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏
𝑎 𝑇
This equation with a starting value of V = b on the right side converges upon
iteration to a liquid or liquid-like root.
Liquid & Liquid-Like Roots of the Generic Cubic Equation of State:
❖ An equation forequivalent to above Eq. is obtained when vapor Eq. is
solved for the same Z in the numerator of the final fraction:
1+β−𝑍
𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑞𝛽
❖ For iteration a starting value of Z= 𝛽 is substituted on the right side. Once Z
is known, the volume root is V =ZRT/P
❖ Equations of state, such as the van der Waals and Redlich/ Kwong
equations, which express Z as functions of 𝑇𝑟 and 𝑃𝑟 only, yield two-
parameter corresponding states correlations.
❖ The Soave/Redlich/Kwong (SRK) equation and the Peng/Robinson(PR)
equation in which the acentric factor enters through function 𝛼(𝑇𝑟 , 𝜔) as an
additional parameter, yield three-parameter corresponding-states
correlations.
❖ Example 3.8: Given that the vapor pressure of n-butane at 350K is 9.4573 bar, find the
molar volumes of (a) Saturated–vapor and (b) Saturated–Liquid, n-butane at these conditions
as given by the(i)Van der waals eqn. (ii)Redlich/Kwong equation(iii)SRK Eqn. (iv) PR eqn.
❖ Critical properties of n-butane : 𝑇𝐶 = 425.1𝐾, 𝑃𝐶 = 37.96 𝑏𝑎𝑟 and 𝜔 = 0.200

Eqn of
𝜶(𝑻𝒓 ) 𝝈 𝝐 𝛀 𝝍 𝒁𝑪
State

Data: Vdw 1 0 0 1/8 27/64 3/8

𝑃 = 9.4573 𝑏𝑎𝑟, −1/2
RK 𝑇𝑟 1 0 0.05664 0.42748 1/3
𝑇 = 350 K,
𝑉 =?
SRK 𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 + 1 0 0.08664 0.42748 1/3
𝑅 = 83.14 𝑚3 𝑏𝑎𝑟/(𝑚𝑜𝑙 𝐾)
𝑇𝐶 = 425.1𝐾 PR 𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 ++
1+ 2 1− 2 0.0778 0.45724 0.30740
𝑃𝐶 = 37.96 𝑏𝑎𝑟
1 2
𝜔 = 0.200  𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 +
= 1 + 0.48 + 1.574𝜔 − 0.176𝜔2 1 − 𝑇𝑟 2

1 2
++
 𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 = 1 + 0.37464 + 2.5426𝜔 − 0.26992𝜔2 2
1 − 𝑇𝑟
Vapor & Vapor-Like Roots of the Generic Cubic Equation of State:
(𝑍 − 𝛽)
𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑃𝑟 Ψ 𝛼 𝑇𝑟
𝛽=Ω 𝑞=
𝑇𝑟 Ω𝑇𝑅
Iterative solution of above Eq. starts with the value Z = 1 substituted on the right
side. The calculated value of Z is returned to the right side and the process
continues to convergence.
The final value of Z yields the volume root through V = Z RT/P.
Liquid & Liquid-Like Roots of the Generic Cubic Equation of State:
1+β−𝑍
𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑞𝛽
❖ For iteration a starting value of Z= 𝛽 is substituted on the right side. Once Z is
known, the volume root is V =ZRT/P
 n-butane 𝜔 0.2 R 83.14
0.823
Temp. (T), K 350 Critical Temp. (Tc), K 425.1 Reduced Temp.(Tr), K
3
Pressure(P), Critical Pressure (Pc), Reduced Pressure (Pr),
9.4573 37.96 0.2491
bar bar bar
Eqn of
𝜶(𝑻𝒓 ) 𝝈 𝝐 𝛀 𝝍 𝒁𝑪 𝜶(𝑻𝒓 ) 𝛽 𝑞
State
Vdw 1 0 0 1/8 27/64 3/8 1 0.03782 4.099179
−1/2
RK 𝑇𝑟 1 0 0.05664 0.42748 1/3 1.10208 0.02622 6.604378

SRK 𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 + 1 0 0.08664 0.42748 1/3 1.1512508 0.02622 6.899067

PR 𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 ++
1+ 2 1− 2 0.0778 0.45724 0.30740 1.1681038 0.02354 8.338139

1 2 𝑃𝑟 Ψ 𝛼 𝑇𝑟
𝛼𝑆𝑅𝐾 𝑇𝑟 ; 𝜔 +
= 1 + 0.48 + 1.574𝜔 − 0.176𝜔2 1− 𝑇𝑟2 𝛽=Ω 𝑞=
𝑇𝑟 Ω𝑇𝑅
1 2
𝛼𝑃𝑅 𝑇𝑟 ; 𝜔 ++
= 1 + 0.37464 + 2.5426𝜔 − 0.26992𝜔2 1 − 𝑇𝑟2
 Van der waals eqn: ∈= 𝟎 , 𝝈 = 𝟎 , 𝜷 = 𝟎. 𝟎𝟑𝟕𝟖𝟐 , 𝒒 = 𝟒. 𝟎𝟗𝟗𝟏𝟕𝟗
(i) Van der waals equation: (vapor volume) (i) Van der waals equation: (Liquid volume)
(𝑍 − 𝛽) 1+β−𝑍
𝑍 = 1 + 𝛽 − 𝑞𝛽 𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽 𝑞𝛽
i Z0 Z1 V=ZRT/P
i Z0 Z1 V=ZRT/P 1
2
0.03782
0.04705
0.04705
0.05197
190.9336593

1 1.00000 0.88864 2666.8682 3

4
0.05197
0.05500
0.05500
0.05700
2 0.88864 0.87077 5
6
0.05700
0.05838
0.05838
0.05935
3 0.87077 0.86750 7 0.05935 0.06005
8 0.06005 0.06057
4 0.86750 0.86689 9 0.06057 0.06095
0.06095 0.06123
5 0.86689 0.86677
10
11 0.06123 0.06144
0.06144 0.06159
6 0.86677 0.86675
12
13 0.06159 0.06171

7 0.86675 0.86674 14
15
0.06171
0.06180
0.06180
0.06187

8 0.86674 0.86674 16
17
0.06187
0.06192
0.06192
0.06195
9 0.86674 0.86674 18
19
0.06195
0.06198
0.06198
0.06200
10 0.86674 0.86674 20
21
0.06200
0.06202
0.06202
0.06203
22 0.06203 0.06204
23 0.06204 0.06205
24 0.06205 0.06205
RK eqn: ∈= 𝟎 , 𝝈 = 𝟏 , 𝜷 = 𝟎. 𝟎𝟐𝟔𝟐𝟐 , 𝒒 = 𝟔. 𝟔𝟎𝟒𝟑𝟕𝟖
(ii) RKequation: (Liquid volume)
(ii) RK equation: (vapor volume) 1+β−𝑍
(𝑍 − 𝛽) 𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽 i Z0 Z1 V=ZRT/P
1 0.02622 0.03416 133.2652
i Z0 Z1 V=ZRT/P
2 0.03416 0.03803
1 1.00000 0.861917 2555.319 3 0.03803 0.04016
2 0.861917 0.837191 4 0.04016 0.04140
3 0.837191 0.831958 5 0.04140 0.04214
4 0.831958 0.830813 6 0.04214 0.04259
5 0.830813 0.830561 7 0.04259 0.04286
6 0.830561 0.830505 8 0.04286 0.04303
7 0.830505 0.830493 9 0.04303 0.04314
8 0.830493 0.83049 10 0.04314 0.04320
11 0.04320 0.04324
9 0.83049 0.83049
12 0.04324 0.04327
10 0.83049 0.83049
13 0.04327 0.04329
11 0.83049 0.83049 14 0.04329 0.04330
12 0.83049 0.83049 15 0.04330 0.04330
13 0.83049 0.83049 16 0.04330 0.04331
14 0.83049 0.83049 17 0.04331 0.04331
 SRK eqn: ∈= 𝟎 , 𝝈 = 𝟏 , 𝜷 = 𝟎. 𝟎𝟐𝟔𝟐𝟐 , 𝒒 = 𝟔. 𝟖𝟗𝟗𝟎𝟔𝟕
(ii) SRK equation: (Liquid volume)
(ii) SRK equation: (vapor volume)
1+β−𝑍
(𝑍 − 𝛽) 𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽 i Z0 Z1 V=ZRT/P
1 0.02622 0.03382 127.80954
2 0.03382 0.03736
i Z0 Z1 V=ZRT/P 3 0.03736 0.03920
1 1.00000 0.85459 2520.25589 4 0.03920 0.04021
2 0.85459 0.82717 5 0.04021 0.04078
3 0.82717 0.82099 6 0.04078 0.04110
4 0.82099 0.81954 7 0.04110 0.04129
5 0.81954 0.81920 8 0.04129 0.04139
6 0.81920 0.81912 9 0.04139 0.04146
10 0.04146 0.04149
7 0.81912 0.81910
11 0.04149 0.04151
8 0.81910 0.81910 12 0.04151 0.04152
9 0.81910 0.81909 13 0.04152 0.04153
10 0.81909 0.81909 14 0.04153 0.04153
15 0.04153 0.04154
16 0.04154 0.04154
PR eqn: ∈= 𝟏 − 𝟐, 𝝈 = 𝟏 + 𝟐, 𝜷 = 𝟎. 𝟎𝟐𝟑𝟓𝟒 , 𝒒 = 𝟖. 𝟑𝟑𝟖𝟏𝟑𝟗
(ii) PR equation: (vapor volume) (ii) PR equation: (Liquid volume)
(𝑍 − 𝛽) 1+β−𝑍
𝑍 = 1 + 𝛽 − 𝑞𝛽 𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽 𝑞𝛽
i Z0 Z1 V=ZRT/P
i Z0 Z1 V=ZRT/P 1 0.02354 0.02919 109.29250
1 1.00000 0.84039 2455.05584 2 0.02919 0.03201
2 0.84039 0.80839 3 0.03201 0.03353
3 0.80839 0.80059 4 0.03353 0.03438
4 0.80059 0.79860 5 0.03438 0.03486
5 0.79860 0.79808 6 0.03486 0.03514
7 0.03514 0.03530
6 0.79808 0.79795
8 0.03530 0.03539
7 0.79795 0.79792
9 0.03539 0.03545
8 0.79792 0.79791 10 0.03545 0.03548
9 0.79791 0.79790 11 0.03548 0.03550
10 0.79790 0.79790 12 0.03550 0.03551
13 0.03551 0.03551
14 0.03551 0.03552
15 0.03552 0.03552
Vapor Volumes
Vapor Volume
Exp 2482
Van der 2666.86
RK 2555.319
SRK 2520.255
PR 2455.05

Liquid Volumes:
Liquid Volume
Exp 115
Van der 190.93
RK 133.2652
SRK 127.809
PR 109.292
GENERALIZED CORRELATIONS FOR GASES:
❖ Pitzer Correlations for the Compressibility Factor:
❖ The correlation for Z takes the form 𝑍 = 𝑍 𝑂 + 𝜔𝑍 ′
❖ Where Z O 𝑎𝑛𝑑 𝑍 ′ are functions of both 𝑇𝑟 𝑎𝑛𝑑 𝑃𝑟 .
❖ When 𝜔 = 0 as is the case for the simple fluids, the second term disappears, and 𝑍 𝑜
becomes identical with Z.
❖ Thus a generalized correlation for Z as a function of 𝑇𝑟 𝑎𝑛𝑑 𝑃𝑟 based on data for just
argon, krypton, and xenon provides the relationship 𝑍 𝑂 = 𝐹 𝑂 𝑇𝑟 , 𝑃𝑟 By itself, this
represents a two-parameter states correlation for Z.
❖ Since the second term of Eq. is a relatively small correction to this correlation, its
omission does not introduce large errors, and a correlation for 𝑍 𝑜 may be used alone
for quick but less accurate estimates of Z than are obtained from a three-parameter
correlation.
❖ Equation is a simple linear relation between Z and 𝜔 for given values 𝑇𝑟 𝑎𝑛𝑑 𝑃𝑟 .
❖ Experimental data for Z for non simple fluids plotted vs. 𝜔 at constant 𝑇𝑟 𝑎𝑛𝑑 𝑃𝑟 do
indeed yield approximately straight lines, and their slopes provide values for Z' from
which the generalized 𝑍 ′ = 𝐹 ′ 𝑇𝑟 , 𝑃𝑟 can be constructed.
Pitzer Correlations for the Second Virial Coefficient:
❖ The tabular nature of the generalized compressibility-factor correlation is a
disadvantage, but the complexity of the functions Z 𝑜 𝑎𝑛𝑑 𝑍 ′ precludes their accurate
representation by simple equations.
❖ However, we can give approximate analytical expression to these functions for a
limited range of pressures. The basis for this is the simplest form of the virial equation:
𝐵𝑃 ෠ 𝑟
𝐵𝑃
𝑍 =1+ =1+
𝑅𝑇 𝑇𝑟
𝐵𝑃𝐶
෠
𝐵=
𝑅𝑇𝐶
𝐵෠ = 𝐵𝑂 + 𝜔𝐵′
𝑂
𝑃𝑟 ′
𝑃𝑟
𝑍 =1+𝐵 + 𝜔𝐵
𝑇𝑟 𝑇𝑟
𝑂 𝑂 𝑃𝑟 ′ ′ 𝑃𝑟
𝑍 =1+𝐵 ; 𝑍 =𝐵
𝑇𝑟 𝑇𝑟
Second virial coefficients are function of temperature only, similarly 𝐵𝑂 𝑎𝑛𝑑 𝐵′ are
function of reduced temperature only.
0.422 0.172
𝐵𝑂 = 0.083 − 1.6 𝐵′ = 0.139 − 4.2 valid only for low pressures
𝑇𝑟 𝑇𝑟
Pitzer Correlations for the third Virial Coefficient:
2
1
𝑍 = 1 + 𝐵𝜌 + 𝐶𝜌 𝜌 = = 𝑚𝑜𝑙𝑎𝑟 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
𝑉
2
෠
𝐵𝑃𝑟 𝑃𝑟
𝑍 =1+ +𝐶 መ
𝑇𝑟 𝑍 𝑇𝑟 𝑍
𝐵𝑃𝐶
෠
𝐵=
𝑅𝑇𝐶
𝐵෠ = 𝐵𝑂 + 𝜔𝐵′
𝐶𝑃𝐶2
𝐶መ = 2 2
𝑅 𝑇𝐶
𝐶መ = 𝐶 𝑂 + 𝜔𝐶 ′

0.02432 0.00313
𝐶𝑂 = 0.01407 + −
𝑇𝑟 𝑇𝑟10.5
′
0.05539 0.00242
𝐶 = −0.02676 + 2.7 −
𝑇𝑟 𝑇𝑟10.5
GENERALIZED CORRELATIONS FOR LIQUIDS:
❖ Although the molar volumes of liquids can be calculated by means of generalized
cubic equations of state, the results are often not of high accuracy.
❖ Values for both phases are provided in Tables E.l through E.4. Recall, however, that
this correlation is most suitable for nonpolar and slightly polar fluids.
❖ In addition, generalized equations are available for the estimation of molar volumes
of saturated liquids. The simplest equation, proposed by Rackett, is an example:
1−𝑇𝑟 2/7
𝑉 𝑠𝑎𝑡 = 𝑉𝐶 𝑧𝐶
❖ The only data required are the critical constants.
𝑃𝑟 1+(1−𝑇𝑟 2/7 )
𝑧 𝑠𝑎𝑡 = 𝑧𝐶
𝑇𝑟
❖ Lydersen, Greenkorn, and Hougen developed a two-parameter corresponding-states
correlation for estimation of liquid volumes. It provides a correlation of reduced
density 𝜌𝑟 as a function of reduced temperature and pressure. By definition
𝜌 𝑉𝐶
𝜌𝑟 ≡ =
𝜌𝐶 𝑉
❖ With above Eq. for determination of liquid volumes if the value of the critical volume
is known.
❖ A better procedure is to make use of a single known liquid volume (state 1) by the
identity,
𝜌𝑟1
𝑉2 = 𝑉1
𝜌𝑟2
V2 = required volume
V1 = known volume
𝜌𝑟1 , 𝜌𝑟2 = reduced densities read from plot
❖ This method gives good results and requires only experimental data that are usually
available.
❖ Example 3.9: Determine the molar volume of n-butane per kmol at 510K is 25 bar,
by each of the following. (i) The ideal gas equation (ii) The generalized
compressibility factor correlation (iii) The generalized virial coefficient correlation
❖ Critical properties of n-butane : 𝑇𝐶 = 425.1𝐾, 𝑃𝐶 = 37.96 𝑏𝑎𝑟 and 𝜔 = 0.200

(i) The ideal gas equation:

Data: 𝑹𝑻 83.14 × 10−3 × 510 𝑚3
𝑃 = 25 𝑏𝑎𝑟, 𝑽= = = 1.691
𝑷 25 𝑘𝑚𝑜𝑙
𝑇 = 310 K,
𝑉 =? (ii)The generalized compressibility factor correlation:
𝑅 = 83.14 × 10−3 𝑚3 𝑏𝑎𝑟/(𝐾𝑚𝑜𝑙 𝐾) 𝑇 510 𝑃 25
𝑇𝑟 = = = 1.2, 𝑃𝑟 = = = 0.659
𝑇𝐶 = 425.1𝐾 𝑇𝐶 425.1 𝑃𝐶 37.96
𝑃𝐶 = 37.96 𝑏𝑎𝑟 𝑍 𝑂 𝑎𝑛𝑑 𝑍 ′ 𝑣𝑎𝑙𝑢𝑒𝑠 𝑡𝑎𝑘𝑒𝑛 𝑓𝑟𝑜𝑚 𝑡𝑎𝑏𝑙𝑒 𝐸1 𝑎𝑛𝑑 𝐸2
𝜔 = 0.200 At 𝑇𝑟 = 1.2 𝑎𝑛𝑑 𝑃𝑟 = 0.6, 𝑍 𝑂 = 0.8779, 𝑍 ′ = 0.0326
At 𝑇𝑟 = 1.2 𝑎𝑛𝑑 𝑃𝑟 = 0.8, 𝑍 𝑂 = 0.8330, 𝑍 ′ = 0.0499
Interpolate to 𝑃𝑟 = 0.659
At 𝑇𝑟 = 1.2 𝑎𝑛𝑑 𝑃𝑟 = 0.659, 𝑍 𝑂 = 0.8646, 𝑍 ′ = 0.0377
At 𝑇𝑟 = 1.2 𝑎𝑛𝑑𝑃𝑟 = 0.659, 𝑍 𝑂 = 0.8646, 𝑍 ′ = 0.0377
𝑍 = 𝑍 𝑂 + 𝜔𝑍 ′
𝑍 = 0.8646 + 0.2 ∗ 0.0377 = 0.87214
𝑍𝑅𝑇 83.14 × 10−3 × 510 𝑚3
𝑉= = 0.87214 × = 1.4792
𝑃 25 𝑘𝑚𝑜𝑙
(iii) The generalized virial coefficient correlation:
𝑃
𝑂 𝑟
𝑃
′ 𝑟
𝑍 =1+𝐵 + 𝜔𝐵
𝑇𝑟
𝑇𝑟
𝑂
0.422 0.422
𝐵 = 0.083 − 1.6 = 0.083 − 1.6
= −0.232
𝑇𝑟 1.2
′
0.172 0.172
𝐵 = 0.139 − 4.2 = 0.139 − 4.2
= 0.059
𝑇𝑟 1.2
0.659 0.659
𝑍 = 1 − 0.232 × + 0.2 × 0.059 × = 0.879
1.2 1.2
𝑍𝑅𝑇 83.14 × 10−3 × 510 𝑚3
𝑉= = 0.879 × = 1.491
𝑃 25 𝑘𝑚𝑜𝑙