TERMODINAMIKA

TEKNIK KIMIA 2
Dr. Ifa Puspasari
PVT BEHAVIOUR
(PURE SUBSTANCE)
PT Diagram
PT Diagram
PT Diagram
PT Diagram
PT Diagram
PT Diagram
PT Diagram
PT Diagram
PT Diagram
PT Diagram
PV Diagram
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Critical Behaviour
Equation of State (EOS)
• From PT-diagram, PV-diagram
• It is suggested that P-V-T are correlated
• For any pure species, only two of P-V-T are independent
• Can construct correlation for P-V-T
• Since P-V-T are correlated, we can write:

𝑓 𝑃, 𝑉, 𝑇 = 0 Equation of State

• Most familiar form, EOS for ideal gas

𝑃𝑉 = 𝑅𝑇
Equation of State (EOS)
• If V is considered as a function of T and P

𝑉 = 𝑉 𝑇, 𝑃

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

1 1 𝜕𝑉 1 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝑉 𝑉 𝜕𝑇 𝑃
𝑉 𝜕𝑃 𝑇

β : Volume expansivity -κ : Isothermal compressibility

Equation of State (EOS)
• From math point of view,

𝑉 = 𝑉 𝑇, 𝑃

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝑃 𝑇

1
𝑑𝑉 = 𝛽𝑑𝑇 − 𝜅𝑑𝑃
𝑉
• Common for liquid
• If β = 0 and κ = 0 incompressible fluid

𝑉2
ln = 𝛽 𝑇2 − 𝑇1 − 𝜅 𝑃2 − 𝑃1
𝑉1
Example 1
For liquid acetone at 20°C and 1 bar,
−1
𝛽 = 1.487 × 10−3 °C 𝜅 = 62 × 10−6 bar−1 𝑉 = 1.287 cm3 g−1

For acetone, find:

𝜕𝑃
a) The value of 𝜕𝑇 𝑉 at 20°C and 1 bar.
b) The pressure generated by heating at constant V from
20°C and 1 bar to 30°C.
c) The change in volume for a change from 20°C and
1 bar to 0°C and 10 bar
Ideal Gas
• PV = RT
• Assumptions for ideal gas:
• No intermolecular interaction
• Internal energy is function of T only
• Molecules occupy no space
• Applicable range (with good approximation):
• High T (> 0 °C), low P (1-2 atm)
EOS : Virial Equations
• Non-ideal
• Represents PV along isotherm by power series:

𝑃𝑉 = 𝑎 + 𝑏𝑃 + 𝑐𝑃2 + 𝑑𝑃3 + ⋯

𝑃𝑉 = 𝑎 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯

• a : function of T
• B’, C’, D’ … : function of T & species
EOS : Virial Equations
EOS : Virial Equations
𝑃𝑉 = 𝑎 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯

• Define a = RT

• At T = 273,16 K

3
lim 𝑃𝑉 273,16 K = 𝑎 = 22711.8 cm bar/(mol K)
𝑃→0

22711.8
𝑅= = 83.1447 cm3 bar/(mol K)
𝑇
EOS : Virial Equations
𝑃𝑉 = 𝑎 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯

𝑃𝑉 = 𝑅𝑇 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷′ 𝑃3 + ⋯

𝑃𝑉
𝑍= = 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2 + 𝐷 ′ 𝑃3 + ⋯
𝑅𝑇

Compressibility factor
Deviation from ideal gas behaviour

•Z=1 ideal gas

EOS : Virial Equations
• Alternate form:
𝐵 𝐶 𝐷
𝑍 = 1+ + 2+ 3+⋯
𝑉 𝑉 𝑉

• From statistical mechanics:

𝐵
: results from “two-body” interactions
𝑉

𝐶
: results from “three-body” interactions
𝑉 2
EOS : Virial Equations
• Virial coefficient – relationship between 2 forms

𝐵
𝐵′ =
𝑅𝑇

𝐶 − 𝐵 2
𝐶′ =
𝑅𝑇 2

𝐷 − 3𝐵𝐶 + 2𝐵 3
𝐷′ =
𝑅𝑇 3

and so on
EOS : Virial Equations
• Two-terms truncation of virial equations
𝑃𝑉 𝐵𝑃
𝑍= =1+
𝑅𝑇 𝑅𝑇
𝑃𝑉 𝐵
𝑍= =1+
𝑅𝑇 𝑉

• Three-terms truncation of virial equations

𝑃𝑉 𝐵 𝐶
𝑍= =1+ + 2
𝑅𝑇 𝑉 𝑉
Example 2
Reported values for the virial coefficients of isopropanol
vapour at 200°C are:

𝐵 = −388 cm3 mol−1 𝐶 = −26,000 cm6 mol−2

Calculate V and Z for isopropanol vapour at 200°C and

10 bar by:
a) The ideal-gas equation
b) Two-terms truncation of virial equations
c) Three-terms truncation of virial equations
Cubic EOS

• Cubic  Cube  “power of 3”

• General form:

𝑃𝑉 3 + 𝑎𝑉 2 + 𝑏𝑉 + 𝑐 = 0

• Intended for wide range of T and P

• Applicable to liquids as well as gases & vapours

Cubic EOS
• Many versions:
• van der Waals (vdW)
• Redlich – Kwong (RK)
• Soave – Redlich – Kwong (SRK)
• Peng – Robinson (PR)
• Benedict – Webb – Rubin (BWR)
• and much more
Cubic EOS
Cubic EOS
Cubic EOS
van der Waals EOS
𝑅𝑇
• Correction of ideal gas law: 𝑃 =
𝑉

• include “size” of molecules (&”repulsive forces”)

𝑅𝑇
𝑃=
𝑉−𝑏
• include “attractive forces”
• attractive forces α 1/r6

𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉
van der Waals EOS
• Parameters a and b can be determined:
• empirically for each individual compound
• estimate from:

2
27 𝑅 𝑇𝑐
𝑎=
64 𝑃𝑐

𝑅 𝑇𝑐
𝑏=
8 𝑃𝑐
Redlich-Kwong EOS
• “modification of van der Waals”:
• more accurate

𝑅𝑇 𝑎
𝑃= − 12
𝑉−𝑏 𝑇 𝑉 𝑉+𝑏

• a & b are different than those for van der Waals’s

Generalized Cubic EOS
𝑅𝑇 𝑎 𝑇
𝑃= −
𝑉−𝑏 𝑉 + 𝜖𝑏 𝑉 + 𝜎𝑏

• Where
• 𝜖 and 𝜎 : pure numbers
• a(T) and b : substance dependence

𝛼 𝑇𝑟 𝑅2 𝑇𝑐2 𝑅𝑇𝑐
𝑎 𝑇 =𝜓 𝑏=Ω
𝑃𝑐 𝑃𝑐
Generalized Cubic EOS
• Table: Parameter assignments for EOS
Generalized EOS
• express Z as a function of Tr and Pr

𝑇 𝑃
𝑇𝑟 = 𝑃𝑟 =
𝑇𝑐 𝑃𝑐

• based on 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 behaviour to about the same degree.”
Generalized EOS : Example
• van der Waals EOS
𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉

• from PV diagram, we can see that:

• slope of tangential line at critical point is zero

𝜕𝑃 𝜕 2𝑃
=0 =0
𝜕𝑉 𝜕𝑉 2 at C−pt
𝑇 at C−pt 𝑇
 𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉

𝜕𝑃 −𝑅𝑇𝑐 2𝑎
= 2
+ 3=0 1
𝜕𝑉 𝑇 at C−pt
𝑉𝑐 − 𝑏 𝑉𝑐

• and
𝜕 2𝑃 −2𝑅𝑇𝑐 6𝑎
= + 4=0 2
𝜕𝑉 2 𝑇 at C−pt
𝑉𝑐 − 𝑏 3 𝑉𝑐
 3
× 1 + 2
𝑉𝑐
−3𝑅𝑇 2𝑅𝑇
2
+ 3
=0
𝑉𝑐 𝑉𝑐 − 𝑏 𝑉𝑐 − 𝑏
𝑉𝑐 = 3𝑏
• Put it back into 1 , and solve for a

9
𝑎 = 𝑉𝑐 𝑅𝑇𝑐
8
 9
• replace 𝑉𝑐 = 3𝑏 and 𝑎 = 𝑉𝑐 𝑅𝑇𝑐 into vdW at critical point
8
𝑅𝑇𝑐 𝑎
𝑃𝑐 = − 2
𝑉𝑐 − 𝑏 𝑉𝑐

• solve for b, we will get

𝑅 𝑇𝑐
𝑏=
8 𝑃𝑐
• then solve for a, we will get
2
27 𝑅 𝑇𝑐
𝑎=
64 𝑃𝑐
Generalized EOS : Example
• van der Waals EOS

𝑅𝑇 𝑎
𝑃= − 2
𝑉−𝑏 𝑉

• Instead of using empirical values of a and b

• Use

27 𝑅 𝑇𝑐 2 𝑅 𝑇𝑐
𝑎= 𝑏=
64 𝑃𝑐 8 𝑃𝑐

Generalized van der Waals EOS

Generalized Z-Chart
Generalized EOS
• Generalized EOS based on 2-parameter theorem of
corresponding states is far better than ideal gas law

• but it is still not as good as experimental results

• except Ar, Kr, Xe “Simple fluid”

• introduce 1 more variable, “acentric factor, ω”

3-parameter theorem of corresponding states

Acentric Factor

• characterize how “nonspherical” a molecule is

• calculated based on “Simple fluid” (Ar, Kr, Xe)

• definition

𝑃sat at 𝑇 =0.7
𝑟
𝜔 ≡ −1.0 − log10
𝑃𝑐
Generic Cubic EOS
• Vapour:
𝑍−𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽
𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑃𝑟 𝜓𝛼 𝑇𝑟
𝛽=Ω 𝑞=
𝑇𝑟 Ω𝑇𝑟

• Liquid:

1+𝛽−𝑍
𝑍 = 𝛽 + 𝑍 + 𝜖𝛽 𝑍 + 𝜎𝛽
𝑞𝛽
Example 3
Given that the vapour pressure of n-butane at 350 K is
9.4573 bar, find the molar volumes of:
a) Saturated-vapour
b) Saturated-liquid
of n-butane at these conditions as given by the
Redlich/Kwong equation.
Generalized EOS
• Pitzer’s correlation

Z = Z0 + ω Z1

Z : Compressibility factor of interested fluid

Z0 : Compressibility factor of simple fluid, f(Tr, Pr)
Z1 : Correction parameter, f(Tr, Pr)
ω : Acentric factor, f(species)

find from Tables (Lee/Kesler), Charts

Generalized EOS
• Pitzer’s correlation

Z = Z0 + ω Z1

• accuracy is good for non-polar or slightly polar gases

• big error for highly polar gases

• can be used for both gases and liquids

Generalized Virial EOS
• Problem with Pitzer’s 1st-correlation
data for Z0 and Z1 are not readily available
• Pitzer proposed another correlation
• Uuse in conjunction with Virial equation

𝑃
0 𝑟
𝑃
1 𝑟
𝑍 = 1+𝐵 + 𝜔𝐵
𝑇𝑟 𝑇𝑟

𝑍 = 𝑍 0 + 𝜔 𝑍1 Pitzer’s 1st-correlation
Generalized Virial EOS
• Pitzer’s correlation for 2nd virial coefficient
𝑃
0 𝑟
𝑃
1 𝑟
𝑍 = 1+𝐵 + 𝜔𝐵
𝑇𝑟 𝑇𝑟
• where

0
0.422
𝐵 = 0.083 − 1.6
𝑇𝑟

1
0.172
𝐵 = 0.139 − 4.2
𝑇𝑟
Generalized Virial EOS
• Correlation for 3rd virial coefficient
2
𝑃𝑟 𝑃𝑟
𝑍 =1+𝐵 +𝐶
𝑇𝑟 𝑍 𝑇𝑟 𝑍
• where
𝐵 = 𝐵0 + 𝜔𝐵1

𝐶 = 𝐶 0 + 𝜔𝐶 1
0.02432 0.00313
𝐶0 = 0.01407 + −
𝑇𝑟 𝑇𝑟10.5

0.05539 0.00242
𝐶1 = −0.02676 + 2.7 −
𝑇𝑟 𝑇𝑟10.5
Example 4
Determine the molar volume of n-butane at 510 K and
25 bar by each of the following:
a) The ideal-gas equation.
b) The generalized compressibility-factor correlation.
c) The correlation for second virial coefficient.
d) The correlation for third virial coefficient.
Example 5
What pressure is generated when 1 (lb mol) of methane is
stored in a volume of 2 (ft)3 at 122 (°F)? Base calculations
on each of the following:
a) The ideal-gas equation.
b) The Redlich/Kwong equation.
c) A generalized correlation.
Liquids
• Prediction of liquid volume

• Rackett equation

𝑉 sat = 𝑉𝑐 𝑍𝑐 1−𝑇𝑟 0.2857

only for saturated liquid

• Generalized density correlation

𝑉𝑐
𝑉=
𝜌𝑟
Liquids
• if volume at another condition is known

𝜌r1
𝑉2 = 𝑉1
𝜌r2

• Use Chart for generalized correlation to find ρr1, ρr2