02 Chapter 03 Compiled

CHAPTER 3
Volumetric Properties of Pure

Fluids: Part 1
Norhaniza binti Yusof

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Topic Outcomes
Week Topic Topic Outcomes
2-3 Volumetric Properties of Pure Fluids It is expected that students are
able to:
Introduction to volumetric properties
Determine the state/phase of a
PVT behaviour of pure substances given fluid at given conditions.
Volumetric properties from equations of Calculate the volumetric

state: properties using the equations of
o Ideal gas equation state and generalized correlations
o Virial equation for a given system.
o Generic cubic equations
Identify the applicability and
Volumetric properties from generalized limitation of every equation of
correlations: state.
o Gases
o Liquid Determine the volumetric
properties from thermodynamic
Volumetric properties from tables and diagrams.
thermodynamic Tables and Diagrams

Scope of Lecture
Introduction to volumetric properties
PVT behaviour of pure substances
Volumetric properties from equations of state

PVT Behavior of Pure
Substances
3 A Fluid region
Pc Liquid region C
Fusion curve
Pressure
Vaporization
curve
Solid region B
Gas region
Triple Vapor
2 point region
Sublimation
1
curve
Temperature Tc

PT Diagram for Pure Substances
Fliq = 2
(divariant)
3 A Fluid region
Pc Liquid region C
Fusion curve DOF for No. of
Pressure
the system species

Vaporization
curve Fvap. curve = 1
B (univariant) F=2+N
Solid region
Ftp = 0 Gas region Independent No. of
(invariant) Triple Vapor variables (T, P) phases
2 point region Supercritical
Sublimation T > Tc
1
curve
Temperature Tc
Note: DOF, degree of freedom Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
PV Diagrams for Pure Substances
In a PV diagram, the phase boundaries becomes areas/region
Sol., liq. & gas regions Liq., liq./vap. regions & vap. with isotherms
Single-phase (sat.)
vap. at cond. T
Triple point
Single-phase (sat.) Subcritical T

liqs. at boiling T consist of 3 segments
Note: Sol., solid; liq., liquid; vap., vapor; sat., saturated; cond., condensation; T, temperature
PVT Surface for a Real Substance
P P
CP CP
Solid Liquid
T Gas
Vapor
T
Triple line
Note: CP., critical point Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
PVT Surface (Cont.)
Constant temperature line

Pure Substances Phase
Any fluid could be in one of below conditions :
Single-phase liquid
Single-phase gas
2-phases, liquid & gas
Generally, if the system is at any T or P;
Condition T and P Phase
T > Tc Gas
T < Tc and P > Pc Liquid
T < Tc and P < Pc See boiling point T > Tbpt Gas
T < Tc and P < Pc See boiling point T < Tbpt Liquid
T < Tc and P < Pc See boiling point T = Tbpt 2-phase (saturated)

*For H2O, Tc = 374 oC and Pc = 220 bar
Note: Tc, critical temperature, Pc, critical pressure, Tbpt, biling point temperature
Determination of Pure Substances Phase
Boiling point and vapor pressure could be obtained from :
B
Antoine equation logPsat A
T C
Cox Chart
E.g.: Antoine equation for H2O;
log10 P (mmHg) = 7.96681 1668.21 / (T oC + 228)
Liquid phase: V is almost stable and not depend on P and T.
Gas phase: V of pure substance is depend on T and P.
Mathematic relations between P, V, T of pure substance is called as

EQUATION OF STATE

Single-Phase Region
From the regions of the diagram (PV) where a single phase exists,
implies a relation connecting P, V & T express by function equation
f (P, V, T ) = 0 PVT equation of state (EoS)
Simplest EoS ideal gas law
Valid for low P

PV = RT Will be discussed later
To solve the equation,

V = f (P , T ) or P = f (V , T) or T= f (P , V)
Note: P, pressure; EoS; equation of state Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Example
V = f (P, T) V = V (P, T) Hence,
dV
Partial derivative in the equation dT dP
V
V V
dV dT dP
T P P T Integration
V2
Divide by V ln T2 T1 P2 P1
V1
Volume expansivity,
For liquid phase

dV 1 V 1 V
dT dP incompressible fluid
V V T P V P T
and are very small ( 0).

Isothermal compressibility,
Notes
Gas
Ideal gas Non-ideal gas
PV = ZRT Equations of state (from PVT

Valid at low pressure data).
Z=1 Generalized correlations
Equations of state
Theorem of corresponding states

Equation of State
Equation
of State
Cubic
Ideal Gas Virial
Equation
Equation Equation
of State
Redlich/
Van Der Redlich/ Peng/
Kwong/ Generic
Waals Kwong Robinson
Soave
Vapor & Liquid &

Vapor-Like Liquid-Like
Roots Roots

Virial Equations of State

Virial Equations (Gas Phase)
A useful auxiliary thermodynamic property is defined by the equation
PV
Z
RT
Compressibility factor
There are 2 types of virial equations / virial expansions :
B C B 2 D 3BC 2B 2
B C D
RT RT 2 RT 3
PV B, C, D, B, C, D etc.
Z 1 B P C P 2 DP 2 virial coefficients
RT
PV B C D
Z 1 2 3 .... Only depend on T.
RT V V V Obtained from PVT data.
Note: T, temperature Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Application of the Virial Equations
CH4
Low to moderate P (P < 15 bar)
2 terms
PV BP
Z 1 B P Z 1
RT RT
High P up to 50 bar (below the Pc)
Truncated to 3 terms
PV B C
Z 1 B P C P 2 Z 1 2
RT V V
Note: P, pressure; Pc, critical pressure Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
The Ideal Gas
Virial expansion arise on account of molecular interaction.
Term B/V arises on account of interactions between pairs of
molecules
The C/V2 term, on account of 3-body interactions.
For ideal gas interaction molecular is assume not existed.

As the P of real gas is reduced at constant T
V & the contribution of the terms B/V, C/V2, etc., .
As P 0, V becomes , then Z approaches unity,
=1
PV = ZRT (low P only)

Internal energy
Internal energy of a REAL GAS is a function of P & T
P dependency is the result of forces between the

molecules.
If such forces did not exist (IDEAL GAS behavior) the
internal energy of gas depends on T only
U = U(T) (Ideal gas)

Property Relations for an Ideal Gas
Heat capacity at constant V (CV) is a func. of T only
U dU
Cv C v T dU C v dT U C v dT
T v dT
Enthalpy (H) is a func. of T only

H U PV UT RT HT
Heat capacity at constant P (CP) is a func. of T only

H dH
Cp C p T dH C pdT H C pdT
T p dT
Relation between CP and CV

dH dU
Cp Cv R
dT dT
This equation does not imply that CP and CV are themselves constant for an ideal
gas, but only that they vary with T in such a way that their difference is equal to R.
Equations for Process Calculations
For a unit mass or a mole of IDEAL GAS in any mechanically
reversible closed-system process:
dQ dW C v dT
dQ C v dT PdV
dW PdV
RT RT PV
P V T
V P R
dV dP Cv Cp
dQ C v dT RT dQ C pdT RT dQ dT PdV
V P R R
dV dP dW PdV
dW RT dW RdT RT
V P
These equations may be applied to the following processes

Adiabatic Process
Isothermal process: U H 0
V2 P
Q W RTln RTln 2
V1 P1
Isobaric process: U C v dT H C pdT
Q H C pdT W R T2 T1
Isochoric process: U C v dT H C pdT
Q U C v dT W0

Adiabatic Process (Const. Heat Capacities)
Equations Other expressions
TV 1 constant
Cp 1/
1 / P1V1 P2 RT P 1/
TP constant Cv W 1 1 2 1
1 P1 1 P
1
PV constant
Work
W U C v dT C v T The process should be mechanically

reversible!
Alternative forms
RT 2 RT1 P2 V2 P1V1
W
1 1

Example 1 (Ideal gas)
One mol of an ideal gas with Cp = (7/2)R and Cv = (5/2)R expands

from P1 = 8 bar and T1 = 600 K to P2 = 1 bar by each of the following
paths:
a) Constant volume
b) Constant temperature
c) Adiabatically
Assuming mechanical reversibility, calculate W, Q, U, and H for

each process.

Example 2 (Virial Equation)
Reported values for the virial coefficients of isopropanol vapor at
200 C are:
B = 388 cm3 mol1 C = 26000 cm6 mol2
Calculate V and Z for isopropanol at 200 C and 10 bar by:
a) The ideal-gas equation
b) Truncated virial equation to 3 terms

Tutorial 1
For methyl chloride at 100 C the 2nd and 3rd virial coefficients are:
B = 242.5 m3 mol 1 C = 25, 200 cm6 mol 2
Calculate the work of mechanically reversible, isothermal

compression of 1 mol of methyl chloride from 1 bar to 55 bar at
100 C. Base calculations on the following forms of the virial equations:
B C PV
a) Z 1 2 b) Z 1 B P C P 2
V V RT
B C B2
Where B C
RT RT 2

N02 1-310 12.00 1.00 P.M Feb 21, 2013 (Thu)
CHAPTER 3
Fluids: Part 2
Mohd Asmadi Bin Mohammed Yussuf


Scope of Lecture
Cubic equation of state
Generic cubic
Example & Tutorial

Cubic Equation of State
Cubic
Equation
of State
Redlich/
Kwong/ Generic
Soave
Vapor & Liquid &

Roots Roots

Generic Cubic Equation of State
The simplest equations capable of representing both liquid and vapor

behavior but not for dual-phase condition.
More accurate for a wide range of T and P
RT V
P

V b V b V 2 V
Where b , , , and are parameters which is general depend on T

and (for mixture) composition .
Note: T, temperature; P, pressure; cubic equation of state ,15 < p < 50 bar
Equation of State Parameters
When in polynomial form :
RT c 27R 2 Tc2
b a
8Pc 64Pc
RT 3 a ab
V b c
3
V V 0
Pc Pc Pc
Where
Pc and Tc pressure and temperature in critical point
a and b +ve constants.

Cubic Equation of State
Cubic
Equation
of State
Redlich/
Kwong/ Generic
Soave
Vapor & Liquid &

Roots Roots

van der Waals
=a =b
RT V A Generic Cubic EoS

P

V b V b V 2 V (previous slide)
==0
Reduces to van
der Waals EoS
Will be
RT c
b discussed later
RT a 8Pc
P 2
V b V 27R 2 Tc2
a
64Pc
Note: EoS; equation of state Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Redlich/Kwong
Equation, R 2 Tc2 R 2 Tc2
a 0.42748
Pc Pc
a Tr Tr-1/2
RT a T RT a
P P 0.5
V b V V b V b Tr V bV
RT c RT
b 0.08664 c
Pc Pc
RT 2 a RT b PT b ab
1.5 0.5 2
Solve by cubic
V
3
V
V PT 0.5 0

P PT 0.5

equation solver.

V for Gas & Liquid Phases (RK)
V for gas phase V for liquid phase
RT a T V b
P RT 2 2 bRT a ab
V b V V b P V3
P
V b
P
0.5 V
PT PT 0.5
0

Multiple &
rearrange
RT a V b
V b 0.5
P T PV V b
3 RT 2 ab
Vi V
i
P PT 0.5
Vi 1
RT a V b bRT a
Vi1 b 0.5 i b2 0.5
P T PV i Vi b P PT
Solve by iteration method, use b as an initial Vo.
Note: RK, Redlich/Kwong Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Redlich-Kwong-Soave & Peng-Robinson
Redlich-Kwong-Soave Peng-Robinson
RT a RT a
P P
V b V bV V b V V b bV b

1 S 1 Tr0.5 2
S 0.37464 1.54226 0.269922
R 2 Tc2
S 0.48508 1.55171 0.156132 a 0.45724
Pc
R 2 Tc2
Acentric factor (App. B) b 0.07780
Pc

Parameters for all Cubic Equation of State
EoS a( Tr) Zc
van der Waals 1 0 0 1/8 27/64 3/8

1
Redlich/ Kwong Tr 2 1 0 0.08664 0.42748 1/3
Redlich-Kwong-
SRK Tr ; 1 0 0008664 0.42748 1/3
Soave
Peng-Robinson PR Tr ; 1 2 1 2 0.07779 0.45724 0.30740

SRK Tr ; 1 0.48508 1.574 0.1762 1 Tr1/2
2

PR Tr ; 1 0.37464 1.54226 0.269922 1 Tr1/2
2
Note: Please text book p. 98 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Generic Cubic
Vapor & Vapor-Like Roots of the Generic Cubic EoS
RT a T V b
V b
P P V bV b
Solution for V may be by

Trial
Iteration
With the solve routine of a software package
Initial estimate for V is the ideal-gas value RT/P

Dimensionless Quantities
An equation for Z equivalent to equation above is obtained
through
substitute
RT a T V b ZRT
V b V
P P V bV b P
2 dimensionless quantities leads to simplification

RT R 2 Tc2
b c a Tc
Pc Pc
bP P a T Tr
r q
RT Tr bRT Tr

Determination of Z
Therefore,
Z
Z 1 q
Z Z
Iteration
Start with Z = 1 Substituted on the right side.
Calculated Z Returned to the right side
Process continues to convergence
Final Z yields the volume root through V = ZRT/P

Generic Cubic (Cont.)
Liquid & Liquid-Like Roots of the Generic Cubic EoS
V in the numerator of the final fraction to give :

RT a T V b
V b
P P V bV b
RT bP VP
V b V bV b
a T
Starting value V = b.
An equation for Z equivalent to the equation above :
1 Z
Z Z Z
q

Iteration
For iteration Z = . Once Z is known, the volume root is
ZRT
V
P
EoS which express Z as a function of Tr & Pr

Called generalized
Their general applicability

to all gases & liquids.
A Generic Cubic Equation of State
An important class of cubic equations results from the preceding

equation with the assignments
=b =a(T) =(+)b = b2
RT a T
P
V b V bV b
Tr R 2 Tc2 & are pure numbers

a T
Pc same for all substances
RT a(T) is specific to each EoS
b c
Pc
Determination of EoS Parameters
Suitable estimates of EoS parameters are usually found from values for
the critical constants Tc and Pc critical isotherm exhibits a horizontal
inflection at the critical point!
At critical point ( Pc, Tc, Vc & Zc ) : Replace Pc, Tc and Vc

8a
Vc 3b T
P
c
2P 27Rb
0 2 0
V Tc V Tc a Pc Vc 3
Pc Zc 0.375
27b2 RT c 8
From van der Waals equation :

Then,
P RT 2a
3 0
V T V b V
2
27R 2 Tc2 RT c
2P 2RT 6a a b
2 0 64Pc 8Pc
V T V b V
3 4
EoS Parameters (Cont.)
An analogous procedure may be applied to the generic cubic

equation
RT a T
P
V b V bV b
Previous slide
Yielding expressions for parameters
and
R 2 Tc2 RT c Pure numbers,
a Tc b Independent of substance
Pc Pc Determined for a particular EoS
from the values assigned to &

EoS Parameters (Cont.)
R 2 Tc2
a Tc
Pc
This result may be extended to T other than the critical by

Introduction of a dimensionless function
Tr R 2 Tc2
a Tc unity at the Tc
Pc
Function (Tr) : an empirical expression

specific to a particular equation of state.
Note: Tc; critical temperature Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Theorem of Corresponding States
All fluids, when compared at the same Tr & Pr, have approximately the
same Z, and all deviate from ideal-gas behavior to about the same
degree .
T P
Tr Pr
Tc Pc
This theorem is very nearly exact for the simple fluids (Ar, Kr, Xe).
However, systematic deviations are observed for more complex fluids.
Note: Z; compressibility factor ; Tr, reduce temperature; Pr, reduced pressure

Acentric Factor (Cont.)
Approximate T dependence of the reduced vapor pressure

Therefore, an acentric factor is introduced as follow:
Acentric factor
1.0 log Prsat Tr 0.7
At Tr = 0.7
= 0 (Ar, Kr & Xe)
This value of can be determined for any fluid from Tc, Pc and a single
vapor-pressure measurement made at Tr = 0.7
App. B lists the values of and the critical constants Tc, Pc, and Vc for a
number of fluids.

All fluids having the same value of , when compared at the same Tr & Pr,
have about the same value of Z, and all deviate from ideal-gas behavior to
about the same degree.

Example 3
Given that the vapor pressure of n-butane at 350 K is 9.4573
bar, find the volumes of (a) saturated-vapor and (b)
saturated-liquid n-butane at these conditions as given by the
Redlich/Kwong equation.

Example 4
Calculate Z and V for ethylene at 25 C and 12 bar by the

following equations:
a) The Redlick/Kwong equation

b) The Soave/Redlich/Kwong equation
c) The Peng/Robinson equation

Tutorial 2
Calculate Z and V for ethylene at 50 C and 15 bar by the

following equations:
a) The Redlick/Kwong equation

b) The Soave/Redlich/Kwong equation
c) The Peng/Robinson equation

N02 2-6, 11.00 1.00P.M Feb 17, 2013 (Mon)
CHAPTER 3
Fluids: Part 3
Mohd Asmadi Bin Mohammed Yussuf


Scope of Lecture
Generalized Correlations for Gases

Compressibility factor, Z
2nd virial coefficient, B
Generalized Correlations for Liquids
Examples & Tutorials

Generalized Correlations for
Gases
4.0
1.0
2.4
1.8
0.9
Z0
Tr = 0.8
0.9 1.0 1.1 1.5
0.8
1.3
0.7
0.0 0.5 1.0 1.5 2.0 2.5
Pr

Pitzer Correlations for the Z
The correlation for Z takes form :
Equally suitable for

Z Z 0 Z1 gases & liquids
Where Z0 and Z1 are functions of both Tr and Pr .
From Table E1E4, require interpolation, see App. F
Error
Non-polar/slightly polar < 2-3%
Highly polar larger error
When = 0 simple fluids. Z Z0 Ar, Kr, Xe

Lee/ Kesler Correlation for Z0 = F0 (Tr, Pr)
1.2
4.0
1.0
Tr = 0.7 Gases 1.5

0.8
0.9
1.2
Z0
0.6 1.0
Two-phase
region
0.4
C
0.9
0.2
Compressed
liquids (Tr < 1.0)
0
0.05 0.1 0.2 0.5 1.4 2.0 5.0 10.0
Pr

Quantum Gases (H2, He, Ne)
Do not conform to the same corresponding-states behavior as do
normal fluids
The correlation is accommodated by use of T-dependent effective

critical parameters.
E.g. Hydrogen
43.6 20.5 51.5

Tc K
21.8
Pc bar
44.2

Vc cm3mol1 9.91
1 1 1
2.016T 2.016T 2.016T
T = absolute temperature in K

Pitzer Correlations for B
Correlations for 2nd Virial Coefficientn(comb Eq 3.61 and 3.63)
BP 0 Pr 1 Pr
Z 1 1 B B
RT Tr Tr
Validity at low to moderate P Simple and recommended
Tr > Tr 3, there appears to Most accurate for

be no limitation on the P non-polar species

Virial Correlations (Cont.)
The simplest form of the virial
Z Z 0 Z1
equation :
Compare
BP BP P
Z 1 Z 1 c r
Pr Pr
RT RT T
c r Z 0 1 B 0 Z1 B 1
Tr Tr
2nd correlations, yields
BP c
B B 0 B1 2nd virial coefficients = f(T) only
RT c
B0 & B1 = f(Tr) only
0.422 0.172
Pr P B 0 0.083 B 1 0.0.139
Z 1 B 0 B1 r Tr1.6 Tr4.2
Tr Tr
Note: f, function Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Comparison of Correlation for Z0
Region above the dashed line
Points: Lee/ Kesler correlation
the 2-correlations differ by <2%
4.0
1.0
2.4
1.8
0.9
Z0
Tr = 0.8
0.9 1.0 1.1 1.5
0.8
1.3
0.7
0.0 0.5 1.0 1.5 2.0 2.5
Pr
Straight lines: virial-coefficient correlation

App. Validity of the Ideal-Gas Eqn.
10
Z0 = 1.02
1
Region where Z0 lines between
0.98 &1.02
Z0 = 0.98
0.1
Pr
Ideal-gas eqn. is a reasonable

0.01 approximation to reality
0.001
0 1 2 3 4
Tr

Generalized Correlations for
Liquid
3.5
Tr = 0.3
0.4
0.5
3.0 0.6
0.7
0.8
2.5 0.9
1.0
r Tr = 0.95
2.0
0.97
0.99
1.5
Saturated liquid
1.0
0 1 2 3 4 5 6 7 8 9 10
Pr

Molar Volume of Sat. Liquids
The generalized cubic equation of state low accuray
The Lee/Kesler correlation includes data for subcooled liquids

Suitable for non-polar & slightly polar fluids
Estimation of molar volumes of saturated liquids
Data required crirical conts. (App. B)

(1 Tr )0.2857
V sat
V Z
c c Results accurate 1 or 2%

Generalized Density Correlation
2-parameter corresponding-states correlation for estimation of liquid
volumes.
Vc
r
c V
Density at the critical point
Known volume
r1
Required volume V2 V1 Reduced densities
r2 read from next page
Give good results and requires only experimental data (usually

available).

Generalized Density Correlation (Cont.)
3.5
Tr = 0.3
0.4
0.5
3.0 0.6
0.7
0.8
2.5 0.9
1.0
r Tr = 0.95
2.0
0.97
0.99
1.5
Saturated liquid
1.0
0 1 2 3 4 5 6 7 8 9 10
Pr
Examples & Tutorials

Example 4 (Gases)
Determine the molar volume of n-butane at 510K and 25 bar by, (a) the
ideal-gas equation; (b) the generalized compressibility-factor correlation; (c)
the generalized virial-coefficient correlation.
Solution 4:
RT cm3
V V 1696.1
P mol
b) The generalized compressibility-factor correlation
510 25
Tr 1.200 Pr 0.659 0.200
425.1 37.96
Z 0 0.865 Z1 0.038 Z Z 0 Z1 0.873

Solution 4 (Cont.)
ZRT cm3
V 1480.7
P mol
c) The generalized virial-coefficient correlation
510 0.422 0.172

Tr 1.200 B 0 0.083 B 1 0.139
425.1 Tr1.6 Tr4.2
Pr P
Z 1 B 0 B1 r 0.879
Tr Tr
ZRT cm3
V 1489.1
P mol

Example 5 (Gases)
What pressure is generated when 1 (lb mol) of CH4 is stored in a
volume of 2 ft3 at 122 F using (a) the ideal-gas equation; (b) the
Redlich/Kwong equation; (c) a generalized correlation.
Solution 5:
RT 0.7302(122 459.67) P 212.4 atm

P
V 2
b) The RK equation
581.67 (T )R 2
Tc2 atm
Tr 1.695 a T r
453.94
343.1 Pc ft6
RT RT a(T)
b c 0.4781 ft3 P 187.49 atm
Pc V b V(V b)

Solution 5 (Cont.)
c) The generalized compressibility-factor correlation (high P)
ZRT Z(0.7302)( 122 459.67) P 212.4 Z atm

P
V 2
P Z
Pr P PcPr
45.4 0.2138
581.67
Tr 1.695
Z starts at Z0 = 1 343.1
Pr1 = 4.68
Pr Tr = 1.695
Table E.3 & E.4 Z0 & Z1
Z = Z0 + Z1 Converges Final Z P ZRT/V 189.0 atm

(Z = 0.890)
Example 6 (Gases)
A mass of 500 g of gases ammonia is contained in a 30000 cm3 vessel
immersed in a constant-temperature bath at 65 C. Calculate the pressure
of the gas by (a) the ideal-gas equation; (b) a generalized correlation .
Solution 6:
Vt cm3
V 1021.2
n mol
RT
P 27.53 bar
V

Solution 6 (Cont.)
c) The generalized virial-coefficient correlation (low P, Pr ~ 3 )
338.15 27.53
Tr 0.834 Pr ~ 0.244
405.7 112.8
0.422 0.172
B 0 0.083 B 1 0.139 0.253
Tr1.6 Tr4.2

Z 1 B 0 B1 PTr
1 0.541
Pr
Tr
r
ZRT
P 23.76 bar
V

Tutorial 3
Calculate the molar volume of saturated liquid and the molar volume of
saturated vapor by Redlich /Kwong equation fo one of the folowing and
compare results with values found by suitable generalized correlations.
a) Propane at 40 C where Psat = 13.71 bar

b) n-Butane at 100 C where Psat = 15.41 bar
Tutorial 4
The vapor-phase molar volume of a particular compound is reported as

23,000 cm3mol1 at 300 K and 1 bar. No other data are available. Without
ideal-gas behavior, determine a reasonable estimate of the molar
volume of the vapor at 300 K and 5 bar.

Example 7 (Liquid)
For ammonia at 310 K, estimate the density of (a) the saturated liquid; (b)
the liquid at 100 bar
Solution 7:
Apply the Rackett equation at the Tr
310
Tr 0.7641 Vc 72.47 Z c 0.242
405.7
(1 Tr )0.2857 cm3 Exp. = 29.14 cm3 mol1

V sat
V Z
c c 28.33 Compares
mol differs = 2.7%

Solution 7 (Cont.)
At 100 bar
100 310 r1 r1,310K, saturated liquid

Pr 0.887 Tr 0.7641 V2 V1 V 310K
112.8 405.7
Fig. 3.16 r2 r2 ,100bar
r 2.38
Exp. value
Vc cm3 2.34 cm3

V 30.45 V2 29.14 28.65
r mol 2.38 mol
Exp. = 29.14 cm3 mol1

differs = 6.5%

Tutorial 5
The specific volume of isobutane liquid at 300 K and 4 bar is 1.824 cm3
g1. Estimate the specific volume at 415 k and 75 bar.
Tutorial 6
The density of liquid n-pentane is 0.630 g cm3 at 18 C and 1 bar.

Estimate its density at 140 C and 120 bar.
Tutorial 7
Estimate the volume change of vaporization for ammonia at 20 C. At

this temperature the vapor pressure of ammonia is 857 kPa.

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CHAPTER 3

Volumetric Properties of Pure

Norhaniza binti Yusof

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Volumetric properties from equations of Calculate the volumetric

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Introduction to volumetric properties

PVT behaviour of pure substances

Volumetric properties from equations of state

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

the system species

Single-phase (sat.) Subcritical T

Constant temperature line

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Generally, if the system is at any T or P;

Condition T and P Phase

T < Tc and P > Pc Liquid

T < Tc and P < Pc See boiling point T > Tbpt Gas

T < Tc and P < Pc See boiling point T < Tbpt Liquid

T < Tc and P < Pc See boiling point T = Tbpt 2-phase (saturated)

E.g.: Antoine equation for H2O;

log10 P (mmHg) = 7.96681 1668.21 / (T oC + 228)

Liquid phase: V is almost stable and not depend on P and T.

Gas phase: V of pure substance is depend on T and P.

Mathematic relations between P, V, T of pure substance is called as

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

f (P, V, T ) = 0 PVT equation of state (EoS)

Simplest EoS ideal gas law

Valid for low P

To solve the equation,

V = f (P, T) V = V (P, T) Hence,

For liquid phase

and are very small ( 0).

Ideal gas Non-ideal gas

PV = ZRT Equations of state (from PVT

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Vapor & Liquid &

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

There are 2 types of virial equations / virial expansions :

Note: T, temperature Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

High P up to 50 bar (below the Pc)

For ideal gas interaction molecular is assume not existed.

PV = ZRT (low P only)

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Internal energy of a REAL GAS is a function of P & T

P dependency is the result of forces between the

U = U(T) (Ideal gas)

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Enthalpy (H) is a func. of T only

Heat capacity at constant P (CP) is a func. of T only

Relation between CP and CV

These equations may be applied to the following processes

Isobaric process: U C v dT H C pdT

Isochoric process: U C v dT H C pdT

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Equations Other expressions

W U C v dT C v T The process should be mechanically

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

One mol of an ideal gas with Cp = (7/2)R and Cv = (5/2)R expands

Assuming mechanical reversibility, calculate W, Q, U, and H for

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Reported values for the virial coefficients of isopropanol vapor at