02 Chapter 03 Compiled

N02 2-6, 11.00 1.00P.
Feb 17, 2013 (Mon)
CHAPTER 3
Volumetric Properties of Pure
Fluids: Part 1
Mohd Asmadi Bin Mohammed Yussuf

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Topic Outcomes
Week
2-3
Topic
Volumetric Properties of Pure Fluids
Topic Outcomes
It is expected that students are
able to:
Introduction to volumetric properties

PVT behaviour of pure substances
Determine the state/phase of a

given fluid at given conditions.
the
volumetric
Volumetric properties from equations of Calculate
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
limitation of every equation of
Volumetric properties from generalized
correlations:
state.
o Gases
o Liquid
the
volumetric
Determine
properties from thermodynamic
properties
from
tables and diagrams.
Volumetric
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
PT Diagram for Pure Substances

Fliq = 2
(divariant)
Pressure
Pc
Fusion curve
Fluid region
A
Liquid region C
DOF
for
the system
Vaporization
curve
Solid region
Gas region
Ftp = 0
(invariant)
Fvap. curve = 1
(univariant)
Triple Vapor
2
point region
Sublimation
curve
Temperature
Note: DOF, degree of freedom
Supercritical
T > Tc
No.
of
species
F=2+N
Independent
variables (T, P)
No. of
phases
Tc
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.)
liqs. at boiling T
Note: Sol., solid; liq., liquid; vap., vapor; sat., saturated; cond., condensation; T, temperature
Subcritical T
consist of 3 segments
PVT Surface for a Real Substance

P
CP
CP
Solid
Liquid
Gas
Vapor
T
Triple line
V
Note: CP., critical point
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 :
Antoine equation
Cox Chart
logPsat A
B
TC
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
PV = RT
Valid for low P

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
Example
V = V (P, T)
V = f (P, T)
Partial derivative in the equation
V
V
dT
dP
T P
P T
dV
Divide by V
Volume expansivity,
dV 1 V
1 V

dT
dP
V V T P
V P T
Hence,
dV
dT dP
V
Integration
ln
V2
T2 T1 P2 P1
V1
For liquid phase

incompressible fluid
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
Ideal Gas
Equation
Virial
Equation
Cubic
Equation
of State
Van Der
Waals
Redlich/
Kwong
Redlich/
Kwong/
Soave
Peng/
Robinson
Generic
Vapor &
Vapor-Like
Roots
Liquid &
Liquid-Like
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
B
RT
C B
RT 2
D 3BC 2B2
D
RT 3
PV
Z
1 BP CP 2 DP 2
RT
B, C, D, B, C, D etc.
virial coefficients
PV
B C
D
Z
1 2 3 ....
RT
V V
V
Only depend on T.
Obtained from PVT data.
Note: T, temperature
Application of the Virial Equations

CH4
Low to moderate P (P < 15 bar)
2 terms
PV
1 BP
RT
Z 1
BP
RT
High P up to 50 bar (below the Pc)

Truncated to 3 terms
PV
1 BP CP 2
RT
Note: P, pressure; Pc, critical pressure
Z 1
B C
2
V V
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
Cv
dU
C v T
dT
dU C vdT
U C vdT
Enthalpy (H) is a func. of T only

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

dH
H
Cp T

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

Cp
dH dU
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 vdT
dQ C vdT PdV
dW PdV
RT
V
dQ C vdT RT
dW RT
dV
V
dV
V
RT
P
dQ C pdT RT
dP
P
dW RdT RT
dP
P
dQ
PV
R
Cv
Cp
dT
PdV
R
R
dW PdV
These equations may be applied to the following processes

Adiabatic Process
Isothermal process: U H 0
Q W RTln
Isobaric process:
Isochoric process:
V2
P
RTln 2
V1
P1
U C vdT
H C pdT
Q H C pdT
W R T2 T1
U C vdT
H C pdT
Q U C vdT
W0
Adiabatic Process (Const. Heat Capacities)

Equations
Other expressions
TV 1 constant
TP
1 /
constant
PV constant
Cp
Cv
P1V1
W
1
P2
P
1
1 /
RT
1 1
1
P2
P
1
1 /
Work
W U C vdT C vT
The process should be mechanically

reversible!
Alternative forms
W
RT2 RT1 P2V2 P1V1
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:
a)
Where
Z 1
B C
V V2
B
B
RT
b)
PV
1 BP CP 2
RT
C B2
C
RT 2
N02 2-6, 11.00 1.00P.M
Feb 17, 2013 (Mon)
CHAPTER 3
Fluids: Part 2

Scope of Lecture
Cubic equation of state

Generic cubic
Example & Tutorial
Cubic Equation of State
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
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 :
RTc
b
8Pc
27R2Tc2
a
64Pc
RTc 3 a
ab
V b
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
Van Der
Waals
Redlich/
Kwong
Redlich/
Kwong/
Soave
Peng/
Robinson
Generic
Vapor &
Vapor-Like
Roots
Liquid &
Liquid-Like
Roots
van der Waals

=a
=b
RT
V
V b V b V 2 V
A Generic Cubic EoS

(previous slide)
==0
Reduces to van
der Waals EoS
RT
a
P
2
V b V
Note: EoS; equation of state
RTc
b
8Pc
Will be
discussed later
27R2Tc2
a
64Pc
Redlich/Kwong
R 2Tc2
R 2Tc2
a
0.42748
Pc
Pc
Equation,
a Tr Tr-1/2
RT
a T
P
V b V V b
RT
a
0.5
V b Tr V b V
b
1.5
0.5 2
ab
RT 2 a RT b PT b
V
V
0.5
0.5
PT
PT
P
RTc
RT
0.08664 c
Pc
Pc
Solve by cubic
equation solver.
V for Gas & Liquid Phases (RK)

V for liquid phase
V for gas phase
RT
a T
V b V V b
V b
P
a
ab
RT 2 2 bRT
0.5 V
0
V b
0.5
P
PT
PT
P
V3
Multiple &
rearrange
V b
RT
a V b
0.5
P T PV V b
ab
RT 2
V
i
P
PT 0.5
bRT
a
b2
0.5
P
PT
RT
a V b
Vi1
b 0.5 i
P
T PVi Vi b
Vi1
Vi
Solve by iteration method, use b as an initial Vo.

Note: RK, Redlich/Kwong
Redlich-Kwong-Soave & Peng-Robinson

Peng-Robinson
Redlich-Kwong-Soave
RT
a
P
V b V b V
1 S 1 Tr0.5
S 0.48508 1.55171 0.156132

Acentric factor (App. B)
RT
a
V b V V b b V b
S 0.37464 1.54226 0.269922
R 2Tc2
a 0.45724
Pc
R 2Tc2
b 0.07780
Pc
Parameters for all Cubic Equation of State
EoS
a( Tr)
Zc
1/8
27/64
3/8
0.08664
0.42748
1/3
0008664
0.42748
1/3
0.07779
0.45724
0.30740
van der Waals

Redlich/ Kwong
Redlich-KwongSoave
Peng-Robinson
1
2
Tr
SRK Tr ;
PR Tr ;
2 1
SRK Tr ; 1 0.48508 1.574 0.1762 1 Tr1/2
PR Tr ; 1 0.37464 1.54226 0.269922 1 Tr1/2
Note: Please text book p. 98
Generic Cubic
Vapor & Vapor-Like Roots of the Generic Cubic EoS
RT
a T
V b
b
P
P V b V 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
RT
a T
V b
b
P
P V b V b
substitute
ZRT
V
P
2 dimensionless quantities leads to simplification

RT
b c
Pc
R 2Tc2
a Tc
Pc
bP
P
r
RT
Tr
a T Tr
bRT
Tr
Determination of Z
Therefore,
Z 1 q
Z
Z Z
Iteration
Start with Z = 1
Calculated Z
Substituted on the right side.
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 :
V
RT
a T
V b
b
P
P V b V b
RT bP VP
a T
V b V b V b
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
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
V b V b V b
Tr R 2Tc2
a T
Pc
& are pure numbers
RT
b c
Pc
a(T) is specific to each EoS
same for all substances
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 ) :
P
0
V Tc
2P
0
2
Tc
Replace Pc, Tc and Vc

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

3 0
2
V b V
V T
2P
2RT
6a
0
3
2
4
V
V
T
Then,
27R2Tc2
a
64Pc
RTc
8Pc
EoS Parameters (Cont.)

An analogous procedure may be applied to the generic cubic
equation
RT
a T
V b V b V b
Previous slide
Yielding expressions for parameters
a Tc
2
c
R T
Pc
RTc
Pc
and
Pure numbers,
Independent of substance
Determined for a particular EoS
from the values assigned to &
EoS Parameters (Cont.)

R 2Tc2
a Tc
Pc
This result may be extended to T other than the critical by
Introduction of a dimensionless function
Tr R 2Tc2
a Tc
Pc
unity at the Tc
Function (Tr) : an empirical expression

specific to a particular equation of state.
Note: Tc; critical temperature
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 .
Tr
T
Tc
Pr
P
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
N29, DP1, 12.00 1.00P.M
Feb 20, 2013 (Thu)
CHAPTER 3
Fluids: Part 3

Scope of Lecture
Generalized Correlations for Gases
Compressibility factor, Z
2nd virial coefficient, B
Generalized Correlations for Liquids

Examples & Tutorials
Generalized Correlations for

Gases
Pitzer Correlations for the Z

The correlation for Z takes form :
Equally suitable for
gases & liquids
Z Z0 Z1
Where Z0 and Z1 are functions of both Tr and Pr .

From Table E1E4, require interpolation, see App. F
Error
Non-polar/slightly polar
Highly polar
< 2-3%
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
Gases
Tr = 0.7
0.8
0.9
Z0
1.5
1.2
0.6
1.0
Two-phase
region
0.4
C
0.9
0.2
0
Compressed
liquids (Tr < 1.0)
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
Tc K
43.6
21.8
1
2.016T
Pc bar
20.5
44.2
1
2.016T
Vc cm3mol1
51.5
9.91
1
2.016T
T = absolute temperature in K
Pitzer Correlations for B

Correlations
BP
0 Pr
1 Pr
Z 1
1 B
B
RT
Tr
Tr
Validity at low to moderate P
Tr > Tr 3, there appears to

be no limitation on the P
Simple and recommended
Most accurate for

non-polar species
Virial Correlations (Cont.)

The simplest form of the virial
equation :
Z Z0 Z1
Compare
BP P
c r
Z 1
RT T
c r
BP
Z 1
RT
Z0 1 B0
Pr
Tr
Z1 B1
Pr
Tr
2nd correlations, yields
BPc
B0 B1
RTc
Z 1 B0
Note: f, function
Pr
P
B1 r
Tr
Tr
2nd virial coefficients = f(T) only

B0 & B1 = f(Tr) only
B0 0.083
0.422
Tr1.6
B1 0.0.139
0.172
Tr4.2
Comparison of Correlation for Z0

Region above the dashed line
the 2-correlations differ by <2%
Points: Lee/ Kesler correlation

4.0
1.0
2.4
1.8
0.9
Z0
Tr = 0.8
0.9 1.0 1.1
0.8
1.5
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
Pr
Region where Z0 lines between

0.98 &1.02
Z0 = 0.98
0.1
Ideal-gas eqn. is a reasonable

approximation to reality
0.01
0.001
2
Tr
Generalized Correlations for

Liquid
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
0.2857
V sat Vc Z(1c Tr )
Data required crirical conts. (App. B)

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
Required volume
V2 V1
r1
r2
Reduced
densities
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
0.6
0.7
0.8
0.9
1.0
3.0
2.5
Tr = 0.95
2.0
0.97
0.99
1.5
Saturated liquid
1.0
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
V
P
cm3
V 1696.1
mol
b) The generalized compressibility-factor correlation

Tr
510
1.200
425.1
Pr
25
0.659
37.96
Z0 0.865 Z1 0.038
0.200
Z Z0 Z1 0.873
Solution 4 (Cont.)
ZRT
cm3
V
1480.7
P
mol
c) The generalized virial-coefficient correlation
Tr
510
1.200
425.1
B0 0.083
Z 1 B0
0.422
Tr1.6
B1 0.139
0.172
Tr4.2
Pr
P
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:
P
RT 0.7302(122 459.67)
V
2
P 212.4atm
b) The RK equation
581.67
Tr
1.695
343.1
(T r )R
a T
Pc
RT
b c 0.4781ft3
Pc
Tc2
453.94
atm
ft6
RT
a(T)
187.49atm
V b V(V b)
Solution 5 (Cont.)
c) The generalized compressibility-factor correlation (high P)
P
ZRT Z(0.7302)( 122 459.67)
V
2
Pr
P
Z
45.4 0.2138
Z starts at Z0 = 1
P PcPr
Tr
581.67
1.695
343.1
Pr1 = 4.68
Pr
Tr = 1.695
Table E.3 & E.4
Z0 & Z 1
Z = Z0 + Z1
P 212.4 Z atm
Converges
Final Z
P ZRT/V 189.0atm
(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
27.53bar
V
Solution 6 (Cont.)
c) The generalized virial-coefficient correlation (low P, Pr ~ 3 )
Tr
338.15
0.834
405.7
B0 0.083
0.422
Tr1.6
27.53
Pr ~
0.244
112.8
B1 0.139
Z 1 B0 B1
PT
r
r
0.172
Tr4.2
0.253
P
1 0.541 r
Tr
ZRT
23.76bar
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
Tr
310
0.7641
405.7
sat
(1 Tr )0.2857
c c
VZ
Vc 72.47
cm3
28.33
mol
Compares
Zc 0.242
Exp. = 29.14 cm3 mol1

differs = 2.7%
Solution 7 (Cont.)
At 100 bar
r 2.38
Fig.
3.16
310
100
0.7641
Pr
0.887 Tr
405.7
112.8
Vc
cm3
V
30.45
r
mol
V2 V1
r1
r2
310K
r1,310K,saturatedliquid
r2 ,100bar
Exp. value
2.34
cm3
V2 29.14
28.65
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.
Homework
Chapter 3 : 3.34, 3.35, 3.43, 3.45, 3.46,
Dateline
: Feb 27, 2014 (Thu)

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N02 2-6, 11.00 1.00P.

Feb 17, 2013 (Mon)

Mohd Asmadi Bin Mohammed Yussuf

Introduction to volumetric properties

Determine the state/phase of a

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Introduction to volumetric properties

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

PVT Behavior of Pure

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

PT Diagram for Pure Substances

Note: DOF, degree of freedom

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

PV Diagrams for Pure Substances

Liq., liq./vap. regions & vap. with isotherms

PVT Surface for a Real Substance

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

PVT Surface (Cont.)

Constant temperature line

Pure Substances Phase

T < Tc and P > Pc

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

Determination of Pure Substances Phase

E.g.: Antoine equation for H2O;

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

PVT equation of state (EoS)

Simplest EoS ideal gas law

Valid for low P

To solve the equation,

Note: P, pressure; EoS; equation of state

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Partial derivative in the equation

For liquid phase

Equations of state (from PVT

Valid at low pressure

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Virial Equations of State

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Virial Equations (Gas Phase)

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Application of the Virial Equations

High P up to 50 bar (below the Pc)

Note: P, pressure; Pc, critical pressure

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

The Ideal Gas

Term B/V arises on account of interactions between pairs of

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,

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia