Volumetric Properties of Pure Substance: Dire Dawa Institute of Technology School of Chemical & Bio-Engineering

Volumetric properties of pure
substance
Lecture 7
1
School of Chemical & Bio- Engineering Dire Dawa Institute of Technology
Aim
Estimating values of Q and W for processes:

• Use laws of thermodynamics (1st and 2nd ) to relate Q &W to change of
properties (e.g., U –based on 1st law)
Relate U to measurable property parameters such as P-v-T.
•Estimate/determine the unknown measurable parameter from PvT

• Use experimental data or tabulated data for PvT
• Apply EOS to predict the unknown value
Finally, calculation of Q and W (process parameters or path dependent

parameters)
2
School of Chemical & Bio- Engineering © Yinebeb Dire Dawa Institute of Technology
i. Qualitative PvT behavior of pure substances
 The TD state of pure substance can be described in terms of two

independent properties; i.e., only two of the P, V and T are
independent.
 Phase rule: F = 2 -  + C; for pure substance C=1 and F= 3 - 
 State of matter: solid, liquid, and gas

i. Solid phase:
• The molecules are arranged in a three-dimensional
pattern (lattice) that is repeated throughout.
• Strong intermolecular forces;
• The molecules cannot move relative to each
other but continually oscillate about their
equilibrium position.
• Shape and volume do not change without
exchange of energy
3
ii. Liquid phase:

• The molecular spacing in the liquid phase is not much
different from that of the solid phase, except the molecules
are no longer at fixed positions relative to each other and
they can rotate and translate freely.

• The intermolecular forces are weaker
relative to solids.
• Volume do not change, shape can change
without exchange of energy.
iii. Gas phase:

• Very small intermolecular so that molecules move randomly,
colliding with each other and the walls of the container.
• Molecules are at a higher energy level than
they are in the liquid or solid phases.
• Both volume and shape can change without
exchange of energy.
4
 At certain condition a substance at equilibrium may exhibit only one
of the 3 possible states or more than one.
 Vapor pressure:
• microscopic view:
Evaporation
Molecules can escape
only from surface.
Boiling
Vapor Pressure: Pressure exerted by vapor
Molecules phase
can escape (on
from
container or liquid phase) at equilibrium with liquid.
bulk leads to formation of
bubbles inside bulk of liquid 5
 Vapor pressure:
• microscopic view:
Vacuum
760 mm
PB = PA
for Hg
Vapor pressure
10 mm
760 mm
6
 Vapor pressure:
• Consider situation where substance is present in two states and
one of the two states is vapor.
Case I: One phase is vapor and other is liquid
• Some of the substance in liquid phase has tendency to
move to vapor Phase (evaporation)
also
• Some of the substance in vapor phase has tendency to
move to liquid Phase (condensation)
• Mismatch in the above two tendencies  net transfer of material
from one phase to the other
• Transfer will result in evening the mismatch in the two tendencies
An arrangement of material in the two phase occurs where after there’s
no net transport of substance from one phase to other: Equilibrium/
Phase Equilibrium / V-L phase equilibrium. 7
• System exerts fixed pressure that depends only on T and nature of

substance and is called Vapor pressure
Case II: One phase is vapor and other is solid
• Some of the substance in solid phase has tendency to move to
vapor Phase (sublimation)
also
• Some of the substance in vapor phase has tendency to move to
solid Phase (condensation)
• Mismatch in the two tendencies  net transfer of material from
one phase to the other
• Transfer will result in evening the mismatch in the two tendencies
An arrangement of material in the two phase occurs where after there’s
no net transport of substance from one phase to other: Equilibrium/
Phase Equilibrium/ S-V phase equilibrium/ 8
• System exerts fixed pressure that depends only on T and nature of

substance and is called Vapor pressure
• phase diagrams:
 Variables of interest: P, V & T
 Complete representation: 3-Dimension (T, V & P) space
P-v-T surface of a substance that contracts on

P-v-T surface of a substance that contracts on freezing. freezing. 9
• phase diagrams:
• Ease in comprehension: Two dimension space – One of the three variables
value is fixed
• P-V diagram (Temperature fixed)
• T-V diagram (Pressure fixed)
• P-T diagram (Total volume fixed)
P
T
P
T
V T
V
10
• P-T diagram:
 For some combination of values of P,
V & T, system in a single phase Fusion curve
F = 2; Given V, T & P both can vary
Liquid
 For some combination of values of P Solid Vaporization
P, V & T, system can exist in two curve
phases: F = 1
Sublimation curve
Vapor/Gas
Triple Point
T
 For some combination of values of P, V & T, system
can exist in three phases: F = 0 i.e., only a fixed triplet
of T, V & P values: Triple Point 11
• P-T diagram:
 Liquid: Reduction in P and constant
T - vaporization
 Gas: Reduction in T and constant P - Pc c
Liq
condensation
P Solid
 Vaporization curve doesn’t extend
indefinitely. Ends at critical point ‘c’ Vaporization
curve
Vap
T Tc
Neither of the above two phenomena occurs
beyond the two dashed lines: fluid region
12
• P-T diagram:
Gas region divided into two
sub-regions: P c
Liq c
a.Vapor – Condensation
P Solid
can occur both by Vaporization
curve
increasing in P at
constant T & also by Vap
reduction in T at T T c
at constant P (gas region with T < Tc)

b. Supercritical: Region with T > Tc, including
13
the fluid region
Solid/Liquid Subcooled
Saturated
• P-V diagram: Liquid
c
P-T diagram: Phase
boundary – curves Superheated
Saturated
P
Vapor
P-V diagram: Phase Tc
Liquid/Vapor TA
boundary – area Solid
Solid/Vapor
V
Fixed mass of system: distributes in two phases
– various points corresponds to different fraction
of mass in the two phases 14
Solid/Liquid Subcooled
Saturated
Liquid
c
Saturated
Superheated
P
Vapor
Tc
Liquid/Vapor TA
Solid
Critical isotherm:
Solid/Vapor
Horizontal inflection point
V
at ‘c’
 P    2P 
  0  2   0
 V  Tc  V  Tc 15
i. Qualitative PvT behavior of pure substances-summary
•The pressure at which the liquid–vapor transition or solid–vapor transition occurs is

called the vapor pressure. Vapor pressure increases with increasing temperature.
•There is a unique temperature and pressure at which the solid, liquid, and vapor
states can all exist in equilibrium with each other. This is called the triple point.
•There is a unique temperature above which no liquid phase occurs regardless of
pressure. This is called the critical temperature (TC).
•There is a unique pressure above which no vapor phase occurs regardless of
temperature. This is called the critical pressure (PC).
•A material that is both above the critical pressure and above the critical temperature
is called a supercritical fluid.
•A vapor that is at a boiling point is called a saturated vapor, and a liquid that is at a
boiling point is called a saturated liquid.
•A vapor that is at a temperature above its boiling point is called a superheated vapor.
•A liquid that is at a temperature below its boiling point is called a subcooled liquid.
•A liquid that is at a pressure above its vapor pressure is called a compressed liquid.
16
ii. Eos for pure substances
a. Single Phase Region

F = 2  f(P,V,T) = 0
Considering V as fn. of T & P: V = V(T,P)
 V   V 
dV    dT    dP
 T  P  P  T
D1  V 
Volume expansivity:   
V  T  P
1  V  D
Isothermal compressibility:     
V  P  T
17
Useful for liquid phase because both  and 

remain nearly constant for wide range of
T & P values
dV
  dT  dP
V
18
For liquid acetone at 20 0C and 1 bar

  1.487  103 o C   62 106 bar 1
V  1.287 cm 3 - g
For acetone find

a. The value of  P / T  V
b. The pressure generated by heating at
constant volume from 20 0C and 1 bar to
30 0C.
c. The change in volume for a change from
20 0C and 1 bar to 00C and 10 bar
19
b. EOS for Gas:

• characteristics of ideal gas:
• The gas molecules have zero volume.
• The particles are in constant motion, and collisions are
perfectly elastic.
• There are no intermolecular attractions or repulsions
between the molecules.
20
P-V diagram: PV along an Isotherm in

c
vapor region may be expressed in the
function of P by a power series:
PV  a  bP  cP  ... 2 P
Or if b  aB’, c  aC’ : TB

PV  a 1  B / P  C / P 2  ...  TA
It is called virial EOS

• b, c, … and so B/, C/ are fn. of T and species V
•In practice only finite number of terms are used;
•‘a’ is fn. only of temperature i.e., at a given T, it has same
value for all species. 21
Experimental data of PV as function of P for different

gases at constant T H2
PV N2
Limiting value of
(PV) as P  0 Air
same for all gases
O2
Lim P  0(PV) or (PV)*:
independent of gas, 0 P
depends only on T
In Virial eqn., put P = 0
 PV   a  f (T )
*
22
• Can be used to build a Temperature

scale which is independent of any PV N2
material property:
• Simplest form of f(T) is: Air
 PV  *
 a  RT O2
Where, R is a constant
0 P
• Value of 273.16 K is value assigned to triple point of water
 PV  *
t  R  273.16 K
 PV  *
At any other T (in Kelvin): T  273.16
 PV  *t
23
• Establishes Kelvin temperature scale through the temperature

range for which values of (PV)* experimentally accessible .
• AS(PV)t* extrapolated to the zero-pressure state, and

the value is: (PV)t*= 22711.8 cm3 bar mol-1
Hence, R
 PV  *
t
 83.1447 cm 3 bar mol 1 K 1
273.16
As P0, gas behaves as ideal gas,

 scale is called ideal-gas temperature scale
24
PV D
Compressibility factor (Z): Z 
RT
For ideal gas: Z  1
Virial EOS: PV  a 1  B P  C P  ...

/ / 2
& Using a = RT and Z = PV/(RT)

Z  1  B P  C P  ...
/ / 2
25
An alternative expression of Z also in common use is

B C
Z  1   2  ...
V V
B/, C/, … and B, C, … are known as virial coefficient
B/, C/, … and B, C, … are related as

B C  B 2
B/  ; C/ 
RT  RT  2
Above relations holds strictly for infinite series but
are used for truncated expansions also
26
Virial EOS has firm basis in theory; physical

significance can be assigned to terms
B/V: Interaction between pairs of molecules
C/V2: Three-body interaction
27
Two-body i/a is much more common than

three-body i/a
Three-body i/a are much more common than
four body i/a
Suggests that
B/V >> C/V2 >> D/V3 >> …
Virial EOS converges rapidly, only first few
terms of the series is required.
28
Experimental data: isotherm (Z v/s P)

Start at Z = 1 (for P=0) and are nearly
straight line for low to moderate pressure
(upto 5 bars, subcritical T)
Suggests following approximation
Z  1  B P  C P  ...  1 B P
/ / 2 /
B
A common form of this eqn. is (using B/ 
RT
)
PV BP
Z 1 (1)
RT RT 29
Similarly, virial volume expansion form may

also be truncated to two terms for low P
PV B
Z  1 (2)
RT V
Eqn. (1) is at least as accurate as Eqn. (2) and

more convenient to use
 for low P if two terms are being use than

Eqn.(1) is preferred
30
For P > 5 bars but below critical point

Expansion to three terms often provide
acceptable accuracy
However, in this regime volume expansion
form is more accurate
PV B C
Z  1  2 (1)
RT V V
Virial coefficient beyond C are rarely known
 Eqn. with more than three terms are not used
31
Reported values of virial coefficient for

isopropanol at 200 0C are
B  388 cm - mol 3 -1
& C  - 26000 cm - mol 6 -2
Calculate V and Z for isopropanol vapor at 200 0C

and 10 bar by
a. The ideal gas equation
b. Two term virial pressure expansion
c. Three term virial volume expansion
32
Solution:
Absolute temperature: T = 273.15 + 200
= 473.15 K
R = 83.14 cm3 bar mol-1 K-1
(a) For an ideal gas

Z 1
and V  RT   83.14 473.15  3934 cm3mol 1
P 10
33
PV BP
Solution: (b) Z  1
RT RT
RT
V B  3934  388  3546 cm3 mol-1
P
B C
(c) Z  1  2 can be written as
V V
RT  B C 
Vi 1  1   2 
P  Vi Vi 
i denotes iteration number

34
i = 0, V0 = 3934 (ideal gas value)

 388 26000 

V1  39341     3539
2 
 3934  3934 
 388 26000 
V2  39341     3495
2 
 3539  3539 
Continue iterating till Vi+1 – Vi is insignificant

(less than 1%)
After i = 5, the final value obtained is
V1  3488
35

Volumetric Properties of Pure Substance: Dire Dawa Institute of Technology School of Chemical & Bio-Engineering

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Volumetric Properties of Pure Substance: Dire Dawa Institute of Technology School of Chemical & Bio-Engineering

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Volumetric properties of pure

Estimating values of Q and W for processes:

Relate U to measurable property parameters such as P-v-T.

•Estimate/determine the unknown measurable parameter from PvT

Finally, calculation of Q and W (process parameters or path dependent

 The TD state of pure substance can be described in terms of two

 Phase rule: F = 2 -  + C; for pure substance C=1 and F= 3 - 

 State of matter: solid, liquid, and gas

ii. Liquid phase:

iii. Gas phase:

• System exerts fixed pressure that depends only on T and nature of

• System exerts fixed pressure that depends only on T and nature of

P-v-T surface of a substance that contracts on

at constant P (gas region with T < Tc)

•The pressure at which the liquid–vapor transition or solid–vapor transition occurs is

a. Single Phase Region

Useful for liquid phase because both  and 

For liquid acetone at 20 0C and 1 bar

For acetone find

b. EOS for Gas:

P-V diagram: PV along an Isotherm in

It is called virial EOS

Experimental data of PV as function of P for different

• Can be used to build a Temperature

• Establishes Kelvin temperature scale through the temperature

• AS(PV)t* extrapolated to the zero-pressure state, and

As P0, gas behaves as ideal gas,

Virial EOS: PV  a 1  B P  C P  ...

& Using a = RT and Z = PV/(RT)

An alternative expression of Z also in common use is

B/, C/, … and B, C, … are known as virial coefficient

B/, C/, … and B, C, … are related as

Virial EOS has firm basis in theory; physical

B/V: Interaction between pairs of molecules

C/V2: Three-body interaction

Two-body i/a is much more common than

Experimental data: isotherm (Z v/s P)

Similarly, virial volume expansion form may

Eqn. (1) is at least as accurate as Eqn. (2) and

 for low P if two terms are being use than

For P > 5 bars but below critical point

Reported values of virial coefficient for

Calculate V and Z for isopropanol vapor at 200 0C

R = 83.14 cm3 bar mol-1 K-1

(a) For an ideal gas

i denotes iteration number

i = 0, V0 = 3934 (ideal gas value)

Continue iterating till Vi+1 – Vi is insignificant

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