SECTION 1

THERMODYNAMICS,
DATA METHODS
AND
TECHNICAL COMPUTING

1.1

THERMO, DATA METHODS & TECHNICAL COMPUTING

Basic data needs for design

Physical properties
Vapour-liquid equilibrium
Critical properties
Thermal properties
Transport properties
Chemical engineering references
Characteristics of petroleum streams
Computer methods
QUEST/DISTEX
PEGASYS
PROII/PROvision with EDL III

1.2

BASIC DATA NEEDS FOR DESIGN

First and most important use of physical properties is in
heat and material balance calculations
Uncertainties in data/predictions directly affect results
Three essential properties:
+ Vapour- liquid equilibria (VLE)
+ Enthalpy
+ Density (volume)

1.3

BASIC DATA NEEDS FOR DESIGN

(Continued)
Importance of VLE is due to importance of distillation
in separations
VLE includes vapour pressures
If separation by extraction, liquid - liquid equilibria become
important

Enthalpy includes heat capacity (specific heat), heat

of vaporisation, heat of mixing, heat of reaction
Transport properties (especially viscosity and thermal
conductivity) and surface tension are primarily used
in design of equipment

1.4

DENSITY AND PVT RELATIONSHIP

For vapor of known composition, knowing any two from set
(P,V,T) fixes the third
Usual problem: Given P and T, calculate (or V)
V = Volume, ft3/lb-mol (m3/kg-mol)
= 1/V = Molar Density, lb-mol/ft 3 (kg-mol/m3)

Often work in terms of compressibility factor, Z

Z = PV/RT
Z = Measure of deviation from PVT behavior of ideal gas
If P = psia, V = ft3/lb-mol, T = R R = 10.732
If P = kPa, V = m3/kg-mol, T = K R = 8.3145

1.5

SUMMARIZING PVT BEHAVIOR

Gases
Ideal gas as P 0, PV = RT
At low pressures, Z = PV/RT is approximately a linear function of P

Liquid
For T << Tc, V is almost constant for P < Pc
Density calculations: Blend specific gravity, not API gravity
API Gravity = 141.5 - 131.5
SG

1.6

THERMAL EXPANSION OF LIQUIDS

1.7
50
Vol. @ T
Vol. @ 15oC

Mol
ABP

500

Blue Book Section 8

1.0
0

15

250
o
C

500
1.7

VAPOUR - LIQUID EQUILIBRIA

Whenever a liquid and vapour exist in equilibrium, it is
possible to determine the composition of each phase
Vapour-Liquid-Equilibrium (V-L-E) relationships are the
basis for Bubble Point, Dew Point and Flash
calculations

1.8

LOW-PRESSURE VAPOUR-LIQUID EQUILIBRIA

Pressure: Generally under 200 psia (14 bara)
Simplest Case: Raoults Law
Non-ideal Liquid Solutions: Activity Coefficients
Real Vapour Mixtures: Fugacity Coefficients

1.9

IDEAL SYSTEM - EQUILIBRIUM CONSTANTS

Raoults Law:

pi = Pixi

pi - Partial Pressure of component i in the Vapor Phase

Pi - Vapor Pressure of component i @ the System Temperature

Daltons Law:

pi = Pyi
Pixi = Pyi
yi /xi = Pi/P = Ki

P
xi
yi
Ki

- Total System Pressure

- Molar fraction of i in Liquid Phase
- Molar fraction of i in Vapor Phase
- Equilibrium Constant

Ki = f(T,p)
Good up to about 4 atm for systems compromised of similar compounds

1.10

EXAMPLE: RAOULTS LAW BEHAVIOR

BENZENE (1) / TOLUENE (2)
1 10 00 00 0

PPreressssuurere, ,mmmm oof fHHgg

8 80 00 0
T To ot at al lP Pr er es ss su ur er e

6 60 00 0

P a r tia l P r e s s u r e o f
P a r tia l P r e s s u r e o f
B e n ze n e P 1
B e n ze n e P 1

4 40 00 0
P Pa ar tr itai al l P Pr er es ss su ur er e o of f
T To ol ul ue en ne e P P2 2

2 20 00 0

0 0. 0. 0

0 0. 2. 2

0 0. 4. 4

0 0. 6. 6

0 0. 8. 8

1 1. 0. 0

MM o ol el e F Fr ar ac ct itoi on n o of f B Be en nz ze en ne e
i ni n L Li qi qu ui di d P Ph ha as se e, , x xi i
B Ba as si si s: : P Pa ar tr itai al lP Pr er es ss su ur er e a an nd d T To ot at al lP Pr er es ss su ur er e a at t 9 90 0 C C

1.11

EXAMPLE: RAOULTS LAW BEHAVIOR

BENZENE (1) / TOLUENE (2)

tionn oof fBBeennzzeennee

MMoolele FFraracctio
inin VVaappoouur rPPhhaassee, ,yyi i

1 1. 0. 0

0 0. 8. 8
E E q qu ui lii lbi br ir ui umm L Li ni ne e
0 0. 6. 6

0 0. 4. 4

RR e ef ef er er en nc ce e L Li ni ne e x xi i = = y yi i

0 0. 2. 2

0 0. 0. 0

0 0. 2. 2

0 0. 4. 4

0 0. 6. 6

0 0. 8. 8

1 1. 0. 0

MM o ol el e F Fr ar ac ct it oi on n o of f B B e en nz ze en ne e
i ni n L Li qi qu ui di d P P h ha as se e, , x xi i

1.12

EXAMPLE: RAOULTS LAW BEHAVIOR

BENZENE (1) / TOLUENE (2)

Temperature,C
C
Temperature,

1 12 20 0

D De ew w P Po oi ni nt t C Cu ur vr ve e

1 11 10 0

V Va ap po ou ur r
1 10 00 0
L Li qi qu ui di d+ + V Va ap po ou ur r
9 90 0

B Bu ub bb bl el e P Po oi ni nt t C Cu ur vr ve e
L Li qi qu ui di d

8 80 0

0 0. 0. 0

0 0. 2. 2

0 0. 4. 4

0 0. 6. 6

0 0. 8. 8

1 1. 0. 0

MM o ol el e F Fr ar ac ct itoi on n o of f B Be en nz ze en ne e x xi , i , y yi i

1.13

BUBBLE POINT EQUILIBRIA

Convert Liquid Stream Composition to Mole Fraction
Assume Temperature or Pressure:
If P is Fixed, Guess T
If T is Fixed, Guess P

Trial - and - Error Solution:

If P is Fixed, Find T at which yi = Kixi = 1.0
If T is Fixed, Find P at which yi = Kixi = 1.0

1.14

BUBBLE POINT CALCULATIONS

USING IDEAL GAS LAW
Example: Find the bubble point temperature at 828 kPa for mixture of C3, iC4, & nC4
that has liquid mole fractions 0.0133, 0.9516 & 0.0351, respectively

Vapour Pressure kPa:

Component

Vapour Pressure
of i at
25C

Vapour Pressure
of i at
50C

Vapour Pressure
of i at
75C

Vapour Pressure
of i at

100C

C3

970

1750

2900

4600

iC4

350

700

1200

1970

nC4

240

500

930

1550

1.15

BUBBLE POINT CALCULATIONS

USING GAS LAW (Continued)

Ki = Pi/Ptot at System temperature

Component

C3
iC4
nC5

Ki
of i at
25C

Ki
of i at
50C

Ki
of i at
75C

Ki
of i at
100C

1.1715

2.1135

3.5024

5.5556

0.4227

0.8454
0.2899

1.4493
0.6039

2.3792
1.1232

1.8720

1.16

BUBBLE POINT CALCULATIONS

USING GAS LAW (Continued)
Yi = Xi*Ki @ system temperature

Component

Liquid molar
fraction

Yi@
25C

Yi@
50C

Yi@
75C

Yi@
100C

C3

0.0133

0.0156

0.0281

0.0466

0.0739

iC4

0.9516

0.4022

0.8045

1.3791

2.2641

nC5

0.0351

0.0102

0.0212

0.0394

0.0657

Total

1.0000

0.4280

0.8538

1.4651

2.4037

Using Linear interpolation:

Using rigorous method:

Bubble point = 56C

EDL III
= 58C

1.17

DEW POINT EQUILIBRIA

Convert Vapour Stream Composition to Mole Fraction
Assume Temperature or Pressure:
If P is Fixed, Guess T
If T is Fixed, Guess P

Trial-and-Error Solution:
If P is Fixed, Find T at which xi = yi/Ki = 1.0
If T is Fixed, Find P at which xi = yi/Ki = 1.0

1.18

DEW POINT CALCULATIONS

USING IDEAL GAS LAW
Example: Find the dew point temperature at 910 kPa for mixture of iC4, nC4, and
iC5 that has vapour mole fractions 0.459, 0.5393 and 0.0017, respectively.

Vapour Pressure kPa:

Component

Vapour Pressure
of i at
25C

Vapour Pressure
of i at
50C

Vapour Pressure
of i at
75C

Vapour Pressure
of i at
100C

iC4

350

700

1200

1970

nC4

240

500

930

1550

iC5

92

205

410

730

1.19

DEW POINT CALCULATIONS

USING IDEAL GAS LAW - CONTINUED

Ki = Pi/Ptot at System temperature

Ki
of i at
25C

Ki
of i at
50C

Ki
of i at
75C

Ki
of i at
100C

iC4

0.3846

0.7692

1.3187

2.1648

nC4

0.2637

0.5495

1.0220

1.7033

iC5

0.1011

0.2253

0.4505

0.8022

Component

1.20

DEW POINT CALCULATIONS

USING IDEAL GAS LAW - CONTINUED
Xi = Yi/Ki @ system temperature
Component

Vapour molar
fraction = 1

Xi@
25C

Xi@
50C

Xi@
75C

Xi@
100C

iC4

0.4590

1.1934

0.5967

0.3481

0.2120

nC4

0.5393

2.0448

0.9815

0.5277

0.3166

nC5

0.0017

0.0168

0.0075

0.0038

0.0021

Total

1.0000

3.2551

1.5858

0.8796

0.5308

Using linear interpolation:

Using rigorous method:

Dew point = 71C

EDL III
= 70C

1.21

NON - IDEAL SYSTEMS

Activity coefficient corrects for non-ideal liquid
solutions
Necessary in calculations involving Polar Compounds
(e.g. sour water strippers)

Equilibrium constants for non-ideal vapor phase are

obtained from a variety of computerized correlations
in EDL III, e.g.
DCUBEOS
FUGLIQ
NRTLVLE

1.22

CHARACTERIZATION FACTOR
An index of chemical character:

K=

(Tb)
SG

1/3

K - Characterization Factor
Tb - Absolute Boiling Point in R (1.8 * K)
SG - Specific Gravity, 60F(15C)

Applies to entire boiling point range of the crude

Use to get specific gravity of petroleum fractions (cuts)
Use to get specific heat of petroleum fractions
1.23

CHARACTERIZATION FACTOR (Continued)

Petroleum fractions:
10 < K < 15
K = 10, highly aromatic
K = 15, paraffinic

Crudes:
10.5 < K < 12.9
K = 10.5, highly aromatic
K = 12.9, highly paraffinic

1.24

CRITICAL PROPERTIES
Our Primary Use
Compressibility of Gases
Correlations for Equilibrium Constants

True-Critical - for Pure Compounds

Pseudo-Critical - for Mixtures
Used as Correlating Parameters

1.25

CRITICAL PROPERTIES
Phase Diagram

1.26

CRITICAL POINTS
Pure substances have a single critical point
Unique point of phase envelope where density and composition of
vapor phase are identical with those of liquid phase
Some physical properties may be correlated by reduced
temperature (t/tc) and reduced pressure (p/pc)

Pseudo-critical temperature and pressure are used for

mixtures/fractions to predict properties
Since composition of two phases are the same,
fractionation of a mixture is impossible at critical point
Degree of approach to critical point of a mixture serves as rough
guide to feasibility of separation of components by fractionation.

1.27

THERMAL PROPERTIES
Specific Heat
Latent Heat of Vaporization
Enthalpy
Compression
Mollier Diagrams
Heats of Reaction
Reference: Section 7 of Blue Book
1.28

SURFACE TENSION
AND TRANSPORT PROPERTIES
Use of surface tension and transport
properties in equipment design
Surface Tension
Use models to predict
Extension of models to mixtures

Vapor Viscosity and Thermal Conductivity

Theoretical methods work well
Extension to mixtures

1.29

SURFACE TENSION AND

TRANSPORT PROPERTIES (Continued)
Liquid Viscosity: Difficult to Predict
Strong dependence on molecular size, structure, temperature
Blue Book is convenient reference

Liquid Thermal Conductivity: Easier to Predict

Less variable than viscosity
Simple estimates are frequently acceptable

1.30

SURFACE TENSION:
A VAPOR-LIQUID INTERFACIAL PROPERTY
Important in correlations for design of trays in
distillation columns, separator drums, etc.
Usually given in units of Dynes/cm
Surface Tension = 0 at (true) Critical Point
When Tr < 0.9, Surface Tension is a linear function
of temperature

1.31

VISCOSITY
Viscosity is a key property in fluid flow
Introduced Through Reynolds Number: Re = dv/

Dynamic Viscosity () normally expressed in cP (mPa s)

Kinematic Viscosity () is Dynamic Viscosity () divided by
mass density ()
Normally expressed in centistokes (cSt)

Theoretical prediction methods for vapor viscosity reliable at

low to moderate pressures
Liquid Viscosity must generally be measured at least at two
temperatures
For Hydrocarbons and Petroleum fractions, ExxonMobil Blue Book
Charts allow linear interpolation (and extrapolation)
Blend using Blending Index or Viscosity Modulus

1.32

THERMAL CONDUCTIVITY
Thermal conductivity () used in heat conduction in flow
systems through the Prandtl number
Pr = Cp/
Thermal conductivity generally expressed in Btu/hr.ft.F
(W/mK)
Liquid thermal conductivity can be estimated reasonably
well, except near critical point
Vapour thermal conductivity prediction methods are
reliable at low to moderate pressures
1.33

PRINCIPAL CHEMICAL ENGINEERING REFERENCES

ExxonMobil Internal References:
ExxonMobil Network of Consultants
ExxonMobil Design Practices - Selection Criteria, Design
Considerations, Correlation and Calculation Procedures
International Practices- Criteria for design, materials, fabrication,
procurement, erection, inspection and testing
General Information and Instructions - Site specific conditions &
practices
Process Engineering Manuals - FCCU, APS, VPS (Lubes and
Fuels), Amine Treating, Separations Guide, etc.
Application Technology Set - Technical Computing Tools
EDL III Manual
ExxonMobil Guide to PRO/II

1.34

OTHER USEFUL REFERENCES

FOR CHEMICAL ENGINEERS

Perrys Chemical Engineering Handbook - Robert H. Perry and

Don W. Green
API Technical Data Book for Refining
Gas Processors of America Handbook - GPSA
Fractional Operations and Design - Kister
Technical Paper 410 (Fluid Flow) - Crane
Applied Process Design of Chemical and Petrochemical Plants,
Volumes I, II, and III - Earnest E. Ludwig
Control Valve Handbook - Fisher Controls International, Inc.

1.35

BLUE BOOK

DESCRIPTION
Collection of physical property data (mostly for hydrocarbons)
Original core for ExxonMobil Data Library (EDL)
USE
Originally used as prime source for physical and thermodynamic
property data
Used currently to supplement EDL for quick estimates
Provides background for EDL correlations and calculation
procedures
OVERVIEW OF CONTENTS
Physical Constants and Conversion Factors
Pure Component Properties
Characteristics of Petroleum Fractions
Average Boiling Point, Gravity and Characterization Factor
All other properties can be derived from any two of the above
three

1.36

BLUE BOOK (Continued)

FREQUENTLY USED CHARTS

Page 4 -50, Vapour Pressure of Hydrocarbons
Estimate boiling point temperature at different pressures from single data point.
Useful in estimating relieving temperatures for PR valve fire loads

Page 7-39, Latent Heat of Vaporization of Paraffin Hydrocarbons

Useful in estimating latent heat for the calculation of PR valve fire loads

Pages 8-11 through 8-17

API Gravity, Specific Gravity and Density Interconversions

Pages 8-31 through 8-35

Estimation of liquid density vs. temperature from a single data point

Pages 9-11 through 9-13

Conversion of kinematic viscosities from various units to centistokes

Pages 9-30 through 9-31

Estimation of petroleum fraction kinematic viscosities

Pages 9-42 through 9-43

Estimation of kinematic viscosity vs. temperature from two data points

Section 11, Distillation Conversions

Provides explanation of different types of laboratory distillations
Contains correlations for converting lab distillation data from one type to another
Provides useful background in understanding how DISTEX works

1.37

DISTILLATION CONVERSION
AND
PSEUDO-COMPONENTS

1.38

DISTILLATION TYPES
15/5 - 15 trays / 5:1 reflux
TBP - Ambiguous term. Preferable term is 15/5.
Stem Correction - When thermometers are used the
entire stem is not immersed. Need to correct for this.
ASTM Distillations - D-86, D-158, D-1160 (Page 11.21 of
Blue Book).
GC Distillations - Gas Chromatography (GCD) has
largely replaced the 15/5. For GCD, the IBP is taken
as 0.5 vol% point. The FBP is defined as the 99.5 vol%
point.
1.39

CONVERSION OF ASTM DISTILLATION

TO A 15/5 DISTILLATION
Establish type of data reported
Stem corrected?
Procedure name?

Plot data to arrive at smooth curve

Stem correct the smooth curve, if not done by
laboratory
Use charts in Blue Books to convert this stem
corrected curve to 15/5

1.40

DISTILLATION CONVERSION EXAMPLE

Liquid
Volume%

ASTM
Temp. C

50% - 10%
Increment
Temp. C

90% - 50%
Increment
Temp C

15/5
Temp C

175

-18.0

157

10

180

-16.0

164

50

190

-0.3

90

-0.1

190

205

+9.0

214

95

210

+10.0

220

FBP

218
50% - 10% = 190-180=10C
90% - 50% = 205-190=15C

1.41

PROPERTIES OF FRACTIONS
Basis of property prediction is the pseudocomponent
breakdown
Each boiling-range fraction treated as pure component
Physical properties of pure component are calculated
from NBP and specific gravity

1.42

PSEUDO - COMPONENTS
If a component analysis is not available, a composition in
terms of Pseudo components can be obtained from the
distillation curve and gravity.
How do we represent the components? The same
component can be represented in many different ways:

API Method
- 177 A 45.0
Specific Gravity Method - 177 S 0.80
Watson K Method
- 177 K 11.6
How do we get Pseudo - Components?

1.43

PSEUDO - COMPONENT BOILING POINT

If you only have an ASTM distillation curve, convert it to a 15/5

distillation
Divide the curve into rectangles, each rectangle representing a
pseudo component (have more points near cutpoints) and the
regions with high slope
Tops of the rectangle are the Volume Average Boiling Points: 50%
of each component boils lower than the top of the rectangle,
50% boils higher

1.44

Generating Pseudo Components From Assay Data

1.45

PSEUDO-COMPONENT GRAVITY
Have TVABP and Volume percents of each fraction
Have specific gravity of total assay
Calculate characteristic factor, K, of total feed
K=

(Tb)
S.G.

1/3

K - Characterization Factor
Tb - Absolute Boiling Point in R (TMeABP)
Sp. Gr. - Specific Gravity, 60F (15C)

(For narrow boiling fractions, can assume TVABP = TMeABP

Use same equation, solved for S.G., to calculate S.G. of
each pseudocomponent
1.46

AVERAGE BOILING POINTS

Type of Average
Boiling Point

Abbreviation

Correlated Physical
Property

1. Molal ABP

None, Spell Out

TPC, Liquid
Thermal Expansion

2. Weight ABP

WABP

TC

3. Volume ABP

VABP

Liquid Cp, Viscosity

4. Mean ABP

MeABP, or MABP

MW, Watson K, ,
Ppc , HCOMB

1-3 Can Be Calculated by Linear Blends of Boiling Points of

Fractions with Amount of Each Fraction.
MeABP Correlates with Mol Wt.

1.47

MOLAL & WEIGHT AVERAGE BOILING POINTS

Molal ABP

WABP

Mol.Fr.

Comp

MW

BPoC Mol.Fr. x BP Mol.Fr. x MW Wt.Fr. x BP

0.10

C3

44.1

-42.1

-4.21

4.41

-3.27

0.40

IC4

58.1

-11.7

-4.68

23.24

-4.80

0.50

NC4

58.1

-0.5

-0.25

29.05

-0.26

-9.14

56.70

-8.33

1.00

AVG MW

1.48

VOLUME & MEAN AVERAGE BP

VABP
Comp
NC6
NC7
NC8

Vol.Fr.
0.17
0.73
0.10
1.00

B.P.oC (VF x BP)

11.68
68.7
71.83
98.4
12.57
125.7
96.08

kg/m3
663
687
706
685

Moles/m3 Mole
MW
mix
Fraction
86.2
1.307
0.189
100.2
5.008
0.721
114.2
0.618
0.090
6.933
1.000

Avg. Density = VF x kg/m3 = 685

S.G. = 685/1000 = 0.685
API = 141.5 - 131.5 = 75.0
S.G.

(not required in latest version of Blue Book)

M.W. = kg/m3 = 685 = 98.8

Moles/m3 6.933
MeABP = 99oC (Blue Book P 2.60)

1.49